Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
  • C08F271/02—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00 on to polymers of monomers containing heterocyclic nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3415—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
  • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
  • C08L61/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic and acyclic or carbocyclic compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
  • C08L93/04—Rosin
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
  • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
  • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Definitions

• the present invention relates to a resin composition, a laminate, a semiconductor chip with a resin composition layer, a substrate for mounting a semiconductor chip with a resin composition layer, and a semiconductor device. Specifically, the present invention relates to a resin composition useful as an underfill material.
• semiconductor chips hereinafter sometimes abbreviated as “chips”
• semiconductor chip mounting substrates hereinafter sometimes abbreviated as “substrates”
• flip-chip mounting has attracted attention.
• the gap between the chip and the substrate is filled with an underfill material, which is then hardened.
• an underfill material also referred to as a pre-applied underfill material
• one of the important characteristics required for the underfill material is to maintain insulation reliability.
• voids bubbles
• peeling of the cured underfill material from the chip and substrate is suppressed. There is a need.
• Patent Document 1 describes an underfill material that uses a radically polymerizable monomer as the main resin. This patent document 1 describes the addition of a silane coupling agent for the purpose of improving the adhesion to the chip.
• the present invention has been made in view of such problems, and includes a resin composition, a laminate, a semiconductor chip with a resin composition layer, and a semiconductor chip mounting with a resin composition layer, which are excellent in low void property and chip adhesiveness. It is an object of the present invention to provide a substrate for a semiconductor device and a semiconductor device.
• an aminotriazine novolac resin A
• an inorganic filler (D) contains
• the inorganic filler (D) has a functional group (d) containing one or more selected from the group consisting of a (meth)acrylic group, a vinyl group, a styryl group, and a phenyl group (D1).
• the compound (B) comprises a compound (B1) and a compound (B2)
• the compound (B1) is a maleimide compound (BA-1) having a weight average molecular weight of 3,000 or more and 9,500 or less and a citraconimide compound (BB-1) having a weight average molecular weight of 3,000 or more and 9,500 or less.
• One or more selected from the group consisting of The compound (B2) is selected from the group consisting of a maleimide compound (BA-2) having a weight average molecular weight of 300 or more and less than 3,000 and a citraconimide compound (BB-2) having a weight average molecular weight of 300 or more and less than 3,000.
• each weight average molecular weight is a standard polystyrene-equivalent value determined by a gel permeation chromatography method.
• the inorganic filler (D1) contains a reaction product of the compound (d1) having the functional group (d) and the inorganic filler (d2) having no functional group (d) ] The resin composition as described in . [4] [ 3]. [5] [3] or [ 4].
• the compound (d1) having the functional group (d) contains one or more selected from the group consisting of a silane compound having a (meth)acrylic group and/or a vinyl group and a silane compound having a styryl group
• Inorganic filler (d2) contains one or more selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide
• [7] The resin composition according to any one of [1] to [6], wherein the inorganic filler (D) has an average particle size of 3 ⁇ m or less.
• R 1 each independently represents a hydrogen atom, a methyl group, or an ethyl group; l, m, and n each independently represent an integer of 0 to 10; (l + m + n) indicates an integer from 1 to 20.)
• each R 2 independently represents a hydrogen atom, a methyl group, or an ethyl group; o, p, q, r, and s each independently represents an integer of 0 to 10; , (o + p + q + r + s) represents an integer from 1 to 20.) [10]
• the content of the compound (B1) is 45 parts by mass or more and 90 parts by mass or less with respect to a total of 100 parts by mass of the compound (B1) and the compound (B2), [1] to [9], wherein the content of the compound (B2) is 10 parts by mass or more and 55 parts by mass or less with respect to a total of 100 parts by mass of the compound (B1) and the compound (B2).
• the maleimide compound (BA-1) consists of a maleimide compound represented by the following formula (3) and a bismaleimide compound containing a maleimide group at both ends of a structural unit represented by the following formula (4) and a molecular chain.
• n3 represents an integer of 1 to 30.
• 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 1 to 16 carbon atoms.
• the maleimide compound (BA-2) contains one or more selected from the group consisting of a maleimide compound represented by the following formula (5) and a maleimide compound represented by the following formula (6) [1] to [11] ]
• the resin composition according to any one of the above.
• each R 8 independently represents a hydrogen atom, a methyl group, or an ethyl group, and each R 9 independently represents a hydrogen atom or a methyl group.
• each R 10 independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n 4 represents an integer of 1 to 10.
• a semiconductor device comprising the semiconductor chip with a resin composition layer according to [22].
• a resin composition a laminate, a semiconductor chip with a resin composition layer, a substrate for mounting a semiconductor chip with a resin composition layer, and a semiconductor device, which are excellent in low void property and chip adhesiveness. can.
• this embodiment A mode for carrying out the present invention (hereinafter simply referred to as "this embodiment") will be described below.
• the following embodiment is an example for explaining the present invention, and the present invention is not limited only to this embodiment.
• (meth)acryloxy means both “acryloxy” and its corresponding "methacryloxy”
• (meth)acrylonitrile means “acrylonitrile” and its corresponding "methacrylonitrile”.
• (meth)acrylic means both “acrylic” and its corresponding "methacrylic”
• (meth)acrylate means both “acrylate” and its corresponding "methacrylate”.
• (meth)allyl means both “allyl” and the corresponding "methallyl”.
• “ ⁇ ” in the present specification unless otherwise specified, means that the numerical values at both ends are included as the upper limit and the lower limit, and the unit for the upper limit and the lower limit shall be the same. .
• the term "resin solid content” or “resin solid content in the resin composition” refers to the inorganic filler (D), curing catalyst (E), and the component excluding the solvent, and "100 parts by mass of resin solid content” means that the total of the components excluding the inorganic filler (D), the curing catalyst (E), and the solvent in the resin composition is 100 parts by mass. It means that
• the resin composition of the present embodiment comprises an aminotriazine novolac resin (A) (hereinafter also simply referred to as “resin (A)”), a maleimide compound (BA) (hereinafter also simply referred to as “compound (BA)”) and containing one or more compounds (B) selected from the group consisting of citraconimide compounds (BB) (hereinafter also simply referred to as “compounds (BB)”) and an inorganic filler (D), wherein the inorganic
• the filler (D) contains an inorganic filler (D1) having a functional group (d) containing one or more selected from the group consisting of a (meth)acrylic group, a vinyl group, a styryl group, and a phenyl group,
• the compound (B) comprises a compound (B1) and a compound (B2), wherein the compound (B1) is a maleimide compound (BA-1) having a weight average molecular weight of 3,000 or more and 9,
• the resin composition of the present embodiment is configured in this way, it is excellent in low void property and chip adhesion. Since the resin composition of the present embodiment has such properties, it is suitably used as an underfill material for flip chip mounting.
• a resin composition having excellent low void properties and chip adhesiveness can be obtained in the present embodiment, the present inventors presume as follows. Generally, a resin composition containing a maleimide compound and/or a citraconimide compound as a main component does not provide sufficient chip adhesiveness, and voids or voids generated by heat during semiconductor chip mounting or thermal curing (during post-curing). , it is difficult to suppress peeling from the chip and substrate after curing.
• the aminotriazine novolac resin (A) has a triazine skeleton, it can react favorably with maleimide groups and/or citraconimide groups.
• the resin (A) can suitably control the rate of the radical polymerization reaction of the compound (B), and the resin composition containing the resin (A) and the compound (B) can be applied to the unevenness existing on the surfaces of the chip and the substrate. It can be hardened while following. Therefore, the resin composition can have an excellent anchoring effect to the semiconductor chip and the substrate, and can exhibit excellent chip adhesiveness with excellent low void property to the semiconductor chip and the substrate. Further, since the resin (A) has a novolak skeleton bonded to the triazine skeleton, it can contain many hydroxy groups and amino groups even after curing.
• the resin composition containing the resin (A) and the compound (B) has excellent chip adhesiveness, and such a resin composition can be used during semiconductor chip mounting and heat curing (post Voids can also be favorably suppressed by heat during curing.
• the inorganic filler (D1) contained in the resin composition of the present embodiment has a predetermined functional group (d), and this functional group (d) is reactive with the compound (B). Because of the high temperature, it is considered that a strong chemical bond is formed between the compound (B) and the inorganic filler (D1) by the heat during the semiconductor chip mounting and post-curing. As a result, it is possible to suppress voids that may occur after semiconductor chip mounting and during post-curing. can be suppressed.
• the interaction between the resin (A) and the compound (B) and the interaction between the compound (B) and the inorganic filler (D1) work synergistically to achieve the
• the resin composition has excellent chip adhesiveness, and by using such a resin composition, it is possible to suitably suppress voids that are normally likely to occur due to heat during semiconductor chip mounting or thermal curing (during post-curing). It is speculated that Also, from the same point of view, it is presumed that peeling of the cured product from the chip and the substrate can be suitably suppressed even after the semiconductor chip is mounted and after post-curing. However, the reason is not limited to this.
• the resin composition of the present embodiment contains an aminotriazine novolac resin (A) from the viewpoint of obtaining excellent reactivity with the compound (B) and obtaining a resin composition having low void properties and excellent chip adhesiveness.
• an aminotriazine novolak resin (A) any phenol-formaldehyde resin (phenol resin) having a triazine ring in the molecule may be used, and known resins can also be used.
• Such an aminotriazine novolac resin (A) can be produced by a known method, for example, by modifying a phenolic resin with a nitrogen compound such as melamine.
• the aminotriazine novolak resin (A) can be used singly or in an appropriate mixture of two or more.
• the content of the aminotriazine novolak resin (A) provides excellent reactivity with the compound (B), and provides excellent low void properties and chip adhesion. It is preferably 1 to 60 parts by mass with respect to 100 parts by mass in total of the aminotriazine novolak resin (A) and the compound (B). Since excellent reactivity with the compound (B) is obtained, and even more excellent low void property and chip adhesion are obtained, the content of the aminotriazine novolak resin (A) is It is more preferably 15 to 60 parts by mass, still more preferably 15 to 50 parts by mass, and even more preferably 17 to 45 parts by mass, relative to the total 100 parts by mass with the compound (B). 20 to 40 parts by mass is even more preferable.
• aminotriazine novolac resin (A) excellent reactivity with the compound (B) can be obtained, and further excellent low void property and chip adhesiveness can be obtained.
• 500 is preferred, and 500 to 5,000 is more preferred.
• a weight average molecular weight is a value of standard polystyrene conversion calculated
• aminotriazine novolac resin (A) excellent reactivity with the compound (B) can be obtained, and even more excellent low void properties and chip adhesiveness can be obtained. It is preferably 10 to 25% by mass, more preferably 15 to 25% by mass, based on 100% by mass.
• the aminotriazine novolac resin (A) excellent reactivity with the compound (B) can be obtained, and further excellent low void properties and chip adhesion can be obtained.
• eq. is preferably 100 to 180 g/eq. It is more preferable that the content is 130 to 170 g/eq. is more preferable.
• the hydroxy group equivalent means mg of potassium hydroxide required to acetylate the hydroxy groups contained in 1 g of the aminotriazine novolak resin. Specifically, it is measured according to JIS K 0070.
• the aminotriazine novolac resin (A) is represented by the following formula (1), since it exhibits even better reactivity with the compound (B) and provides even better low void properties and chip adhesion. It preferably contains one or more selected from the group consisting of compounds and compounds represented by the following formula (2).
• each R 1 independently represents a hydrogen atom, a methyl group, or an ethyl group. Each R 1 is preferably a hydrogen atom or a methyl group, because better reactivity with compound (B) can be obtained, and even better low void properties and chip adhesion can be obtained.
• l, m, and n each independently represent an integer of 0 to 10; l, m, and n are each independently an integer of 1 to 6, since better reactivity with the compound (B) is obtained, and even better low void property and chip adhesion are obtained. is preferred.
• (l+m+n) represents an integer of 1-20.
• (l+m+n) is preferably an integer of 3 to 18 because better reactivity with compound (B) can be obtained, and even better low void property and chip adhesion can be obtained.
• the compounds represented by the formula (1) are, for example, compounds in which the number of R 1 groups and the number thereof are different, compounds in which the numbers of l, m, and n are different, and compounds in which the number of (l + m + n) is It may be a mixture containing different compounds and the like.
• each R 2 independently represents a hydrogen atom, a methyl group, or an ethyl group. It is preferable that each R 2 is independently a hydrogen atom or a methyl group, since more excellent reactivity with the compound (B) can be obtained, and even more excellent low void property and chip adhesiveness can be obtained.
• . o, p, q, r, and s each independently represent an integer of 0 to 10; o, p, q, r, and s are each independently from 1 to 4, because better reactivity with the compound (B) can be obtained, and even better low void properties and chip adhesion can be obtained.
• (o + p + q + r + s) is preferably an integer of 5 to 20 because better reactivity with compound (B) can be obtained, and even better low void property and chip adhesion can be obtained.
• the compounds represented by the formula (2) include, for example, compounds in which the number of R 2 groups and the number thereof are different in the formula (2), compounds in which the numbers of o, p, q, r, and s are different, (o + p + q + r + s ) may be a mixture containing compounds having different numbers of .
• the aminotriazine novolac resin (A) is represented by the formula (1), since it can obtain even better reactivity with the compound (B), and even better low void properties and chip adhesion. and a compound represented by formula (2). As such a mixture, even better reactivity with the compound (B) can be obtained, and even better low void properties and chip adhesion can be obtained.
• the mass ratio of the compound represented by (2) (compound represented by formula (1) (parts by mass): compound represented by formula (2) (parts by mass)) is 50:50 to 90:10. and more preferably 60:40 to 85:15.
• aminotriazine novolak resin (A) a commercially available product may be used.
• LA-7054 trade name
• LA-7751 trade name
• the resin composition of the present embodiment contains one or more compounds (B) selected from the group consisting of maleimide compounds (BA) and citraconimide compounds (BB) from the viewpoint of low void properties and excellent chip adhesion.
• Compound (B) is not particularly limited as long as it contains one or more selected from the group consisting of a maleimide group and a citraconimide group in the molecule.
• the compound (B) preferably does not show reactivity with the flux activator (C) described below.
• Compound (B) can be used individually by 1 type or in mixture of 2 or more types.
• the maleimide compound (BA) has excellent reactivity with the aminotriazine novolak resin (A) and provides excellent low void properties and chip adhesion. is preferably included.
• the maleimide compound (BA) is less likely to react with the flux activator during storage or heat treatment than the epoxy compound, and the deactivation of the flux activator is less likely to occur.
• the compound (B) includes a compound (B1) and a compound (B2), and the compound (B1) is a maleimide compound (BA-1) having a weight average molecular weight of 3,000 or more and 9,500 or less and a weight average One or more selected from the group consisting of citraconimide compounds (BB-1) having a molecular weight of 3,000 or more and 9,500 or less, and the compound (B2) is a maleimide having a weight average molecular weight of 300 or more and less than 3,000. It is one or more selected from the group consisting of compound (BA-2) and citraconimide compound (BB-2) having a weight average molecular weight of 300 or more and less than 3,000.
• the resin composition of the present embodiment is even more excellent in low void properties and chip adhesion.
• the reason for this is not clear, but the inventors presume as follows. That is, by including the compound (B1) having a relatively high molecular weight in the resin composition, the stress generated during cure shrinkage during semiconductor chip mounting or thermal curing (during post-curing) is alleviated. Therefore, the effect of improving adhesiveness by using the resin (A) is further promoted.
• the resin composition also contains a compound (B2) having a relatively low molecular weight.
• the compound (B1) preferably contains a maleimide compound (BA-1), since it provides even better low void properties and chip adhesion.
• the compound (B2) preferably contains a maleimide compound (BA-2) because it provides even better low void properties and chip adhesion.
• the maleimide compound (BA-1) preferably has a weight-average molecular weight of 3,200 or more and 8,000 or less, because it provides even better low void properties and chip adhesion. It is more preferably 300 or more and 6,000 or less.
• the weight average molecular weight is preferably 3,200 or more and 8,000 or less, since even more excellent low void properties and chip adhesiveness can be obtained. , 300 or more and 6,000 or less.
• the weight average molecular weight of the maleimide compound (BA-2) is preferably from 350 to 2,800, preferably from 400 to 2,800, because even more excellent low void property and chip adhesiveness can be obtained. It is more preferably 500 or less.
• the weight average molecular weight is preferably 350 or more and 2,800 or less, and 400 or more and 2 , 500 or less.
• the maleimide compound (BA) is not particularly limited as long as it is a resin or compound having one or more maleimide groups in the molecule.
• the maleimide compound (BA) can be used singly or in combination of two or more.
• maleimide compounds examples include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidophenyl)methane, 4,4-diphenylmethanebismaleimide, bis(3,5-dimethyl-4 -maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethanemaleimide, o-phenylenebismaleimide, m- Phenylenebismaleimide, p-phenylenebismaleimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, 4 -methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide
• the compound (B) is in the form of a prepolymer obtained by polymerizing a maleimide compound, a prepolymer obtained by polymerizing a maleimide compound with another compound such as an amine compound, or the like, and the resin composition according to the present embodiment. can also be contained in
• n3 represents an integer of 1-30.
• R 11 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms.
• R 12 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms.
• Each R 13 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms.
• Each n5 independently represents an integer of 1 or more and 10 or less. Details of the structural unit represented by formula (4) will be described later.
• each R 8 independently represents a hydrogen atom, a methyl group, or an ethyl group.
• Each R9 independently represents a hydrogen atom or a methyl group.
• each R 10 independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.
• n4 represents an integer of 1-10.
• R 10 is preferably a hydrogen atom.
• each R 10 independently represents a hydrogen atom or a methyl group
• n 2 represents an integer of 1 or more, preferably an integer of 1-10.
• the bismaleimide compound may have a plurality of structural units represented by formula (4), in which case R 11 , R 12 and R in the plurality of structural units represented by formula (4) 13 may be the same or different.
• R 11 , R 12 , and R 13 in the structural unit represented by formula (4) and the number of structural units represented by formula (4) in the bismaleimide compound is It may be a mixture of different compounds.
• R 11 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms. .
• R 11 is a linear or branched alkylene because the resin composition has a suitable viscosity when the resin composition layer is mounted on the chip, and the increase in melt viscosity during mounting can be controlled favorably. is preferably a group, more preferably a linear alkylene group.
• the number of carbon atoms in the alkylene group is 2 to 14 because the resin composition has a more suitable viscosity when the resin composition layer is mounted on the chip, and the increase in melt viscosity during mounting can be more suitably controlled. is preferred, and 4 to 12 is more preferred.
• Examples of linear or branched alkylene groups include methylene, ethylene, propylene, 2,2-dimethylpropylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene.
• the number of carbon atoms in the alkenylene group is 2 to 14 because the resin composition has a more suitable viscosity when the resin composition layer is mounted on the chip, and the increase in melt viscosity during mounting can be more suitably controlled. is preferred, and 4 to 12 is more preferred.
• Linear or branched alkenylene groups include, for example, vinylene group, 1-methylvinylene group, arylene group, propenylene group, isopropenylene group, 1-butenylene group, 2-butenylene group, 1-pentenylene group, 2 -pentenylene group, isopentylene group, cyclopentenylene group, cyclohexenylene group, dicyclopentadienylene group, and the like.
• R 12 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms. .
• R 12 is a linear or branched alkylene because the resin composition has a suitable viscosity when the resin composition layer is mounted on the chip, and the increase in melt viscosity during mounting can be suitably controlled. is preferably a group, more preferably a linear alkylene group.
• the number of carbon atoms in the alkylene group is 2 to 14 because the resin composition has a more suitable viscosity when the resin composition layer is mounted on the chip, and the increase in melt viscosity during mounting can be more suitably controlled. is preferred, and 4 to 12 is more preferred.
• the above R 11 can be referred to as the linear or branched alkylene group.
• the number of carbon atoms in the alkenylene group is 2 to 14 because the resin composition has a more suitable viscosity when the resin composition layer is mounted on the chip, and the increase in melt viscosity during mounting can be more suitably controlled. is preferred, and 4 to 12 is more preferred.
• the linear or branched alkenylene group the above R 11 can be referred to.
• R 11 and R 12 may be the same or different, but from the viewpoint of easier synthesis of the bismaleimide compound, they are preferably the same. preferable.
• each R 13 is independently a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkyl group having 2 to 16 carbon atoms. It represents a branched alkenyl group.
• Each of R 13 is independently a hydrogen atom or a carbon
• a linear or branched alkyl group having a number of 1 to 16 is preferable, and among R 13 , 1 to 5 groups (R 13 ) are linear or branched alkyl groups having 1 to 16 carbon atoms.
• R 13 are more preferably hydrogen atoms, and among R 13 , 1 to 3 groups (R 13 ) are linear or branched groups having 1 to 16 carbon atoms. More preferably, it is an alkyl group and the remaining groups (R 13 ) are hydrogen atoms.
• the number of carbon atoms in the alkyl group is 2 to 14 because the resin composition has a more suitable viscosity when the resin composition layer is mounted on the chip, and the increase in melt viscosity during mounting can be more suitably controlled. is preferred, and 4 to 12 is more preferred.
• Linear or branched alkyl groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, 1-ethylpropyl group, n-butyl group, 2-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 2-pentyl group, tert-pentyl group, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, n-heptyl, n-octyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylpentan-3-yl, and n-nonyl groups.
• the number of carbon atoms in the alkenyl group is 2 to 14 because the resin composition has a more suitable viscosity when the resin composition layer is mounted on the chip, and the increase in melt viscosity during mounting can be more suitably controlled. is preferred, and 4 to 12 is more preferred.
• Linear or branched alkenyl groups include, for example, vinyl group, allyl group, 4-pentenyl group, isopropenyl group, isopentenyl group, 2-heptenyl group, 2-octenyl group, and 2-nonenyl group. be done.
• n 5 represents an integer of 1-10.
• a bismaleimide compound has maleimide groups at both ends of its molecular chain. Both ends mean both ends in the molecular chain of the bismaleimide compound. , at the chain end of R 11 , at the chain end at the N atom of the maleimide ring, or at both ends.
• the bismaleimide compound may have maleimide groups other than both ends of the molecular chain.
• the maleimide group is represented by formula (8) and the N atom is bonded to the molecular chain of the bismaleimide compound.
• the maleimide groups bonded to the bismaleimide compound may all be the same or different, but the maleimide groups at both ends of the molecular chain are preferably the same.
• each R 11 independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. Both R 11 are preferably hydrogen atoms from the viewpoint that they can more preferably react with the resin (A).
• the number of carbon atoms in the alkyl group is preferably from 1 to 3, more preferably from 1 to 2, from the viewpoint of more preferably reacting with the resin (A).
• the above R 13 can be referred to as the linear or branched alkyl group.
• Examples of such bismaleimide compounds include maleimide compounds represented by formula (9). These can be used singly or in combination of two or more compounds having different repeating numbers of a in formula (9).
• a represents an integer of 1-10.
• a is an integer of 1 to 6 because the resin composition has a more suitable viscosity when the resin composition layer is mounted on the chip, and the increase in melt viscosity during mounting can be more suitably controlled. is preferred.
• the maleimide compound represented by formula (9) may be a mixture of compounds in which a is different.
• the maleimide compound (BA) has excellent reactivity with the resin (A), has excellent low void properties and chip adhesion, and provides a resin composition having excellent solvent solubility.
• the maleimide compound (BA) tends to have better reactivity with the resin (A), and to have better low void properties, chip adhesion, and solvent solubility.
• maleimide compound (BA-1) As the maleimide compound (BA-1), the above formula ( 3) and maleimide compounds represented by the above formula (4) and bismaleimide compounds containing maleimide groups at both ends of the molecular chain.
• the maleimide compound (BA-2) As the maleimide compound (BA-2), the above formula ( 5) and one or more selected from the group consisting of the maleimide compound represented by the above formula (6).
• maleimide compound a commercially available product may be used.
• MIZ-001 manufactured by Nippon Kayaku Co., Ltd. (trade name, represented by the formula (9) Weight-average molecular weight: 3,900), which contains a maleimide compound and a in formula (9) is a mixture of 1 to 6 (integers).
• the maleimide compound represented by formula (5) include BMI-70 (trade name; bis(3-ethyl-5-methyl-4-maleimidophenyl)methane manufactured by K.I. Kasei Co., Ltd., weight average molecular weight : 550).
• Examples of the maleimide compound represented by formula (6) include MIR-3000-70MT (trade name, manufactured by Nippon Kayaku Co., Ltd., where all R 10 in formula (6) are hydrogen atoms, n 4 is 1 ⁇ 10 mixture, weight average molecular weight: 1,050).
• Examples of the maleimide compound represented by formula (7) include BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd.
• citraconimide compound (BB) examples include, but are not limited to, o-phenylenebiscitraconimide, m-phenylenebiscitraconimide, p-phenylenebiscitraconimide, 4,4-diphenylmethanebiscitraconimide, 2,2- bis[4-(4-citraconimidophenoxy)phenyl]propane, bis(3,5-dimethyl-4-citraconimidophenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidophenyl)methane, bis (3,5-diethyl-4-citraconimidophenyl)methane, 1,3-xylylenebis(citraconimide), N-[3-bis(trimethylsilyl)amino-1-propyl]citraconimide, N-[3-bis( triethyl
• the above bismaleimide compound can be referred to.
• the details of the structural unit represented by the formula (4) are as described above, and the citraconimide group is represented by the formula ( 8) can be referred to.
• the citraconimide compound (BB) can be used singly or in combination of two or more.
• the citraconimide compound (BB) is among the above-mentioned from the viewpoint of obtaining a resin composition having excellent solvent solubility, excellent low void property and chip adhesion, and excellent reactivity with the resin (A).
• a biscitraconimide compound containing a structural unit represented by the above formula (4) and a citraconimide group at both ends of the molecular chain represented by the following formula (11) and one or more selected from the group consisting of a citraconimide compound represented by the following formula (12).
• citraconimide compound (BB-1) As the citraconimide compound (BB-1), a more excellent reactivity with the resin (A) can be obtained, and a more excellent low void property, chip adhesion, and solvent solubility can be obtained. It is preferably a citraconimide compound represented by (10) and/or a biscitraconimide compound containing a structural unit represented by the above formula (4) and citraconimide groups at both ends of the molecular chain.
• n6 represents an integer of 1-30.
• citraconimide compound (BB-2) As the citraconimide compound (BB-2), a more excellent reactivity with the resin (A) can be obtained, and a more excellent low void property, chip adhesion, and solvent solubility can be obtained. It is preferably a citraconimide compound represented by (11) and/or a citraconimide compound represented by the following formula (12).
• each R 8 independently represents a hydrogen atom, a methyl group, or an ethyl group.
• Each R9 independently represents a hydrogen atom or a methyl group.
• each R 10 independently represents a hydrogen atom or a methyl group, and n 4 represents an integer of 1 or more, preferably an integer of 1-10.
• R 10 is preferably a hydrogen atom.
• the content of the compound (B) is not particularly limited. B) with respect to 100 parts by mass in total, preferably 40 to 85 parts by mass, more preferably 50 to 85 parts by mass, even more preferably 55 to 83 parts by mass, and 60 to 80 parts by mass. Even more preferable.
• the compound (B1) The content of is preferably 45 parts by mass or more and 90 parts by mass or less, and 45 parts by mass or more and 85 parts by mass or less with respect to a total of 100 parts by mass of the compound (B1) and the compound (B2). More preferably, it is 45 parts by mass or more and 78 parts by mass or less.
• the content of the compound (B2) is preferably 10 parts by mass or more and 55 parts by mass or less, and 15 parts by mass or more and 55 parts by mass with respect to a total of 100 parts by mass of the compound (B1) and the compound (B2). It is more preferably 22 parts by mass or more and 55 parts by mass or less.
• the maleimide compound (BA -1) content is preferably 45 to 90 parts by mass, preferably 45 to 85 parts by mass, with respect to the total 100 parts by mass of compound (BA-1) and compound (BA-2). is more preferable, and 45 to 78 parts by mass is even more preferable.
• the content of the maleimide compound (BA-2) is preferably 10 to 55 parts by mass with respect to a total of 100 parts by mass of the compound (BA-1) and the compound (BA-2). It is more preferably 55 parts by mass, and even more preferably 22 to 55 parts by mass.
• the content of the citraconimide compound (BB-1) is the compound (BB-1) and the compound (BB- 2) is preferably 45 to 90 parts by mass, more preferably 45 to 85 parts by mass, and even more preferably 45 to 78 parts by mass, based on the total 100 parts by mass of 2).
• the content of the citraconimide compound (BB-2) is preferably 10 to 55 parts by mass with respect to a total of 100 parts by mass of the compound (BB-1) and the compound (BB-2). It is more preferably 55 parts by mass, and even more preferably 22 to 55 parts by mass.
• the content (total amount) of the resin (A) and the compound (B) is It is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 70 parts by mass or more, and may be 80 parts by mass or more.
• the upper limit of the content (total amount) of the resin (A) and the compound (B) may be 100 parts by mass or less, or may be 95 parts by mass or less with respect to 100 parts by mass of the resin solid content.
• the resin composition of the present embodiment preferably further contains a flux activator (C) in order to exhibit flux activity in flip-chip mounting.
• the flux activator (C) is not particularly limited as long as it is an organic compound having one or more acidic sites in its molecule.
• As the acidic site for example, a phosphoric acid group, a phenolic hydroxyl group, a carboxyl group, and a sulfonic acid group are preferable.
• a phenolic hydroxyl group or a carboxyl group is more preferable from the viewpoint of more effectively preventing the migration and corrosion of metals such as copper.
• the flux activator (C) can be used singly or in an appropriate mixture of two or more.
• the flux activator (C) is not particularly limited, but preferably has an acid dissociation constant pKa of 3.8 or more and 15.0 or less in order to sufficiently remove the oxide film at the junction, and the storage stability of the varnish is improved. It is more preferably 4.0 or more and 14.0 or less from the viewpoint of compatibility between the storage stability and the flux activity of a laminate (underfill material with a supporting substrate) provided with a layer of a resin composition.
• the weight average molecular weight or molecular weight of the flux activator (C) in the resin composition of the present embodiment is not particularly limited. From the viewpoint of preventing the flux activator (C) from volatilizing before removing the film, the weight average molecular weight or molecular weight is preferably 200 or more, more preferably 250 or more. In order to have motility as a flux activator and obtain sufficient flux activity, the weight average molecular weight or molecular weight of the flux activator (C) is preferably 8000 or less, more preferably 1000 or less. , 600 or less.
• Examples of the flux activator (C) include, but are not limited to, abietic acid, neoabietic acid, dehydroabietic acid, pimaric acid, isopimaric acid, parastric acid, diphenolic acid, dihydroabietic acid, tetrahydroabietic acid, hydrogenation Rosin resins such as rosin esters and rosin-modified maleic acid resins; N,N'-bis(salicylidene)-1,2-propanediamine, N,N'-bis(salicylidene)-1,3-propanediamine, etc. diamine series; phenolphthalin.
• These flux activators (C) are preferable from the viewpoint of solubility in solvents, storage stability of varnishes, and storage stability of underfill materials with supporting substrates. It is more preferable to include
• the flux activator (C) is dehydroabietic acid, diphenolic acid, dihydroabietic acid, tetrahydroabietic acid, hydrogenated rosin ester, rosin-modified maleic acid resin. , N,N'-bis(salicylidene)-1,2-propanediamine, and N,N'-bis(salicylidene)-1,3-propanediamine. preferable.
• these flux activators have relatively low reactivity, they hardly react with the resin (A) and the compound (B), and sufficient flux activity necessary for removing the oxide film is maintained. It is more preferable from the viewpoint of Further, the flux activator (C) is more preferably a hydrogenated rosin ester in terms of obtaining even better flux activity.
• a commercially available product can be used as the flux activator (C).
• rosin-based resins include Pine Crystal (registered trademark, hereinafter the same) series KR-85 (trade name, hereinafter the same), KR-612, KR-614, KE-100, KE-311, PE-590, KE-359, KE-604, KR-120, KR-140, KR-614, D-6011, and KR-50M; Marquid No. 32 (manufactured by Arakawa Chemical Industries, Ltd.) and the like.
• the content of the flux activator (C) is not particularly limited, but from the viewpoint of ensuring insulation reliability and sufficient flux activity during mounting, It is preferably 5 to 70 parts by mass, more preferably 10 to 50 parts by mass, even more preferably 15 to 40 parts by mass, relative to 100 parts by mass of compound (B).
• the resin composition of the present embodiment further contains an inorganic filler (D) in order to improve flame resistance, improve thermal conductivity, and reduce the coefficient of thermal expansion.
• the inorganic filler (D) By using the inorganic filler (D), the flame resistance and thermal conductivity of a cured product such as a film formed using the resin composition of the present embodiment can be improved, and the coefficient of thermal expansion can be reduced. can.
• the minimum melt viscosity of the resin composition can be suitably controlled.
• the minimum melt viscosity of the resin composition is preferably 200 Pa ⁇ s or more and 30,000 Pa ⁇ s or less because it is suitable for use as an underfill material.
• the resin composition of the present embodiment contains an inorganic filler (D1), which will be described in detail later, as the inorganic filler (D), low void properties and chip adhesiveness are improved.
• the inorganic filler (D) is not particularly limited, but may include, for example, various known inorganic compounds.
• the inorganic compound include, but are not limited to, natural silica, fused silica, amorphous silica, and silica such as hollow silica; aluminum compounds such as boehmite, aluminum hydroxide, alumina, 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 zinc molybdate; boron nitride; barium sulfate; talc such as natural talc and calcined talc; mica; and the like.
• the inorganic filler (D) when it is desired to impart electrical conductivity or anisotropic electrical conductivity to the resin composition of the present embodiment, metal particles such as gold, silver, nickel, copper, tin alloys, and palladium can be used as the inorganic filler (D).
• the inorganic filler (D) includes silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide, more preferably one or more selected from the group consisting of silica, alumina, and boron nitride, more preferably silica .
• These inorganic fillers (D) can be used singly or in admixture of two or more.
• the inorganic filler (D) in the present embodiment is an inorganic filler having a functional group (d) containing one or more selected from the group consisting of (meth)acrylic groups, vinyl groups, styryl groups, and phenyl groups. including material (D1).
• the “phenyl group” (“—C 6 H 5 ”) means a group directly bonded to a silicon atom or a carbon atom, for example, a phenyl group directly bonded to a nitrogen atom. It is distinguished from a group (aminophenyl group) and the like. Since the functional group (d) in such an inorganic filler (D1) is highly reactive with the compound (B), the compound (B) and the inorganic filler ( D1) is thought to form a strong chemical bond. As a result, voids that may occur after semiconductor chip mounting and during post-curing can be suppressed, and peeling of the cured product from the chip and substrate can be suitably suppressed even after semiconductor chip mounting and post-curing. It is considered possible.
• the functional group (d) in the present embodiment is not particularly limited as long as it contains at least one selected from the group consisting of (meth)acrylic groups, vinyl groups, styryl groups, and phenyl groups. From the viewpoint of adhesiveness, it is preferable to further contain a silicon atom, and the silicon atom is a (meth) acrylic group, a vinyl group, a styryl group, and a group containing one or more selected from the group consisting of a phenyl group. Bonding is more preferred.
• a functional group (d) in which a silicon atom is directly bonded to a group containing one or more selected from the group consisting of (meth)acrylic groups, vinyl groups, styryl groups, and phenyl groups is preferably a group containing one or more selected from the group consisting of an acryloxyalkylsilyl group, a vinylsilyl group, a styrylsilyl group, and a phenylsilyl group, consisting of a (meth)acryloxyalkylsilyl group and a vinylsilyl group; A group containing one or more selected from the group is more preferred.
• the number of carbon atoms in the alkyl portion of the (meth)acryloxyalkylsilyl group is preferably 1-6, more preferably 1-3.
• the inorganic filler (D1) in the present embodiment is a compound (d1) having a functional group (d) and an inorganic filler (d2) having no functional group (d) from the viewpoint of low voids and chip adhesion. preferably contains a reactant with The compound (d1) is not particularly limited as long as it can introduce a predetermined functional group to the surface of the inorganic filler (d2). Examples include (meth)acrylic, vinyl, styryl and phenyl A silane coupling agent containing at least one selected from the group consisting of As such a silane coupling agent, a silane coupling agent generally used for surface treatment of inorganic substances can be appropriately employed.
• vinyltrimethoxysilane ⁇ -(meth)acryloxypropyltrimethoxysilane
• other vinylsilane-based silane coupling agents silanes having a (meth)acrylic group and/or a vinyl group).
• compounds phenylsilane-based silane coupling agents (silane compounds having a phenyl group) such as trimethoxyphenylsilane; styrylsilane-based silane coupling agents (silane compounds having a styryl group) such as styryltrimethoxysilane; .
• phenylsilane-based silane coupling agents silane compounds having a phenyl group
• trimethoxyphenylsilane such as trimethoxyphenylsilane
• styrylsilane-based silane coupling agents silane compounds having a styryl group
• silane coupling agents can be used singly or in admixture of two or
• the compound (d1) includes a vinylsilane-based silane coupling agent (silane compound having a (meth)acrylic group and/or a vinyl group), and a styrylsilane-based silane.
• the inorganic filler (d2) is not particularly limited, and the specific examples described above as inorganic compounds that can be contained as the inorganic filler (D) can be applied.
• the method for preparing the reactant is not particularly limited, and various known methods for treatment with a silane coupling agent can be appropriately employed.
• the inorganic filler (d2) is silica
• the above treatment may be carried out in the gas phase or in the liquid phase.
• the content of the functional group (d) in the inorganic filler (D1) is not particularly limited, but when the inorganic filler (d2) is silica, the content of the functional group (d) with respect to 100 parts by mass of silica may be 1 to 10 parts by mass.
• the inorganic filler (d2) is silica
• specific examples of the reactant are not limited to the following, but 0.3 ⁇ m SV-EM1 surface-treated with vinyltrimethoxysilane manufactured by Admatechs Co., Ltd. (trade name), SC1050-MLQ (trade name) surface-treated with vinyltrimethoxysilane, SC2050-MNU (trade name) surface-treated with vinyltrimethoxysilane, and surface-treated with 3-methacryloxypropyltrimethoxysilane.
• Y50SV-AM1 (trade name) surface-treated with vinyltrimethoxysilane
• Y50SP-AM1 (trade name) surface-treated with phenyltrimethoxysilane, and the like.
• YA050C-MJE (trade name), Y50SV-AM1 (trade name), and Y50SP-AM1 (trade name). It preferably contains one or more selected from the group, and more preferably contains one or more selected from the group consisting of YA050C-MJE (trade name) and Y50SV-AM1 (trade name).
• the average particle size of the inorganic filler (D) is not particularly limited. From a corresponding viewpoint, it is preferably 3 ⁇ m or less, more preferably 1 ⁇ m or less, and may be 0.1 ⁇ m or less. Although the lower limit of the average particle size is not particularly limited, it is, for example, 10 nm.
• the "average particle size" of the inorganic filler (D) shall mean the median size of the inorganic filler (D).
• the median diameter is the volume of particles on the larger particle size side and the volume of particles on the smaller particle size side when the particle size distribution of powder is divided into two based on a certain particle size. means a particle size such that each accounts for 50% of the total powder.
• the average particle size (median size) of the inorganic filler (D) is measured by a wet laser diffraction/scattering method.
• the content of the inorganic filler (D) is not particularly limited, but from the viewpoint of ensuring insulation reliability and sufficient flux activity during mounting, the aminotriazine novolac resin (A) and It is preferably 20 to 500 parts by mass, more preferably 50 to 400 parts by mass, even more preferably 70 to 300 parts by mass, based on 100 parts by mass in total with the compound (B).
• the upper limit of the content of the inorganic filler (D) may be 250 parts by mass.
• the content of the inorganic filler (D1) is 20 to 500 parts by mass with respect to the total 100 parts by mass of the aminotriazine novolak resin (A) and the compound (B). parts, more preferably 50 to 400 parts by mass, even more preferably 70 to 300 parts by mass.
• the upper limit of the content of the inorganic filler (D1) may be 250 parts by mass.
• the resin composition of the present embodiment preferably further contains a curing catalyst (E).
• a curing catalyst (E) When the resin composition contains the curing catalyst (E), the reaction rate between the resin (A) and the compound (B) and the polymerization rate of the compound (B) can be more preferably controlled, and moderate moldability is obtained. A resin composition tends to be obtained.
• the curing catalyst (E) is not particularly limited as long as it is a compound capable of promoting the reaction between the resin (A) and the compound (B) and the polymerization reaction of the compound (B). Curing catalyst (E) can be used individually by 1 type or in mixture of 2 or more types.
• the curing catalyst (E) in the present embodiment is not particularly limited, but includes, for example, organic peroxides, imidazole compounds, azo compounds, and tertiary amines such as triethylamine and tributylamine and their derivatives.
• the curing catalyst (E) is one or more selected from the group consisting of organic peroxides and imidazole compounds from the viewpoint of obtaining a good reaction rate and polymerization rate and obtaining a good curing rate. and more preferably both an organic peroxide and an imidazole compound.
• the content of the curing catalyst (E) is not particularly limited, but from the viewpoint of obtaining a good curing speed, it is , preferably 0.05 to 10 parts by mass, more preferably 0.05 to 8 parts by mass.
• organic peroxide in the present embodiment is a compound that releases an active substance (radical) that can promote the reaction between the resin (A) and the compound (B) and the polymerization reaction of the compound (B) by heat.
• an organic peroxide can be used.
• An organic peroxide can be used individually by 1 type or in mixture of 2 or more types.
• the 10-hour half-life temperature of the organic peroxide is not particularly limited, but is preferably 100°C or higher, and more preferably 110°C or higher from the viewpoint of productivity. It is preferable that the organic peroxide satisfies the 10-hour half-life temperature in the above range, since it is possible to increase the temperature of the solvent removal step during production.
• organic peroxides include dicumyl peroxide, di(2-tert-butylperoxyisopropyl)benzene, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5 - Ketone peroxides of bis(tert-butylperoxy)hexyne-3, benzoyl peroxide, di-t-butyl peroxide, methyl ethyl ketone peroxide, and cyclohexanone peroxide; 1,1-di(t-butylperoxy)cyclohexane , and peroxyketals of 2,2-di(4,4-di(t-butylperoxy)cyclohexyl)propane; tert-butyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide Peroxides and hydroperoxides of t-butyl hydro
• the content of the organic peroxide is not particularly limited, but the aminotriazine novolak resin (A) and the compound (B) are combined in order to obtain a better reaction rate and curing rate. It is preferably contained in an amount of 0.05 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, based on a total of 100 parts by mass.
• the imidazole compound is not particularly limited as long as it can promote the reaction between the resin (A) and the compound (B) and the polymerization reaction of the compound (B), and known imidazole compounds can be used.
• An imidazole compound can be used 1 type or in mixture of 2 or more types.
• imidazole compounds examples include 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4,5-triphenylimidazole and the like. Among them, 2-ethyl-4-methylimidazole is preferred because it is easier to control the reaction speed and curing speed.
• the content of the imidazole compound is not particularly limited. It is preferably 0.05 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, based on 100 parts by mass in total.
• the azo compound is not particularly limited as long as it can promote the reaction between the resin (A) and the compound (B) and the polymerization reaction of the compound (B), and known azo compounds can be used.
• Azo compounds can be used singly or in combination of two or more. Examples of azo compounds include 2,2'-azobisbutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4- dimethylvaleronitrile) and the like.
• the content of the azo compound is not particularly limited. It is preferably contained in an amount of 0.05 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, based on 100 parts by mass.
• the resin composition of the present embodiment contains not only the aminotriazine novolac resin (A), the compound (B), and the inorganic filler (D), but also the above-described flux activator (C) and curing catalyst (E). Other components may be contained singly or in combination of two or more.
• the flexibility imparting component is not particularly limited as long as it is a component capable of imparting flexibility to the layer containing the resin composition.
• Such components include, for example, aminotriazine novolak resin (A), compound (B), flux activator (C), inorganic filler (D), and curing catalyst (E) other than polyimide, polyamideimide, Polystyrene, polyolefin, styrene-butadiene rubber (SBR), isoprene rubber (IR), butadiene rubber (BR), (meth)acrylonitrile butadiene rubber (NBR), polyurethane, polypropylene, (meth)acrylic oligomer, (meth)acrylic polymer, and thermoplastic polymer compounds such as silicone resins.
• These flexibility-imparting components can be used singly or in admixture of two or more.
• the resin composition of the present embodiment may contain a silane coupling agent separately from other components, that is, the inorganic filler (D1).
• silane coupling agents include those exemplified as usable in the preparation of the inorganic filler (D1).
• the content of the silane coupling agent is not particularly limited, it can be about 0.05 to 20 parts by mass with respect to the total of 100 parts by mass of the aminotriazine novolak resin (A) and the compound (B).
• the resin composition of the present embodiment may contain, as other components, a wetting and dispersing agent for the purpose of further improving the manufacturability of the laminate and further improving the dispersibility of the filler.
• the wetting and dispersing agent is not particularly limited as long as it is a wetting and dispersing agent generally used for paints and the like.
• BYK-Chemie Japan Co., Ltd. DISPERBYK (registered trademark) -110 (trade name), -111 (trade name), -180 (trade name), -161 (trade name), BYK-W996 ( (trade name), W9010 (trade name), and W903 (trade name).
• These wetting and dispersing agents can be used singly or in admixture of two or more.
• a wetting and dispersing agent When a wetting and dispersing agent is used, its content is not particularly limited, but from the viewpoint of further improving the manufacturability of the laminate, it is 0.1 to 5 parts by mass with respect to 100 parts by mass of the inorganic filler (D). It is preferably 0.5 to 3 parts by mass, more preferably 0.5 to 3 parts by mass. When two or more wetting and dispersing agents are used in combination, the total amount thereof preferably satisfies the above ratio.
• the resin composition of the present embodiment includes, as other components, other thermosetting resins or compounds different from the aminotriazine novolac resin (A) and the compound (B) (hereinafter simply referred to as "other thermosetting resins ) may be included.
• Other thermosetting resins include, for example, cyanate ester compounds, benzoxazine compounds, aromatic primary amine compounds, epoxy compounds, phenolic compounds, modified polyphenylene ether compounds, alkenyl-substituted nadimide compounds, oxetane resins, and polymerizable and a compound having an unsaturated group. These other thermosetting resins can be used singly or in admixture of two or more.
• one or more compounds selected from the group consisting of cyanate ester compounds, benzoxazine compounds, and aromatic primary amine compounds are used from the viewpoint of low void property and chip adhesion.
• (F) can be included.
• the content of the compound (F) may be 1 to 50 parts by mass, or 3 to 35 parts by mass, relative to the total of 100 parts by mass of the aminotriazine novolak resin (A), the compound (B) and the compound (F). It may be parts by mass, and may be 5 to 30 parts by mass.
• the resin composition of the present embodiment may contain various additives for various purposes as long as the desired properties are not impaired.
• Additives include, for example, thickeners, lubricants, defoamers, leveling agents, brighteners, flame retardants, and ion trapping agents. These additives can be used singly or in admixture of two or more.
• the content of these additives is not particularly limited, but is usually 0.01 for each of 100 parts by mass in total of the aminotriazine novolac resin (A) and the compound (B). ⁇ 10 parts by mass.
• the resin composition of this embodiment is excellent in low void property and chip adhesion.
• the resin composition of the present embodiment is used as an underfill material used in the form of a laminate, preferably as a pre-applied underfill material, it is excellent in low void properties and chip adhesion, and in addition, bonding properties and insulation Excellent reliability. Since the resin composition of the present embodiment has various excellent characteristics, it is more useful as an underfill material, and further useful as a pre-applied underfill material. In addition, a laminated body is mentioned later.
• a sheet obtained using the resin composition and a layer containing the resin composition is preferably in a semi-cured state (B stage). Details of the sheet and the resin composition layer will be described later. Since the sheet and the resin composition layer are in a semi-cured state, even more excellent low void properties and chip adhesion can be obtained.
• the semi-cured state (B stage) means that each component contained in the sheet or resin composition layer has not actively started to react (cured), but the sheet or resin composition layer is dried.
• the minimum melt viscosity in a semi-cured state is usually 50,000 Pa ⁇ s or less.
• the lower limit of the lowest melt viscosity is, for example, 10 Pa ⁇ s or more.
• the minimum melt viscosity in the semi-cured state (B stage) is preferably 200 Pa ⁇ s or more and 30,000 Pa ⁇ s or less because it is suitable for use as an underfill material.
• the minimum melt viscosity is measured by the following method.
• a resin piece having a thickness of about 0.4 to 0.6 mm is obtained by laminating a resin composition layer on a support substrate or the like, and this resin piece is used as a sample, and a rheometer (thermofisher Melt viscosity is measured by HAAKE MARS60 (trade name) manufactured by Scientific Co.).
• a rheometer thermofisher Melt viscosity is measured by HAAKE MARS60 (trade name) manufactured by Scientific Co.
• a disposable parallel plate with a plate diameter of 8 mm is used, and in the range of 40 ° C. to 300 ° C., the temperature increase rate is 10 ° C./min, the frequency is 10.0 rad / sec, and the strain is 0.1%.
• the lowest melt viscosity means the lowest viscosity in the range from 40°C to 300°C.
• the production method of the resin composition of the present embodiment is not particularly limited as long as the resin composition having the composition described above can be obtained.
• the resin composition comprises, for example, an aminotriazine novolak resin (A), a compound (B), an inorganic filler (D), optionally a flux activator (C), a curing catalyst (E), It can be prepared by appropriately mixing other components. If necessary, these components may be dissolved or dispersed in an organic solvent to form a varnish.
• a varnish can be suitably used when producing a laminated body. As for a specific manufacturing method, the method for manufacturing a laminate and Examples described later can be referred to.
• the organic solvent is not particularly limited as long as it can suitably dissolve or disperse each component in the resin composition of the present embodiment and does not impair the effects of the resin composition of the present embodiment.
• organic solvents include alcohols such as methanol, ethanol, and propanol; ketones such as acetone, methyl ethyl ketone (hereinafter sometimes abbreviated as "MEK”), and methyl isobutyl ketone; dimethylacetamide, and dimethylformamide.
• amides such as; aromatic hydrocarbons such as toluene and xylene.
• a resin sheet contains the resin composition of this embodiment.
• the resin sheet has a supporting substrate and a resin layer disposed on one side or both sides of the supporting substrate, and the resin layer contains the resin composition of the present embodiment.
• This resin sheet is also called a laminated resin sheet.
• the resin layer of the resin sheet is preferably formed by coating an uncured (A-stage) resin composition on a supporting substrate and then semi-curing (B-stage) the resin composition.
• A-stage uncured
• B-stage semi-curing
• the resin composition in an uncured state is in the form of a varnish, and the varnish is applied to a supporting substrate such as a copper foil using a known method such as a bar coater. ° C. in a dryer for 1 to 60 minutes for semi-curing (to B-stage) to produce a resin sheet.
• the uncured state (A stage) refers to a state in which the resin composition is not substantially cured and is not gelled.
• the resin composition before being applied to the supporting substrate of the resin sheet is, for example, a mixture of constituent components of the resin composition (which may or may not contain a solvent), or the mixture dissolved or dispersed in a solvent. It is in the form of varnish and is in an uncured state (A stage).
• the supporting substrate is not particularly limited, but for example, organic films such as polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylenetetrafluoroethylene copolymer film, and polyimide film; release films coated with a release agent on the surface; conductor foils such as copper foil and aluminum foil; and plate-shaped ones such as glass plates, SUS plates, and FRP.
• organic films such as polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylenetetrafluoroethylene copolymer film, and polyimide film
• release films coated with a release agent on the surface such as polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylenetetrafluoroethylene copolymer film, and polyimide film
• release films coated with a release agent on the surface such as polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylenet
• the coating method is not particularly limited, but includes, for example, a method in which a solution obtained by dissolving the resin composition in a solvent is applied onto the supporting substrate using a bar coater, die coater, doctor blade, baker applicator, or the like.
• a single-layer resin sheet is obtained by molding a resin composition into a sheet.
• the method for producing the single-layer resin sheet is not particularly limited and can be carried out according to a conventional method.
• a method of applying a solution in which a resin composition is dissolved in a solvent onto a supporting substrate and drying it, and then peeling or etching the supporting substrate from the resin sheet can be mentioned.
• a single-layer resin sheet without using a supporting substrate can be formed by forming a sheet by, for example, supplying a solution in which a resin composition is dissolved in a solvent into a mold having a sheet-like cavity and drying it. You can also get
• the drying conditions for removing the solvent are not particularly limited. 1 to 90 minutes at a temperature of 20 to 170° C. is preferred because it progresses.
• the thickness of the resin layer of the resin sheet or single-layer resin sheet can be adjusted by adjusting the concentration of the solution of the resin composition and the thickness of the coating, and is not particularly limited. 0.1 to 500 .mu.m is preferred because it tends to remain.
• a resin sheet or a single-layer resin sheet can be used, for example, as a material for forming wiring circuits on semiconductor wafers and semiconductor chip mounting substrates.
• the laminate of the present embodiment includes a supporting base material and a resin composition layer containing the resin composition of the present embodiment laminated on the supporting base material.
• Such a laminate can be obtained by forming the resin composition of the present embodiment as a layer on a supporting substrate.
• a polymer film can be used as the supporting substrate, although not particularly limited.
• polymer film materials include polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polybutene, polybutadiene, ethylene-propylene copolymer, polymethylpentene, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol.
• vinyl-based resins such as copolymers
• polyester-based resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate
• polyurethane-based resins polyimide-based resins
• supporting substrates include films containing these resins and the like, and release films obtained by applying a release agent to the surface of these films.
• films containing one or more resins selected from the group consisting of polyester-based resins, polyimide-based resins, and polyamide-based resins and release films obtained by applying a release agent to the surface of these films. More preferably, it is a film containing polyethylene terephthalate, which is a type of polyester resin, or a release film obtained by applying a release agent to the surface of a film containing polyethylene terephthalate.
• the thickness of the supporting substrate is not particularly limited. From the viewpoint of better transportability, it is preferably 10 to 100 ⁇ m.
• the lower limit of the thickness of the supporting substrate is more preferably 10 ⁇ m or more, still more preferably 20 ⁇ m or more, further preferably 25 ⁇ m or more, from the viewpoint of ensuring a higher yield in manufacturing the laminate. is even more preferred.
• the upper limit of the thickness of the supporting base material is 80 ⁇ m or less in view of the fact that the supporting base material does not exist as a component of the semiconductor device in the end and is peeled off in the middle of the process and the manufacturing cost of the laminate. and more preferably 50 ⁇ m or less.
• the method of forming a layer containing the resin composition of the present embodiment, ie, a resin composition layer, to produce the laminate of the present embodiment is not particularly limited.
• a varnish obtained by dissolving or dispersing the resin composition of the present embodiment in an organic solvent is applied to the surface of the supporting substrate, heated and / or dried under reduced pressure, and the solvent is removed to solidify the resin composition of the present embodiment to form a resin composition layer.
• the drying conditions are not particularly limited, but the content ratio of the organic solvent to the resin composition layer is usually 10 parts by mass or less, preferably 5 parts by mass or less with respect to the total amount (100 parts by mass) of the resin composition layer. Allow to dry.
• the conditions for achieving such drying also vary depending on the type and amount of organic solvent in the varnish.
• a varnish containing 10 to 200 parts by mass of methyl ethyl ketone with respect to a total of 100 parts by mass of the aminotriazine novolak resin (A) and the compound (B) 2.5% under heating conditions of 90 to 160°C under 1 atmosphere. Drying for ⁇ 15 minutes is a guideline.
• the thickness of the resin composition layer in the laminate of the present embodiment is not particularly limited, but when the resin composition layer is dried, the viewpoint of better removal of relatively low molecular weight volatile matter and the function as a laminate is preferably in the range of 5 to 500 ⁇ m, and more preferably in the range of 10 to 100 ⁇ m, from the viewpoint of achieving the above effectively and reliably.
• a protective film may be separately laminated on the surface of the laminate opposite to the surface having the support substrate for the purpose of storage or the like.
• the semiconductor chip with a resin composition layer of the present embodiment includes a semiconductor chip and a layer (resin composition layer) laminated on the semiconductor chip and formed using the resin composition of the present embodiment.
• the semiconductor chip mounting substrate with the resin composition layer of the present embodiment includes a semiconductor chip mounting substrate and a layer laminated on the semiconductor chip mounting substrate and formed using the resin composition of the present embodiment. (Resin composition layer).
• the semiconductor chip with a resin composition layer of the present embodiment is specified as comprising a semiconductor chip and a layer (resin composition layer) containing the resin composition of the present embodiment laminated on the semiconductor chip.
• the semiconductor chip mounting substrate with a resin composition layer of the present embodiment includes a semiconductor chip mounting substrate and a layer containing the resin composition of the present embodiment laminated on the semiconductor chip mounting substrate (resin composition layer ).
• the method for producing a semiconductor chip with a resin composition layer of the present embodiment is not particularly limited.
• a semiconductor chip with a resin composition layer can be obtained by bonding together so that the resin composition layers of the body face each other, peeling off the support base material in the laminate, and then singulating with a dicing saw or the like.
• the method for producing the semiconductor chip mounting substrate with the resin composition layer of the present embodiment is not particularly limited. It can be obtained by bonding the composition layers so that they face each other, and peeling off the supporting substrate in the laminate.
• a method for bonding the laminate of the present embodiment to a semiconductor wafer or a substrate for mounting a semiconductor chip is not particularly limited, but a vacuum pressure laminator can be preferably used. In this case, it is preferable to apply pressure to the laminate of the present embodiment via an elastic body such as rubber to bond them together.
• the lamination conditions are not particularly limited as long as they are conditions commonly used in the industry, but for example, a temperature of 50 to 140° C., a contact pressure in the range of 1 to 11 kgf/cm 2 , and an atmospheric pressure reduction of 20 hPa or less. done below.
• the bonded laminate may be smoothed by hot pressing with a metal plate.
• the lamination step and the smoothing step can be performed continuously by a commercially available vacuum pressure laminator.
• the laminate attached to a semiconductor wafer or a substrate for mounting a semiconductor-mounted chip is subjected to removal of the support base material before flip-chip mounting of the chip.
• the semiconductor device of the present embodiment includes the semiconductor chip with the resin composition layer of the present embodiment and/or the substrate for mounting the semiconductor chip with the resin composition layer of the present embodiment.
• the method for manufacturing the semiconductor device of the present embodiment is not particularly limited, but for example, a method of mounting the semiconductor chip with the resin composition layer of the present embodiment on a substrate for mounting a semiconductor chip can be mentioned.
• a semiconductor chip may be mounted on the substrate for mounting a semiconductor chip with a resin composition layer of the present embodiment.
• a flip chip bonder compatible with the thermocompression bonding method is preferably used.
• the object to which the resin composition of the present embodiment is applied while flip-chip mounting a semiconductor chip is can be a substrate other than a substrate for mounting a semiconductor chip.
• the resin composition of the present embodiment is used to connect semiconductor chips via a junction between a semiconductor wafer and a semiconductor chip when mounting a semiconductor chip on a semiconductor wafer, or through TSV (Through Silicon Via). It is also possible to use it for the junction between each semiconductor chip of a chip stack, and the effect of this embodiment can be obtained in either case.
• Each part by mass is based on 100 parts by mass of the total amount of aminotriazine novolac resin (A) and compound (B).
• Example 1 As the aminotriazine novolak resin (A), Phenolite (registered trademark) LA-1356 (trade name, DIC Corporation, weight average molecular weight: 1,500, nitrogen content: 19% by mass, hydroxy group equivalent: 146 g/eq.
• Phenolite registered trademark
• LA-1356 trade name, DIC Corporation, weight average molecular weight: 1,500, nitrogen content: 19% by mass, hydroxy group equivalent: 146 g/eq.
• Non-volatile content 60% by mass) 45 parts by mass (27 parts by mass in terms of non-volatile content),
• BMI-70 bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane
• K.I Kasei Co., Ltd., weight average molecular weight 550 22.5 a mass part
• a maleimide compound represented by formula (6) as the third compound (B) MIR-3000-70MT (trade name), Nippon Kayaku Co., Ltd., non-volatile content 70% by mass, weight average molecular weight: 1050)14.
• This varnish was applied to a 38 ⁇ m thick polyethylene terephthalate film (TR1-38 (trade name, support base material), Unitika Ltd.) coated with a release agent on the surface, and dried at 100° C. under 1 atmosphere for 5 minutes. After heating and drying for 1 minute, a laminate having a resin composition layer with a thickness of 30 ⁇ m was obtained.
• TR1-38 trade name, support base material
• Unitika Ltd. polyethylene terephthalate film
• LA-1356 (trade name, manufactured by DIC), which is an aminotriazine novolak resin (A), is a compound represented by the formula (1) (a mixture of compounds represented by the formula (1), in which is a compound in which R 1 is each independently a hydrogen atom or a methyl group, l, m, and n are each independently an integer of 1 to 6, and (l + m + n) is an integer of 3 to 18 group) and a compound represented by formula (2) (a mixture of compounds represented by formula (2), in which each R 2 is independently a hydrogen atom or a methyl group and o, p, q, r, and s are each independently an integer of 1 to 4, and (o + p + q + r + s) is an integer of 5 to 20.
• formula (1) a mixture of compounds represented by the formula (1), in which is a compound in which R 1 is each independently a hydrogen atom or a methyl group, l, m, and n are each independently an integer of 1 to 6, and (
• the mass ratio of the compound (mixture) represented by formula (1) to the compound (mixture) represented by formula (2) (formula (1): formula (2)) is 65 (parts by mass ): 35 (parts by mass).
• YA050C-MJE was a reaction product of silica and 3-methacryloxypropyltrimethoxysilane. That is, YA050C-MJE was evaluated as having a functional group on the silica surface having a structure obtained by reacting at least one silanol group on the silica surface with at least one methoxy group in the following formula (13). .
• Example 2 As the inorganic filler (D), instead of YA050C-MJE of Example 1, slurry silica (Y50SV-AM1 (trade name), Admatechs Co., Ltd., vinylsilane surface-treated silica, solid content 50% by mass, dispersion medium: A varnish was prepared in the same manner as in Example 1, except that 400 parts by mass of MEK (average particle size: 50 nm) (200 parts by mass in terms of nonvolatile matter) was used. Using this varnish, a laminate having a resin composition layer with a thickness of 30 ⁇ m was obtained in the same manner as in Example 1. Y50SV-AM1 was a reaction product of silica and vinyltrimethoxysilane.
• YA050C-MJE was evaluated as having a functional group on the silica surface having a structure obtained by reacting at least one silanol group on the silica surface with at least one methoxy group in the following formula (14). .
• Example 3 As the inorganic filler (D), instead of YA050C-MJE of Example 1, slurry silica (Y50SP-AM1 (trade name), Admatechs Co., Ltd., phenylsilane surface-treated silica, solid content 50% by mass, dispersion medium : MEK, average particle diameter: 50 nm) 400 parts by mass (200 parts by mass in terms of non-volatile matter) was used to prepare a varnish in the same manner as in Example 1. Using this varnish, a laminate having a resin composition layer with a thickness of 30 ⁇ m was obtained in the same manner as in Example 1. Y50SP-AM1 was a reaction product of silica and phenyltrimethoxysilane. That is, YA050C-MJE was evaluated as having a functional group on the silica surface having a structure obtained by reacting at least one silanol group on the silica surface with at least one methoxy group in the following formula (15). .
• Example 4 The amount of YA050C-MJE used in Example 1 was changed to 200 parts by mass (100 parts by mass in terms of nonvolatile matter), and the amounts of LA-1356, BMI-70 and MIR-3000-70MT were changed to 20, respectively.
• a varnish was prepared in the same manner as in Example 1, except that parts by mass (converted to non-volatile content), 27.3 parts by mass (converted to non-volatile content), and 12.2 parts by mass (converted to non-volatile content) were changed. Using this varnish, a laminate having a resin composition layer with a thickness of 30 ⁇ m was obtained in the same manner as in Example 1.
• Example 1 As the inorganic filler (D), instead of YA050C-MJE of Example 1, slurry silica (YA050C-MJM (trade name), Admatechs Co., Ltd., phenylaminosilane surface-treated silica, solid content 50% by mass, dispersion medium : MEK, average particle diameter: 50 nm) 400 parts by mass (200 parts by mass in terms of non-volatile matter) was used to prepare a varnish in the same manner as in Example 1. Using this varnish, a laminate having a resin composition layer with a thickness of 30 ⁇ m was obtained in the same manner as in Example 1.
• YA050C-MJM was a reaction product of silica and phenylaminopropyltrimethoxysilane. That is, YA050C-MJM was evaluated as having a functional group on the silica surface having a structure obtained by reacting at least one silanol group on the silica surface with at least one methoxy group in the following formula (16). .
• Example 2 Change the amount of YA050C-MJE used in Example 1 to 200 parts by mass (100 parts by mass in terms of non-volatile content), do not use LA-1356, and use BMI-70 and MIR-3000-70MT A varnish was prepared in the same manner as in Example 1, except that the amounts were changed to 41.5 parts by mass (as non-volatile content) and 18 parts by mass (as non-volatile content), respectively. Using this varnish, a laminate having a resin composition layer with a thickness of 30 ⁇ m was obtained in the same manner as in Example 1.
• Example 3 (Comparative Example 3) In Example 1, BMI-1000P was not used, and the amount of LA-1356, BMI-70, and MIR-3000-70MT used was 45 parts by weight (in terms of nonvolatile matter) and 38 parts by weight (nonvolatile matter A varnish was prepared in the same manner as in Example 1, except that the content was changed to 17 parts by mass (converted to non-volatile content). Using this varnish, a laminate having a resin composition layer with a thickness of 30 ⁇ m was obtained in the same manner as in Example 1.
• Example 4 (Comparative Example 4) In Example 1, BMI-70 and MIR-3000-70MT were not used, and the amount of LA-1356 and BMI-1000P used was 40 parts by weight (in terms of non-volatile matter) and 60 parts by weight (in terms of non-volatile matter), respectively.
• a varnish was prepared in the same manner as in Example 1, except that the Using this varnish, a laminate having a resin composition layer with a thickness of 30 ⁇ m was obtained in the same manner as in Example 1.
• Image data of the mounted sample was acquired using an ultrasonic precision flaw detection image processing device ( ⁇ -SDS (trade name), manufactured by KJTD Co., Ltd.).
• ⁇ -SDS ultrasonic precision flaw detection image processing device
• the presence or absence of voids in the resin composition layer in the range of the semiconductor chip mounting portion was confirmed from the image data. If the ratio of the area occupied by the portion where voids can be confirmed is less than 10% with respect to the entire area occupied by the resin composition layer in the range of the semiconductor chip mounting portion, A is the case, and 10% or more and less than 20%. was rated as B, the case of 20% or more and less than 30% was rated as C, and the case of 30% or more was rated as D. In addition, it is evaluated that the smaller the ratio of the area occupied by the portion where voids can be confirmed, the higher the insulation reliability can be obtained. , it is evaluated that a laminate with very high insulation reliability can be obtained.
• the obtained laminate was cut into squares of 8 mm ⁇ 8 mm.
• the cut laminate was applied to the 15 ⁇ m copper circuit surface in the pad portion of the semiconductor chip mounting board (WALTS-KIT CC80(W)-0105JY (trade name) manufactured by Waltz Co., Ltd.). It was laminated so that the resin composition layer in was in contact with. After that, the polyethylene terephthalate film in the laminate was peeled off.
• the cured sample (semiconductor chip / resin composition layer / semiconductor Image data is obtained using an ultrasonic precision flaw detection image processing device ( ⁇ -SDS (trade name), manufactured by KJTD Co., Ltd.), and voids in the resin composition layer in the range of the semiconductor chip mounting part. The presence or absence of was confirmed from the image data. If the ratio of the area occupied by the portion where voids can be confirmed is less than 10% with respect to the entire area occupied by the resin composition layer in the range of the semiconductor chip mounting portion, A is the case, and 10% or more and less than 20%.
• ESPEC SPHH-201 trade name
• the obtained laminate was cut into a square of 8 mm ⁇ 8 mm.
• the cut laminate was applied to the 15 ⁇ m copper circuit surface in the pad portion of the semiconductor chip mounting board (WALTS-KIT CC80(W)-0105JY (trade name) manufactured by Waltz Co., Ltd.). It was laminated so that the resin composition layer in was in contact with. After that, the polyethylene terephthalate film in the laminate was peeled off.
• ESPEC SPHH-201 (trade name)
• the cured sample (semiconductor chip/resin composition layer/semiconductor chip mounting substrate) was polished using a rotary polishing device (device name: MetaServ (registered trademark) 3000 (trade name), manufactured by Buehler) to remove only the semiconductor chip. It was removed to obtain a laminate (A) of the resin composition layer and the substrate for mounting a semiconductor chip.
• the surface of the resin composition layer was visually observed, and the state of peeling was confirmed based on whether or not the wiring layer derived from the semiconductor chip was adhered to the surface. When the wiring layer remains entirely on the resin composition layer side, it is indicated as A because no peeling has occurred.
• the resin composition of the present embodiment has low void properties and excellent chip adhesiveness, it can be used as a material for laminates, semiconductor chips with resin composition layers, substrates for mounting semiconductor chips with resin composition layers, and semiconductor devices. It is preferably used.
• the resin composition is suitable as an underfill material, and more suitable as a pre-applied underfill material.

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• 2022
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