Classifications

• • 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
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
• • 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
• • 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
  • C08F4/00—Polymerisation catalysts
  • C08F4/28—Oxygen or compounds releasing free oxygen
  • C08F4/32—Organic compounds
  • C08F4/34—Per-compounds with one peroxy-radical
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/14—Peroxides
• • 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
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
  • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
  • C08L71/12—Polyphenylene oxides
  • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08L79/085—Unsaturated polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/08—Macromolecular additives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J155/00—Adhesives based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09J123/00 - C09J153/00
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/35—Heat-activated
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/46—Manufacturing multilayer circuits
  • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
  • H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer

Definitions

• the present invention relates to a resin composition, and to an adhesive film for interlayer insulation, a laminated substrate, an electronic component, and a semiconductor device that use the resin composition.
• FR-4 stands for "Flame Retardant Type 4," a material made by soaking glass fiber cloth in epoxy resin and then subjecting it to a heat curing treatment.
• FR-4 Flume Retardant Type 4
• adhesive films for interlayer insulation may simply be referred to as “interlayer adhesive films.”
• the boards used for these high-frequency communications will need to be multi-layered and highly integrated to reduce weight and size.
• Patent Document 1 a polyphenylene ether resin composition containing polyphenylene ether and a styrene-butadiene block copolymer having a 1,2 vinyl structure has been proposed as a high-frequency molding material (see, for example, Patent Document 1).
• the polyphenylene ether resin composition disclosed in Patent Document 1 is said to be capable of improving heat resistance and water resistance while having low dielectric properties.
• Patent Document 1 makes no mention whatsoever of the fluidity (in other words, embeddability into a substrate) required for an interlayer adhesive film. Furthermore, the polyphenylene ether resin composition evaluated in Patent Document 1 is only a methacrylic-modified polyphenylene ether.
• the present invention has been made in consideration of the problems associated with the conventional technology.
• the present invention provides a resin composition that has low dielectric properties and good embeddability in substrates. Furthermore, the present invention provides an adhesive film for interlayer insulation, a laminated substrate, an electronic component, and a semiconductor device that use such a resin composition.
• the present invention provides the following resin composition, as well as an adhesive film for interlayer insulation, a laminated substrate, an electronic component, and a semiconductor device that use the resin composition.
• a resin composition comprising (A) a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group, and (B) a compound having a butadiene skeleton with a 1,2 vinyl group, the number average molecular weight of the (B) component being 1,000 to 10,000.
• n 0 or a positive integer
• o:p:q 1-20:60-98:1-20
• a laminated substrate comprising the resin composition described in any one of [1] to [15] above or the cured product of the adhesive film for interlayer insulation described in [16] above.
• a semiconductor device including the laminated substrate described in [17] or the electronic component described in [18].
• the resin composition of the present invention has the effect of having excellent dielectric properties and excellent embeddability in a substrate.
• a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group as component (A)
• the minimum melt viscosity can be lowered. That is, the thermosetting resin as component (A) described above has high bond energy, so the reaction proceeds slowly, and as a result, it is thought that the minimum melt viscosity is lowered.
• the resin composition of the present invention has excellent dielectric properties, adhesiveness, thermal expansion coefficient, and heat resistance reliability after thermal curing.
• the compound having a butadiene skeleton with 1,2 vinyl groups as component (B) has a number average molecular weight of 1,000 to 10,000, so that the fluidity and thermal expansion coefficient can be set to suitable values.
• the adhesive film for interlayer insulation of the present invention is made of the resin composition of the present invention, and has the effect of having excellent dielectric properties and excellent embeddability. Furthermore, the laminated substrate, electronic component, and semiconductor device of the present invention contain a cured product of the resin composition or adhesive film for interlayer insulation of the present invention, and enjoy the effects of the present invention described so far.
• the first embodiment of the resin composition of the present invention is a resin composition including (A) a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group, and (B) a compound having a butadiene skeleton and a 1,2 vinyl group.
• a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group may be referred to as component (A).
• component (B) the compound having a butadiene skeleton and a 1,2 vinyl group may be referred to as component (B).
• the number average molecular weight of component (B) is 1000 to 10000.
• the resin composition of this embodiment has excellent dielectric properties and is also well embedded in a substrate.
• a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group as component (A)
• the minimum melt viscosity can be lowered. That is, the thermosetting resin as component (A) described above has high bond energy, so the reaction proceeds slowly, and as a result, it is thought that the minimum melt viscosity is lowered.
• the resin composition of the present invention has excellent dielectric properties, adhesiveness, thermal expansion coefficient, and heat resistance reliability after thermal curing.
• the compound having a butadiene skeleton with 1,2 vinyl groups as component (B) has a number average molecular weight of 1,000 to 10,000, so that the fluidity and thermal expansion coefficient can be set to suitable values.
• the resin composition of this embodiment may contain other components such as a thermoplastic elastomer component (C), a reaction accelerator component (D), and an inorganic filler (E) in addition to the above-mentioned components (A) and (B).
• a thermoplastic elastomer component (C) a reaction accelerator component (D)
• an inorganic filler (E) in addition to the above-mentioned components (A) and (B).
• the above-mentioned components may be referred to as components (C) to (E) as appropriate.
• the resin composition of this embodiment may contain further resin components other than component (C).
• the component (A) is a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group.
• the inclusion of the component (A) can lower the minimum melt viscosity. That is, a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group has a high bond energy, so the reaction proceeds slowly, and as a result, the minimum melt viscosity is thought to be lowered.
• a thermosetting resin having a methacryloyl group has a low bond energy, so the reaction proceeds rapidly, and as a result, it is presumed that the minimum melt viscosity increases.
• thermosetting resin having a vinylbenzyl group of component (A) can be, for example, a thermosetting resin having a vinylbenzyl group at its terminal.
• a thermosetting resin can be, for example, a thermosetting resin having a vinylbenzyl group at its terminal and a polyphenylene skeleton.
• thermosetting resin having a vinylbenzyl group at the end and a polyphenylene skeleton is a compound having a structure represented by the following general formula (2).
• R2 , R3 , R4 , R8 , and R9 are alkyl groups or phenyl groups having 6 or less carbon atoms and may be the same as or different from each other.
• R5 , R6 , and R7 are hydrogen atoms or alkyl groups or phenyl groups having 6 or less carbon atoms and may be the same as or different from each other.
• R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 are hydrogen atoms, alkyl groups having 6 or less carbon atoms, or phenyl groups, and may be the same as or different from one another.
• -A- is a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.
• -(Y-O)- is represented by the above structural formula (5).
• -(Y-O)- one type of structure or two or more types of structures are randomly arranged.
• R 18 and R 19 are an alkyl group having 6 or less carbon atoms or a phenyl group, and may be the same as or different from each other.
• R 20 and R 21 are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and may be the same as or different from each other.
• a and b are integers from 0 to 100. At least one of a and b is not 0.
• -A- in structural formula (4) may be, for example, a divalent organic group such as methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 1,4-phenylenebis(1-methylethylidene), 1,3-phenylenebis(1-methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, or 1-phenylethylidene.
• -A- in structural formula (4) is not limited to these.
• R 2 , R 3 , R 4 , R 8 , R 9 , R 18 , and R 19 are preferably alkyl groups having 3 or less carbon atoms
• R 5 , R 6 , R 7 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 20 , and R 21 are preferably hydrogen atoms or alkyl groups having 3 or less carbon atoms.
• -(O-X-O)- represented by structural formula (3) or structural formula (4) is a compound represented by the following structural formula (6), structural formula (7), or structural formula (8).
• -(Y-O)- represented by structural formula (5) is a compound represented by the following structural formula (9) or structural formula (10), or a structure in which a compound represented by structural formula (9) and a compound represented by structural formula (10) are randomly arranged.
• the method for producing the compound represented by general formula (2) is not particularly limited.
• the compound represented by general formula (2) can be produced by the following method. First, a bifunctional phenylene ether oligomer is obtained by oxidative coupling of a bifunctional phenol compound and a monofunctional phenol compound. Next, the terminal phenolic hydroxyl group of the obtained bifunctional phenylene ether oligomer is converted to vinylbenzyl ether. In this manner, the compound represented by general formula (2) can be produced.
• the number average molecular weight of the compound represented by general formula (2) is preferably 1,000 to 3,000, more preferably 1,000 to 2,500, and particularly preferably 1,000 to 2,000.
• the compound has better solubility, low dielectric constant, fluidity, and heat resistance.
• the number average molecular weight is 1,000 or more, the resin composition is less likely to become sticky when formed into a coating film.
• the number average molecular weight is 3,000 or less, the resin composition can be effectively prevented from decreasing in solubility in a solvent.
• component (A) the resin composition has improved electrical properties and curability at high frequencies.
• the number average molecular weight described above is a value obtained by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene.
• the (A) component may be a compound represented by general formula (2) used alone or a combination of two or more compounds represented by general formula (2).
• thermosetting resins having vinylbenzyl groups at the terminals of component (A) examples include “OPE2St-2200” and “OPE2St-1200” manufactured by Mitsubishi Gas Chemical Company, Inc.
• thermosetting resin having a maleimide group of component (A) can be, for example, a thermosetting resin having a maleimide group at its terminal.
• thermosetting resin having a maleimide group at the end, used as component (A), can be, for example, a compound containing one or more maleimide groups in the molecule represented by the following general formula (11).
• Monomaleimide compounds and polymaleimide compounds can be suitably used, and are represented by the following general formulas (11), (12), (13), (14) or (15).
• R31 is an r-valent aliphatic, alicyclic, aromatic, or heterocyclic monovalent or polyvalent organic group.
• Xa and Xb are monovalent atoms or organic groups, which may be the same or different, selected from hydrogen atoms, halogen atoms, and aliphatic organic groups.
• r represents an integer of 1 or more.
• R31 is preferably phenyl, alkylphenyl, dialkylphenyl, alkoxyphenyl, benzyl, dodecyl, alkyl, or cycloalkyl.
• Xa and Xb are preferably hydrogen atoms.
• R 32 is a monovalent or divalent organic group which is aliphatic, alicyclic, aromatic, or heterocyclic. Also, s is 0 or 1.
• R 32 when s is 0 and R 32 is a monovalent group, it is preferably phenyl, alkylphenyl, dialkylphenyl, alkoxyphenyl, benzyl, dodecyl, alkyl, or cycloalkyl. Also, in the above general formula (12), when s is 1 and R 32 is a divalent group, it is preferably alkylene, fluorene, or cyclohexylene-alkylene-cyclohexylene.
• R 33 is -C(Xc) 2 -, -CO-, -O-, -S-, -SO 2 -, or a connecting bond, which may be the same or different.
• Xc represents an alkyl group having 1 to 4 carbon atoms, -CF 3 , -OCH 3 , -NH 2 , a halogen atom, or a hydrogen atom, which may be the same or different.
• the substitution positions of the benzene ring are mutually independent.
• t and u represent 0 or an integer of 1 to 10.
• monomaleimide compounds represented by general formula (11) or (12) include N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(2-methoxyphenyl)maleimide, N-benzylmaleimide, N-dodecylmaleimide, N-isopropylmaleimide, and N-cyclohexylmaleimide.
• polymaleimide compounds represented by general formula (13) or (12) include 1,2-dimaleimidoethane, 1,3-dimaleimidopropane, bis(4-maleimidophenyl)methane, bis(3-ethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, 2,7-dimaleimidofluorene, N,N'-(1,3-phenylene)bismaleimide, N,N'-(1,3-(4-methylphenylene))bismaleimide, bis(4-maleimidophenyl)sulfone, bis(4-maleimidophenyl)sulfide, bis(4-maleimidophenyl)ether, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(3-(3-maleimidophenoxy)phenoxy)benzene, bis(4-)
• v is an average value of 0 to 10.
• w is an average value of 0 to 10.
• Aromatic polymaleimides are preferred from the viewpoints of moisture resistance, heat resistance, breaking strength, metal foil peel strength, and low thermal expansion characteristics when made into a printed wiring board.
• bis(3-ethyl-5-methyl-4-maleimidophenyl)methane is more preferred in terms of further reducing the thermal expansion coefficient
• 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane is more preferred in terms of further increasing breaking strength and metal foil peel strength.
• maleimide compounds In order to improve the moldability of the adhesive film, monomaleimides that undergo a gradual curing reaction are preferred. Among these, N-phenylmaleimide is more preferred in terms of cost.
• the above maleimide compounds may be used alone or in combination of two or more types, or at least one of these maleimide compounds may be used in combination with one or more crosslinking agents.
• the proportion of the maleimide compound in component (A) is preferably 50% by mass or more, and more preferably 80% by mass or more. However, it is more preferable to use the maleimide compound alone rather than in combination with another crosslinking agent.
• thermosetting resin having a maleimide group at the end, used as component (A), may be, for example, a maleimide compound represented by the following general formula (16):
• the content of N,N'-(phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide in the maleimide compound represented by general formula (16) by GPC analysis (RI) is usually 90 area % or less, preferably 10 to 80 area %, more preferably 20 to 80 area %, and even more preferably 30 to 70 area %.
• the content of N,N'-(phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide is 90 area % or less, crystallinity decreases, and solvent solubility improves.
• the lower limit of N,N'-(phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide may be 0 area %, but when it is 10 area % or more, the decrease in reactivity can be suppressed.
• the softening point of the maleimide compound represented by general formula (16) is preferably 50 to 150°C, more preferably 80 to 120°C, even more preferably 90 to 110°C, and particularly preferably 95 to 100°C.
• the melt viscosity at 150°C is 0.05 to 100 Pa ⁇ s, preferably 0.1 to 40 Pa ⁇ s.
• the maleimide compound represented by general formula (16) is more preferably one having a structure represented by the following general formula (17). This is because the crystallinity is reduced compared to when the substitution position of the propyl group relative to the benzene ring to which the maleimide group is not bonded in general formula (16) is para-positioned.
• the number average molecular weight of the maleimide compound as component (A) described above is preferably 400 to 3,000, and more preferably 700 to 2500.
• the solubility, low dielectric constant, fluidity, and heat resistance are improved.
• the number average molecular weight of the maleimide compound described above is a value obtained by gel permeation chromatography (GPC) using a calibration curve with standard polystyrene.
• the maleimide compound as component (A) may be any of the maleimide compounds described above, or two or more of these compounds may be used in combination.
• thermosetting resins having maleimide groups as component (A) include maleimide resin manufactured by Kei-I Chemicals Co., Ltd. (product name "BMI70”) and maleimide resin manufactured by Nippon Kayaku Co., Ltd. (product name "MIR-5000-60T”).
• the component (B) is a compound having a butadiene skeleton with 1,2 vinyl groups.
• the adhesiveness can be improved.
• the butadiene-containing resin having 1,2 vinyl groups can achieve better adhesiveness by forming a copolymer or block copolymer structure with styrene.
• the compound having a butadiene skeleton with 1,2 vinyl groups as the component (B) has a number average molecular weight of 1000 to 10000. By setting the number average molecular weight to such a value, the fluidity and the thermal expansion coefficient can be improved.
• the number average molecular weight of the compound as the component (B) is a value obtained by using a calibration curve of standard polystyrene by gel permeation chromatography (GPC).
• Examples of compounds that can serve as component (B) include components (B1), (B2), and (B3) as shown below.
• the (B1) component is a butadiene copolymer having a 1,2 vinyl group.
• a (B1) component by using such a (B1) component, it is possible to reduce the amount of monomer used, and for example, a suitable cured product can be obtained without using a monomer.
• butadiene copolymers having 1,2 vinyl groups do not have a styrene skeleton, so they tend to have weak adhesion (particularly the peel strength of the roughened surface (M surface)).
• M surface roughened surface
• Examples of the (B1) component include 1,2-polybutadiene homopolymers manufactured by Nippon Soda Co., Ltd. (product names "B-3000” and “B-1000") and the partially hydrogenated product "BI-3015".
• the (B2) component is a styrene-butadiene block copolymer having a 1,2 vinyl structure.
• the (B2) component it is possible to improve the peel strength and reduce the thermal expansion coefficient.
• Component (B2) is a block copolymer containing a butadiene block and a styrene block.
• the styrene block is a block obtained by polymerizing styrene
• the butadiene block is a block obtained by polymerizing butadiene.
• the butadiene block consists of only the 1,2 bond structure represented by the following formula (18), or consists of the 1,2 bond structure represented by formula (18) and the 1,4 bond structure represented by formula (19).
• the molar ratio of the 1,2 bond structure represented by formula (18) to the 1,4 bond structure represented by formula (19) contained in the styrene-butadiene block copolymer having a 1,2 vinyl structure of component (B2) is preferably 80:20 to 100:0.
• the weight ratio of the styrene block to the butadiene block in component (B2) is not particularly limited, but examples include 10:90 to 80:20, 10:90 to 70:30, 10:90 to 60:40, 10:90 to 50:50, 20:80 to 80:20, 30:70 to 80:20, and 40:60 to 80:20. Of these, 10:90 to 80:20, 10:90 to 70:30, 10:90 to 60:40, and 10:90 to 50:50 are preferred, and 10:90 to 50:50 is even more preferred.
• the (B2) component is preferably a styrene-butadiene-styrene block copolymer represented by the following structural formula (1), or a hydrogenated product thereof.
• n 0 or a positive integer
• o:p:q 1-20:60-98:1-20
• component (B) By using a styrene-butadiene-styrene block copolymer as shown in the above structural formula (1) as component (B), it is possible to improve the peel strength and reduce the thermal expansion coefficient.
• the method for producing component (B2) is not particularly limited, but for example, styrene-butadiene-styrene block copolymers can be produced by the methods described in JP-A-6-192502, JP-T-2000-514122, JP-A-2007-302901, etc., or methods equivalent thereto.
• component (B2) examples include “1,2-SBS-L42" and “1,2-H-SBS-L” manufactured by Nippon Soda Co., Ltd.
• the (B3) component is a styrene-butadiene copolymer having 1,2 vinyl groups.
• the number average molecular weight of such a styrene-butadiene copolymer there are no particular limitations on the number average molecular weight of such a styrene-butadiene copolymer, as long as it has 1,2 vinyl groups and its number average molecular weight is 1,000 to 10,000.
• Such a styrene-butadiene copolymer is hydrophobic and has few polar groups. Therefore, adding it to a resin composition can improve the low dielectric properties.
• the (B3) component is a random copolymer rather than a block copolymer, it tends to have weak adhesion (peel strength of the glossy surface (S surface)). In other words, it is presumed that if the phenyl groups are not aligned, it will be difficult to develop strength on a flat surface.
• styrene-butadiene copolymer is liquid, the flexibility of the resin composition is improved, and there is also the advantage that the handling properties (reduction of powdering, etc.) of the resin composition are improved when it is in a semi-cured state.
• the (B3) component is preferably a styrene-butadiene copolymer that has crosslinkable 1,2-vinyl in the molecule, which makes it more reactive than a typical styrene-butadiene polymer that has many 1,4-bonds in the main chain.
• the number average molecular weight is low at 10,000 or less, it is believed that the reactivity of the 1,2-vinyl groups in the styrene-butadiene copolymer is also higher. For these reasons, it is believed that this contributes to the curing reaction, and that the resin does not bleed, resulting in an excellent appearance after molding.
• the (B3) component may be, for example, a styrene-butadiene copolymer having the structure shown in the following formula (20).
• the above formula (20) is an example of a styrene-butadiene copolymer, where d represents a 1,2 vinyl group, e represents a styrene group, and f represents a 1,4-bond.
• An example of a structural unit having a 1,2-vinyl group is the structural unit of the following formula (21).
• An example of a structural unit having a 1,4-bond is the structural unit of the following formula (22).
• An example of a styrene group is the structural unit of the following formula (23).
• the copolymer has a repeating structure of the structural unit of formula (21) and a repeating structure of the structural unit of formula (23). It may further contain a repeating structure of the structural unit of formula (22).
• the styrene content in the molecule is preferably 50% by mass or less and the butadiene content is preferably 50% by mass or more, and more preferably the styrene content is 20 to 50% by mass and the butadiene content is 50 to 80% by mass.
• the content of butadiene is within the above range, it is possible to reliably reduce the elastic modulus of the resin composition, and in turn to reduce the thermal expansion coefficient in the plane direction when the resin composition is made into a laminate. If the thermal expansion coefficient in the plane direction can be reduced, it is possible to reduce the warping of the substrate in a package substrate or the like.
• the styrene and butadiene contents in the styrene-butadiene copolymer can be measured, for example, by nuclear magnetic resonance spectroscopy (NMR).
• styrene-butadiene copolymer of component (B3) examples include “Ricon 181” and “Ricon 100” manufactured by CRAY VALLEY.
• the compound as component (B) is preferably a compound having a styrene skeleton.
• the styrene-butadiene block copolymer having a 1,2 vinyl structure as component (B2) is more preferred from the viewpoints of thermal expansion coefficient, adhesion strength, and heat resistance reliability.
• the number average molecular weight of component (B) is not particularly limited as long as it is 1000 to 10000, but is preferably 1000 to 8000, more preferably 1000 to 5000, and particularly preferably 3500 to 5000.
• the film may be dissolved in a solvent and the number average molecular weight of the component dissolved in the solvent may be measured.
• the compound serving as component (B) preferably has 5 to 95% by mass of 1,2 vinyl structures in its butadiene skeleton, more preferably 10 to 95% by mass, and particularly preferably 20 to 95% by mass.
• 1,2 vinyl structures in the butadiene skeleton within the above numerical range, there is an advantage in that the minimum melt viscosity is lowered.
• such a compound is a butadiene resin containing 5 to 95% by mass of 1,2 vinyl structures.
• the content ratio of 1,2 vinyl structures can be measured by FT-IR, NMR, etc.
• the content of component (B) is preferably 10 to 200 parts by mass per 100 parts by mass of component (A). This composition provides advantages in terms of heat resistance and chemical resistance due to the reaction with component (A). Although not particularly limited, the content of component (B) is more preferably 15 to 190 parts by mass, and even more preferably 20 to 100 parts by mass per 100 parts by mass of component (A).
• the component (C) is a thermoplastic elastomer component.
• the thermoplastic elastomer component is preferably, for example, a styrene-based thermoplastic elastomer or a hydrogenated styrene-based thermoplastic elastomer.
• the hydrogenated styrene-based thermoplastic elastomer refers to a hydrogenated styrene-based thermoplastic elastomer
• examples of the hydrogenated styrene-based thermoplastic elastomer include styrene/butadiene/butylene/styrene block copolymer (partially hydrogenated, SBBS) and styrene/ethylene/butylene/styrene block copolymer (fully hydrogenated, SEBS).
• the styrene ratio of the component (C) is preferably 10 to 50%, more preferably 15 to 40%, and even more preferably 20 to 35%.
• thermoplastic elastomer component of component (C) is not particularly limited, but is preferably a styrene/ethylene/butylene/styrene block copolymer (SEBS).
• SEBS styrene/ethylene/butylene/styrene block copolymer
• the number average molecular weight of the thermoplastic elastomer component of component (C) is not particularly limited, but is preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, and particularly preferably 20,000 to 200,000. If component (C) is a compound having a butadiene skeleton with 1,2 vinyl groups, the number average molecular weight of component (C) is more than 10,000.
• the amount of component (C) is 10 to 150 parts by mass, and more preferably 15 to 100 parts by mass, per 100 parts by mass of the total of components (A) and (B).
• the amount of component (C) is 10 to 150 parts by mass, and more preferably 15 to 100 parts by mass, per 100 parts by mass of the total of components (A) and (B).
• the component (D) is a reaction accelerator component.
• the reaction accelerator component as the component (D) is an additive for accelerating the reaction of the components (A) and (B). By including such a component (D), the reaction initiation temperature is shifted to the lower temperature side, and the curing of the resin composition is accelerated.
• the reaction accelerator component of component (D) may be any component that accelerates the reaction between components (A) and (B), and may be any conventionally known reaction accelerator component.
• reaction accelerator components include organic peroxides, inorganic peroxides, and azo compounds. Organic peroxides are preferred as the reaction accelerator component of component (D).
• Organic peroxides include diacyl peroxides such as benzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, parachlorobenzoyl peroxide, and di(3,5,5-trimethylhexanoyl)peroxide; peroxyketals such as 2,2-di(4,4-di(di-tert-butylperoxy)cyclohexyl)propane; isopropyl percarbonate, di -sec-butyl purge carbonate, di-2-ethylhexyl purge carbonate, di-1-methylheptyl purge carbonate, di-3-methoxybutyl purge carbonate, dicyclohexyl purge carbonate and other peroxydicarbonates; tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl per-2-ethyl
• organic peroxide used there are no particular limitations, but since a drying step at, for example, about 60 to 80°C is often required when curing the resin composition, it is preferable to use one with a 10-hour half-life temperature of 100 to 140°C. Furthermore, one with a 10-hour half-life temperature of 110 to 130°C is more preferable.
• the organic peroxide of component (D) includes organic peroxides manufactured by NOF Corporation under the trade names "Percumyl D” and "Perbutyl C.” Component (D) may be used alone or in combination of two or more kinds.
• component (D) When component (D) is contained, the content of component (D) is preferably 0.1 to 5.0 parts by mass, and more preferably 0.5 to 3.0 parts by mass, per 100 parts by mass of the resin components in the composition. By configuring in this way, it is possible to satisfactorily improve heat resistance and adhesion.
• the component (E) is an inorganic filler.
• the inorganic filler is required to have insulating properties and a low thermal expansion coefficient.
• a general inorganic filler can be used.
• examples of inorganic fillers include silica, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, and boron nitride.
• the inorganic fillers may be used alone or in combination of two or more.
• silica fillers and alumina fillers are preferred from the viewpoint of insulation.
• silica fillers are preferred from the viewpoint of dielectric properties and thermal expansion coefficient.
• the inorganic fillers may be surface-treated with a silane coupling agent having one or more functional groups selected from acrylic, methacrylic, styryl, amino, epoxy, and vinyl.
• the inorganic filler is preferably surface-treated with a surface treatment agent such as an aminosilane coupling agent, a ureidosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, a vinylsilane coupling agent, a styrylsilane coupling agent, an acrylate silane coupling agent, an isocyanate silane coupling agent, a sulfide silane coupling agent, an organosilazane compound, or a titanate coupling agent to improve its heat resistance, moisture resistance, and dispersibility.
• a surface treatment agent such as an aminosilane coupling agent, a ureidosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, a vinylsilane coupling agent, a styrylsilane coupling agent, an acrylate silane coupling agent, an
• the thermal expansion coefficient can be improved.
• the shape of the inorganic filler is not particularly limited, and examples include spherical, scaly, needle-like, and amorphous shapes. From the viewpoint of fluidity, spherical shapes are preferred.
• the average particle size is preferably 0.1 to 10 ⁇ m, and more preferably 0.1 to 4 ⁇ m. When the average particle size of the inorganic filler is in this range, it has excellent embedding properties between microstructures.
• the average particle size is the particle size at 50% of the cumulative value in the particle size distribution on a volume basis, measured by a laser diffraction/scattering method. The average particle size can be measured, for example, by a laser scattering diffraction method particle size distribution measuring device: LS13320 (manufactured by Beckman Coulter, Inc., wet type).
• the resin composition contains the (E) component
• the resin composition contains 50% by mass or more of the (E) component, more preferably 50 to 90% by mass, and even more preferably 50 to 85% by mass, of 100% by mass of the non-volatile components in the resin composition.
• the content of the (E) component is defined as a ratio to the total amount of the (A) and (B) components
• the (E) component is contained in an amount of 200 parts by mass or more, more preferably 200 to 900 parts by mass, and even more preferably 400 to 900 parts by mass, of 100 parts by mass of the total of the (A) and (B) components.
• the resin composition of the present embodiment may further contain components other than the components (A) to (E) described above.
• the other components may include various additives such as a solvent, a silane coupling agent, a flame retardant, and a pigment.
• the resin composition may further contain other compounds (for example, other resin components).
• the other resin components include isocyanuric acid (diallylated isocyanuric acid derivative) from the viewpoint of further improving embeddability in a substrate, and a commercially available product thereof is the product name "L-DAIC" by Shikoku Chemical Industry Co., Ltd.
• the resin composition of the present embodiment preferably has, for example, the following properties:
• the minimum melt viscosity of the resin composition is preferably less than 40,000 Pa ⁇ s. By configuring in this way, the embeddability into the substrate is extremely good.
• the minimum melt viscosity of the resin composition is more preferably 10 Pa ⁇ s or more and less than 40,000 Pa ⁇ s, even more preferably 100 Pa ⁇ s or more and less than 30,000 Pa ⁇ s, and particularly preferably 1,000 Pa ⁇ s or more and less than 10,000 Pa ⁇ s. Even when the content of component (E) in 100% by mass of non-volatile components in the resin composition is less than 50% by mass, the minimum melt viscosity of the resin composition is more preferably 10 Pa ⁇ s or more and less than 40,000 Pa ⁇ s, as in the above case, and even more preferably 100 Pa ⁇ s or more and less than 30,000 Pa ⁇ s.
• the minimum melt viscosity of the resin composition is more preferably 100 Pa ⁇ s or more and less than 40,000 Pa ⁇ s, even more preferably 1,000 Pa ⁇ s or more and less than 40,000 Pa ⁇ s, and particularly preferably 5,000 Pa ⁇ s or more and less than 30,000 Pa ⁇ s.
• the minimum melting temperature of the resin composition is preferably less than 200°C, more preferably 80°C or higher and less than 200°C, and even more preferably 100°C or higher and less than 180°C.
• the minimum melt viscosity (Pa ⁇ s) and minimum melt temperature (°C) of the resin composition can be measured by the following method. First, a solution containing the resin composition is applied to a peel-treated PET film using a knife method. The solution on the PET film is then dried continuously at temperatures of 80°C for 2 minutes, 100°C for 2 minutes, and 130°C for 2 minutes to produce a resin film with a thickness of 50 ⁇ m. The resin film produced in this way is laminated to a thickness of 300 ⁇ m, and the melt viscosity is measured using a rheometer.
• the minimum melt viscosity and minimum melt temperature at that time are read, and the values read are the minimum melt viscosity (Pa ⁇ s) and minimum melt temperature (°C) of the resin composition.
• the measurement conditions are as follows: parallel plates with a diameter of 5 mm are used, and measurements are made from 50 to 200°C at a load of 50 gf, a strain of 1%, a frequency of 10 Hz, and a rate of 5°C/min.
• the solution to be applied to the PET film (solution containing the resin composition) can be prepared by dissolving each component constituting the resin composition in toluene as a solvent.
• the solution is prepared so that the solids concentration in the solution is 30% by mass.
• the resin composition contains an inorganic filler as component (E)
• the solution is prepared by dissolving and dispersing each component so that the solids concentration in the solution is 60% by mass.
• the resin composition of the present embodiment can be produced by a conventional method, for example, by mixing the components described above using a mortar and pestle mixer, a pot mill, a three-roll mill, a rotary mixer, a twin-shaft mixer, or the like.
• the resin composition of this embodiment can be suitably used as a resin composition for adhesives and adhesive films used for electronic components.
• the resin composition of this embodiment can also be suitably used as a bonding sheet for layer-to-layer bonding and an interlayer adhesive for multilayer wiring boards.
• the resin composition of this embodiment can be suitably used as an adhesive film for interlayer insulation.
• the resin composition of this embodiment is used for various applications for electronic components, there is no particular restriction on the electronic components to be bonded, and examples of the electronic components to be bonded include various printed wiring boards such as ceramic boards and organic boards, semiconductor chips, and semiconductor devices.
• the resin composition of this embodiment can also be suitably used as a dielectric layer in the rewiring layer of FO-WLP (fan-out wafer level package).
• An adhesive film for interlayer insulation or an interlayer adhesive using the resin composition of this embodiment is included as a cured product of the resin composition in a laminate substrate or semiconductor device that constitutes electronic components, etc. For this reason, it is preferable that a cured product of the resin composition of this embodiment is included in a laminate substrate or semiconductor device that constitutes electronic components, etc.
• the resin composition of this embodiment can also be used as a prepreg using a cured product of the resin composition, or as a high-frequency electronic component having a cured product of the resin composition.
• Example 1 to 17 Comparative Examples 1 to 7
• Example Preparation The components were weighed and mixed to give the mixing ratios (parts by mass) shown in Tables 1 to 4 below, and then dissolved in toluene as a solvent to prepare solutions containing the resin compositions of Examples 1 to 17 and Comparative Examples 1 to 7.
• the resin composition did not contain an inorganic filler as component (E)
• the solution was prepared so that the solids concentration in the solution was 30% by mass.
• the resin composition contained an inorganic filler as component (E) the solution was prepared by dissolving and dispersing each component so that the solids concentration in the solution was 60% by mass.
• Component (A')] A1': manufactured by SABIC, product name "SA-9000", number average molecular weight (Mn) 1700, modified polyphenylene ether resin having a methacrylic group at the end.
• C1 Kraton Polymers, product name "G1652”, number average molecular weight (Mn): 54,000, thermoplastic elastomer (SEBS: styrene 30%).
• C2 Asahi Kasei Corporation, product name "P1500”, number average molecular weight (Mn): 49,000, thermoplastic elastomer (SBBS: styrene 30%).
• C3 ENEOS Materials Corporation, product name "TR2003”, number average molecular weight (Mn): 100,000, styrene-butadiene block copolymer (styrene 43%).
• the “Total resin components (A+B+C+other resins)” column in Tables 1 to 4 shows the total amounts (parts by mass) of components (A), (B), (C) and other resin components in the raw materials used to prepare the resin compositions.
• the “Amount of filler (parts by mass) per 100 parts by mass of the total of (A+B)” column in Tables 2 to 3 shows the ratio (parts by mass) of component (E) per 100 parts by mass of the total of components (A) and (B) used to prepare the resin compositions.
• the prepared resin film was laminated to a thickness of 300 ⁇ m, and the melt viscosity was measured using a rheometer. The minimum melt viscosity and minimum melt temperature at that time were read, and the read values were taken as the minimum melt viscosity (Pa s) and minimum melt temperature (°C) of the resin composition.
• the measurement conditions were as follows: parallel plates with a diameter of 5 mm were used, and the measurement was performed from 50 to 200°C under a load of 50 gf, a strain of 1%, a frequency of 10 Hz, and a rate of 5°C/min.
• the dielectric constant ( ⁇ ) and dielectric loss tangent (tan ⁇ ) of the sample cooled to room temperature were measured in the same manner as described above. The values measured in this manner were taken as the measured values after the heat resistance test and are shown in the "125°C x 24h after" column of Table 4.
• the values of the dielectric constant ( ⁇ ) and dielectric loss tangent (tan ⁇ ) measured before and after the heat resistance test were subtracted from the initial values from the measured values after the heat resistance test to obtain the "amount of change from the initial value”.
• the percentage of the "amount of change from the initial value" divided by the initial value was calculated as the "amount of change from the initial value (%).”
• the results are shown in Table 4. The measurement by the dielectric resonator method was performed at a measurement frequency of 20 GHz.
• thermo expansion coefficient (ppm/K) thermo expansion coefficient (ppm/K)
• thermal expansion coefficient (thickness) ppm/K)
• solder heat resistance were evaluated and measured using the methods shown below.
• the initial values of the dielectric constant ( ⁇ ) and dielectric dissipation factor (tan ⁇ ) in the above-mentioned heat resistance reliability were measured.
• the measurement frequency using the dielectric resonator method was changed to 10 GHz, and the initial values of the dielectric constant ( ⁇ ) and dielectric dissipation factor (tan ⁇ ) in the above-mentioned heat resistance reliability were measured.
• Thermal expansion coefficient (ppm/K) The prepared resin films were laminated to a thickness of 100 ⁇ m, and cured at a temperature of 200° C. for 60 minutes under a pressure of 1 MPa to prepare a sample for measuring the thermal expansion coefficient. The measurement was performed using a tensile method with a thermomechanical analyzer, and the average thermal expansion coefficient from 90 to 100°C was taken as the reading (i.e., the measured value of the thermal expansion coefficient). The measurement conditions were a tensile load of 2 gf, 20°C/ The specimen was annealed at 5° C./min up to 230° C., then cooled to room temperature, and then measured at 5° C./min up to 230° C. The measured thermal expansion coefficient was the thermal expansion coefficient in the planar direction (i.e., the XY direction).
• Thermal expansion coefficient (thickness) (ppm/K)
• the prepared resin film was laminated to a thickness of about 2 mm, and cured at a temperature of 200°C for 60 minutes under a pressure of 1 MPa to prepare a sample for measuring the thermal expansion coefficient (thickness).
• the prepared sample was measured by a compression method using a TMA (thermomechanical analyzer), and the average thermal expansion coefficient from 90 to 100°C was read (i.e., the measured value of the thermal expansion coefficient (thickness)).
• the measurement conditions were a compression load of 1 gf, annealing at 20°C/min up to 250°C, then returning to room temperature, and then measuring at 5°C/min up to 250°C.
• the thermal expansion coefficient is the thermal expansion coefficient in the thickness direction (i.e., Z direction).
• solder heat resistance After bonding copper foil to both sides of the prepared adhesive film, the test pieces were cut into 2 cm x 2 cm squares to prepare test pieces. The prepared test pieces were floated in solder baths heated to 260, 270, 280, 290, and 300 ° C for 1 minute, and their appearance was visually confirmed. The temperature (maximum temperature) of the solder bath at which no change in appearance was observed was used as the evaluation value of solder heat resistance.
• the resin compositions of Examples 1 to 5 had lower minimum melt viscosities and lower minimum melting temperatures than the resin composition of Comparative Example 2. It was impossible to measure the minimum melt viscosity and minimum melting temperature of the resin composition of Comparative Example 1.
• the resin compositions of Examples 9 to 17 had extremely low minimum melt viscosities compared to the resin compositions of Comparative Examples 3 to 7.
• the resin compositions of Examples 9 to 16 and Comparative Examples 3 to 7 contained an inorganic filler (silica filler) as component (E), and the resin compositions of Comparative Examples 3 to 7 showed extremely high minimum melt viscosities.
• the resin compositions of Examples 9 to 16 contained a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group as component (A), so the increase in minimum melt viscosity was suppressed, and the resin compositions had excellent embeddability into a substrate.
• the resin compositions of Examples 9 to 17 also showed good values for copper foil peel strength M (N/cm) and copper foil peel strength S (N/cm), and had excellent adhesion.
• the resin compositions of Examples 9 to 16 also showed good results in terms of thermal expansion coefficient and solder heat resistance.
• the thermal expansion coefficients (ppm/K) of the resin compositions of Examples 9 to 16 were 102, 123, 46, 50, 56, 44, 50, and 55, respectively (all units are ppm/K).
• the thermal expansion coefficients (thickness) (ppm/K) of the resin compositions of Examples 9 to 16 were 39, 55, 46, 56, 50, 38, 42, and 59, respectively (all units are ppm/K).
• the resin compositions of Examples 9 to 14 had dielectric constants ( ⁇ ) of 3.05, 3.12, 3.10, 3.10, 2.89, and 3.06, respectively, at a measurement frequency of 10 GHz, and dielectric dissipation factor (tan ⁇ ) of 0.0014, 0.0015, 0.0013, 0.0011, 0.0015, and 0.0014, respectively.
• the resin compositions of Examples 13 to 16 had dielectric constants ( ⁇ ) of 3.01, 3.08, 3.07, and 3.09, respectively, at a measurement frequency of 20 GHz, and dielectric dissipation factor (tan ⁇ ) of 0.0016, 0.0015, 0.0015, and 0.0013, respectively.
• the resin compositions of Examples 9 to 14 also showed good values of 300°C or 290°C in the evaluation of solder heat resistance.
• the resin composition of Example 17 does not contain any other resin components, and contains the (A) and (B) components as resin components.
• the resin composition of Example 17 does not contain an inorganic filler as the (E) component.
• the resin composition of Example 17 also had a low minimum melt viscosity and a low minimum melt temperature.
• the resin composition of Example 17 had a thermal expansion coefficient (ppm/K) of 102 ppm/K and a thermal expansion coefficient (thickness) (ppm/K) of 73 ppm/K.
• the resin composition of Example 17 can also be suitably used as a dielectric layer in the redistribution layer of a FO-WLP (fan-out wafer level package), for example.
• the resin compositions of Comparative Examples 3 to 7 had thermal expansion coefficients (ppm/K) of 51, 35, 36, 51, and 50, respectively, and thermal expansion coefficients (thickness) (ppm/K) of 37, 47, 29, 37, and 64, respectively (all units are ppm/K).
• the resin compositions of Comparative Examples 3 to 7 also had dielectric constants ( ⁇ ) of 3.12, 3.06, 3.11, 3.12, and 3.12, respectively, at a measurement frequency of 10 GHz, and dielectric dissipation factor (tan ⁇ ) of 0.0014, 0.0012, 0.0013, 0.0014, and 0.0019, respectively.
• the resin composition of Comparative Example 7 also showed a low value of 270°C in the evaluation of solder heat resistance.
• the resin composition of Example 6 uses a styrene-butadiene block copolymer (B2) as the (B) component.
• the resin composition of Example 8 uses a butadiene resin (B1) as the (B) component.
• the resin composition of Example 7 uses a styrene-butadiene copolymer (B3) as the (B) component.
• the resin composition of Example 6 using a styrene-butadiene block copolymer (B2) has better heat resistance reliability (change rate of tan ⁇ ) than the other (B) components, and also shows good results in terms of peel strength M against the matte surface (M surface) of the electrolytic copper foil.
• the thermal expansion coefficients (ppm/K) of the resin compositions of Examples 6 to 8 were 149, 146, and 154, respectively, and the thermal expansion coefficients (thickness) (ppm/K) were 194, 207, and 196, respectively (all units are ppm/K).
• the resin composition of the present invention can be used as a resin composition for adhesives and adhesive films used in electronic components. It can also be used as a bonding sheet or interlayer adhesive for layer-to-layer wiring boards.
• the resin composition of the present invention can also be used as a prepreg using a cured product of the resin composition, or as a high-frequency electronic component having a cured product of the resin composition.

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