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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/06—Interconnection of layers permitting easy separation
• • 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
  • C08L53/005—Modified block copolymers
• • 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
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • 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
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
• • 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
• • 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
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • 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
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • 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
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • 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
  • C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• • 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
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
• • 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
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
  • C08F283/045—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides on to unsaturated polycarbonamides, polyesteramides or polyimides
• • 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
  • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; 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
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • 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
• • 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
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
  • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
  • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
  • H10W74/473—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins containing a filler
• • 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
  • B32B2311/00—Metals, their alloys or their compounds
  • B32B2311/12—Copper
• • 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
  • B32B2457/00—Electrical equipment
  • B32B2457/08—PCBs, i.e. printed circuit boards
• • 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
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/16—Applications used for films

Definitions

• This embodiment relates to a resin film with a support, a method for manufacturing a printed wiring board, and a method for manufacturing a semiconductor package.
• a resin film with a support which has a resin film formed on a support using a resin composition, is sometimes used as an insulating material.
• the resin film may be used, for example, to form an insulating layer by being cured while embedding a circuit of a circuit board, or as an encapsulant for a semiconductor chip.
• the thermosetting resin composition of Patent Document 1 is excellent in dielectric tangent, low thermal expansion, embeddability of wiring, etc., but when the thickness of the resin film is increased, cracks may occur. This problem is likely to occur when using a thermosetting resin that is particularly likely to provide high heat resistance, and when using an inorganic filler that contributes to low thermal expansion. In order to solve the above problem, it is considered effective to improve the flexibility of the resin film.
• insulating materials used in electronic components are required to have dielectric properties capable of reducing transmission loss of high-frequency signals, i.e., low dielectric constant and low dielectric tangent, and as a result, low-polarity components are increasingly being used.
• low-polarity components are difficult to dissolve in the aqueous oxidizing agent used in roughening treatment, and therefore, even if conventional roughening treatment is performed on an insulating layer formed from a resin film containing low-polarity components, there are cases in which sufficient peel strength against the plated metal [hereinafter sometimes simply referred to as "plating peel strength"] cannot be obtained.
• the present embodiment aims to provide a resin film with a support that can form a cured product with excellent plating peel strength, has excellent flexibility, and can suppress the generation of volatile components during heat curing, as well as a method for manufacturing a printed wiring board and a method for manufacturing a semiconductor package that use the resin film with a support.
• a support-attached resin film having a support and a resin film containing a resin composition provided on one surface of the support contains (A) a thermosetting resin, (B) a compound that is liquid at 25°C, has a reactive group, and has a molecular weight of 1,000 or less, and (C) an inorganic filler, A resin film with a support, wherein the surface of the support facing the resin film has an arithmetic mean roughness Ra of 0.06 ⁇ m or more.
• the maleimide resin having one or more N-substituted maleimide groups is a maleimide resin containing a condensed ring of an aromatic ring and an aliphatic ring in its molecular structure and having two or more N-substituted maleimide groups.
• a method for producing a printed wiring board comprising forming an insulating material using the support-attached resin film according to any one of [1] to [11] above.
• a method for producing a semiconductor package comprising forming an insulating material using the resin film with a support according to any one of [1] to [11] above.
• a resin film with a support that can form a cured product with excellent plating peel strength, has excellent flexibility, and can suppress the generation of volatile components during heat curing, as well as a method for manufacturing a printed wiring board and a method for manufacturing a semiconductor package using the resin film with a support.
• solids refers to components other than the solvent, and includes those that are liquid, syrup-like, or waxy at room temperature.
• room temperature refers to 25°C.
• the number average molecular weight in this specification means a value measured in terms of polystyrene by gel permeation chromatography (GPC). Specifically, the number average molecular weight in this specification can be measured by the method described in the Examples.
• This embodiment also includes any combination of the items described in this specification.
• being liquid at 25° C. means that the viscosity calculated by the following measurement method is 100,000 mPa ⁇ s or less.
• ⁇ Method of measuring viscosity> Apparatus: E-type viscometer Cone rotor: 1°34' x R24 Temperature: 25°C Sample volume: 1.0 mL Rotation speed: 20 rpm
• the viscosity at 25° C. means the viscosity measured by the above-mentioned method.
• the reason why the supported resin film of this embodiment is capable of forming a cured product having excellent plating peel strength and excellent flexibility while suppressing the generation of volatile components during heat curing is presumed to be as follows.
• the resin composition contained in the resin film of the supported resin film of this embodiment contains, as a component that improves the flexibility of the resin composition, (B) a compound that is liquid at 25° C. and has a molecular weight of 1,000 or less. Since the (B) reactive liquid compound is a liquid component with a relatively low molecular weight, it can easily penetrate between the molecules of the resin component, and it is believed that the flexibility of the resin film can be improved by effectively weakening the intermolecular interaction of the resin component.
• the surface of the support facing the resin film has an arithmetic mean roughness Ra of 0.06 ⁇ m or more, and therefore the cured resin film has a surface in contact with the support that has good irregularities that can serve as an anchor for the plating metal, which is presumably the reason for the improved plating peel strength.
• the resin composition of the present embodiment contains (A) a thermosetting resin.
• the thermosetting resin (A) may be used alone or in combination of two or more kinds.
• Examples of the alkyl group having 1 to 10 carbon atoms represented by R a1 in the above general formula (A1-1) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. These alkyl groups may be either linear or branched. Examples of the alkyl group contained in the alkyloxy group having 1 to 10 carbon atoms and the alkylthio group having 1 to 10 carbon atoms represented by R a1 include the same as the alkyl group having 1 to 10 carbon atoms described above.
• Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R a1 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group.
• the maleimide resin (A2) is preferably a polymaleimide resin represented by the following general formula (A2-7).
• the content of the (A) thermosetting resin is not particularly limited, but is preferably 5 to 60 mass%, more preferably 8 to 40 mass%, even more preferably 10 to 30 mass%, and particularly preferably 15 to 25 mass%, relative to the total amount (100 mass%) of the resin components in the resin composition of the present embodiment.
• the content of the (A) thermosetting resin is equal to or greater than the lower limit, the heat resistance, moldability, processability, and conductor adhesion tend to be improved.
• the content of the (A) thermosetting resin is equal to or less than the upper limit, the dielectric properties tend to be improved.
• the content of the maleimide resin in the thermosetting resin (A) is not particularly limited, but is preferably 80 to 100 mass%, more preferably 90 to 100 mass%, and even more preferably 95 to 100 mass%, relative to the total amount (100 mass%) of the thermosetting resin (A).
• the content of the maleimide resin is equal to or greater than the lower limit, the heat resistance, moldability, processability, and conductor adhesion tend to be improved, whereas when the content of the maleimide resin is equal to or less than the upper limit, the dielectric properties tend to be improved.
• the reactive liquid compound (B) is not particularly limited as long as it is a compound that is liquid at 25° C., has a reactive group, and has a molecular weight of 1,000 or less.
• the reactive liquid compound (B) may be used alone or in combination of two or more kinds.
• the viscosity of the reactive liquid compound (B) at 25° C. is preferably 1 to 5,000 mPa ⁇ s, more preferably 2 to 1,000 mPa ⁇ s, and even more preferably 4 to 500 mPa ⁇ s.
• the viscosity of the (B) reactive liquid compound at 25° C. is equal to or higher than the above lower limit, the (B) reactive liquid compound tends to be easily prevented from volatilizing.
• the viscosity of the (B) reactive liquid compound at 25° C. is equal to or lower than the above upper limit, better flexibility tends to be easily obtained.
• the viscosity of the reactive liquid compound (B) at 25° C. can be measured by the above-mentioned measuring method.
• Examples include allyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
• dioxane glycol di(meth)acrylate examples include 2-[5-ethyl-5-[(acryloyloxy)methyl]-1,3-dioxane-2-yl]-2,2-dimethylethyl acrylate.
• trifunctional or higher (meth)acrylic acid esters examples include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.
• R b1 is an alkylene group having 1 to 20 carbon atoms.
• the number of carbon atoms in the alkylene group having 1 to 20 carbon atoms represented by R b1 in the above general formulas (B-1) and (B-2) is preferably 4 to 18, more preferably 6 to 15, and even more preferably 8 to 12, from the viewpoints of flexibility and suppression of volatilization.
• the content of the (B) reactive liquid compound is not particularly limited, but is preferably 5 to 60 mass %, more preferably 8 to 40 mass %, even more preferably 10 to 30 mass %, and particularly preferably 15 to 25 mass %, relative to the total amount (100 mass %) of the resin components in the resin composition of the present embodiment.
• the content of the (B) reactive liquid compound is not particularly limited, but is preferably 0.5 to 20 mass%, more preferably 1.0 to 15 mass%, and even more preferably 1.5 to 10 mass%, relative to the total solid content (100 mass%) of the resin composition.
• Examples of the inorganic filler (C) include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, silicon carbide, etc.
• silica, alumina, mica, and talc are preferred, and silica and alumina are more preferred.
• the average particle size of the inorganic filler (C) is not particularly limited, but from the viewpoints of dispersibility and fine wiring property of the inorganic filler (C), it is preferably 0.01 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m, even more preferably 0.2 to 1 ⁇ m, and particularly preferably 0.3 to 0.8 ⁇ m.
• the average particle size of the inorganic filler (C) refers to the particle size at a point corresponding to 50% volume when a cumulative frequency distribution curve of particle sizes is calculated assuming the total volume of the particles to be 100%.
• the average particle size of the inorganic filler (C) can be measured, for example, by a particle size distribution measuring device using a laser diffraction scattering method.
• the shape of the (C) inorganic filler may be, for example, spherical or crushed, with spherical being preferred.
• the content of the inorganic filler (C) is not particularly limited, but is preferably 20 to 95 mass%, more preferably 40 to 90 mass%, and even more preferably 60 to 80 mass%, relative to the total solid content (100 mass%) of the resin composition.
• the content of the inorganic filler (C) is equal to or greater than the lower limit, the low thermal expansion, heat resistance, and flame retardancy tend to be improved.
• the content of the inorganic filler (C) is equal to or less than the upper limit, the moldability and conductor adhesion tend to be improved.
• the resin composition of the present embodiment preferably further contains (D) an elastomer having a molecular weight of more than 1,000 (hereinafter, may be referred to as “(D) elastomer”).
• the resin composition of the present embodiment tends to have better dielectric properties by containing the elastomer (D).
• the term "elastomer” used herein means a polymer having a glass transition temperature of 25°C or lower as measured by differential scanning calorimetry in accordance with JIS K 6240:2011.
• the elastomer (D) may be used alone or in combination of two or more kinds.
• the molecular weight of the elastomer (D) is more than 1,000, preferably 1,050 to 500,000, more preferably 1,100 to 350,000, and even more preferably 1,150 to 200,000.
• the molecular weight of the (D) elastomer is equal to or greater than the lower limit, the heat resistance of the resulting resin composition tends to be better maintained, while when the molecular weight of the (D) elastomer is equal to or less than the upper limit, the dielectric properties and conductor adhesion of the resulting resin composition tend to be better.
• conjugated diene polymer (D1)) means a polymer of a conjugated diene compound.
• conjugated diene polymer By containing the conjugated diene polymer (D1), the resin composition of the present embodiment tends to easily obtain better dielectric properties.
• the conjugated diene polymer (D1) may be used alone or in combination of two or more kinds.
• the conjugated diene compound examples include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, and 1,3-hexadiene.
• the conjugated diene polymer (D1) may be a polymer of one kind of conjugated diene compound, or a copolymer of two or more kinds of conjugated diene compounds.
• the conjugated diene polymer (D1) may also be a copolymer of one or more conjugated diene compounds and one or more monomers other than the conjugated diene compounds.
• the conjugated diene polymer (D1) is a copolymer
• the polymerization mode is not particularly limited, and it may be any of random polymerization, block polymerization, and graft polymerization.
• conjugated diene polymer (D1) a conjugated diene polymer having a plurality of vinyl groups in the side chain is preferred from the viewpoints of compatibility with other resins and dielectric properties.
• the number of vinyl groups that the conjugated diene polymer (D1) has in one molecule is not particularly limited, but from the viewpoints of compatibility with other resins and dielectric properties, it is preferably 3 or more, more preferably 5 or more, and even more preferably 10 or more.
• the upper limit of the number of vinyl groups that the conjugated diene polymer (D1) has in one molecule is not particularly limited, and may be 100 or less, 80 or less, or 60 or less.
• Examples of the conjugated diene polymer (D1) include polybutadiene having a 1,2-vinyl group, butadiene-styrene copolymer having a 1,2-vinyl group, polyisoprene having a 1,2-vinyl group, etc.
• polybutadiene having a 1,2-vinyl group and butadiene-styrene copolymer having a 1,2-vinyl group are preferred, and polybutadiene having a 1,2-vinyl group is more preferred.
• a polybutadiene homopolymer having a 1,2-vinyl group is preferred.
• the 1,2-vinyl group derived from butadiene contained in the conjugated diene polymer (D1) is a vinyl group contained in a structural unit derived from butadiene represented by the following formula (D1-1).
• the content of the structural unit having a 1,2-vinyl group with respect to all structural units derived from butadiene constituting the polybutadiene [hereinafter, may be referred to as the "vinyl group content"] is not particularly limited, but from the viewpoints of compatibility with other resins, dielectric properties and heat resistance, it is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 85 mol% or more.
• the upper limit of the vinyl group content there is no particular limit to the upper limit of the vinyl group content, and it may be 100 mol% or less, 95 mol% or less, or 90 mol% or less.
• the structural unit having a 1,2-vinyl group a structural unit derived from butadiene represented by the above formula (D1-1) is preferable.
• the polybutadiene having a 1,2-vinyl group is preferably a 1,2-polybutadiene homopolymer.
• the number average molecular weight of the conjugated diene polymer (D1) is not particularly limited, but from the viewpoints of compatibility with other resins, dielectric properties, and heat resistance, it is preferably 1,050 to 3,000, more preferably 1,100 to 2,000, and even more preferably 1,150 to 1,500.
• the modified conjugated diene polymer (D2) is a polymer obtained by modifying a conjugated diene polymer.
• the resin composition of the present embodiment tends to have good heat resistance and low thermal expansion properties, while also being more easily able to obtain excellent dielectric properties.
• the modified conjugated diene polymer (D2) may be used alone or in combination of two or more kinds.
• the modified conjugated diene polymer (D2) is preferably a modified conjugated diene polymer obtained by modifying (d1) a conjugated diene polymer having a vinyl group in the side chain [hereinafter, sometimes referred to as "conjugated diene polymer (d1)] with (d2) a maleimide resin having two or more N-substituted maleimide groups [hereinafter, sometimes referred to as "maleimide resin (d2)], from the viewpoints of compatibility with other resins, dielectric properties, and conductor adhesion.
• conjugated diene polymer (d1) conjugated diene polymer having a vinyl group in the side chain
• maleimide resin (d2) a maleimide resin having two or more N-substituted maleimide groups
• conjugated diene polymer (d1) for example, the conjugated diene polymer having a vinyl group in the side chain explained above as the conjugated diene polymer (D1) can be used, and the same applies to the preferred embodiments.
• the conjugated diene polymer (d1) may be used alone or in combination of two or more kinds.
• maleimide resin (d2) for example, a maleimide resin having two or more N-substituted maleimide groups explained as the maleimide resin (AX) above can be used, and the same applies to preferred embodiments.
• the maleimide resin (d2) may be used alone or in combination of two or more kinds.
• X d1 is a divalent group obtained by removing two N-substituted maleimide groups from the maleimide resin (d2), * d1 is a bond site to a carbon atom derived from a vinyl group that the conjugated diene polymer (d1) has in a side chain, and * d2 is a bond site to another atom.
• the modified conjugated diene polymer (D2) preferably has a substituent (x) and a vinyl group (y) in the side chain.
• the extent to which the substituent (x) is present in the modified conjugated diene polymer (D2) can be determined by the extent to which the vinyl group of the conjugated diene polymer (d1) has been modified by the maleimide resin (d2) [hereinafter, sometimes referred to as the "vinyl group modification rate"].
• the vinyl group modification rate is not particularly limited, but from the viewpoints of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance, it is preferably 20 to 70%, more preferably 30 to 60%, and even more preferably 35 to 50%.
• the vinyl group modification rate is a value determined by the method described in the examples.
• the vinyl group (y) is preferably a 1,2-vinyl group possessed by a structural unit derived from butadiene.
• the number average molecular weight of the modified conjugated diene polymer (D2) is not particularly limited, but from the viewpoints of compatibility with other resins, dielectric properties, low thermal expansion, and heat resistance, it is preferably 1,100 to 6,000, more preferably 1,300 to 4,000, and even more preferably 1,500 to 2,000.
• the modified conjugated diene polymer (D2) can be produced by reacting the conjugated diene polymer (d1) with a maleimide resin (d2).
• the method for reacting the conjugated diene polymer (d1) with the maleimide resin (d2) is not particularly limited.
• the conjugated diene polymer (d1), the maleimide resin (d2), a reaction catalyst and an organic solvent are charged into a reaction vessel, and reacted while heating, keeping warm, stirring, etc. as necessary to obtain a modified conjugated diene polymer (D2).
• the ratio (M m /M v ) of the number of moles (M m ) of N-substituted maleimide groups in the maleimide resin (d2) to the number of moles (M v ) of side chain vinyl groups in the conjugated diene polymer (d1) is not particularly limited, but is preferably 0.001 to 0.5, more preferably 0.005 to 0.1, and even more preferably 0.008 to 0.05, from the viewpoints of compatibility of the resulting modified conjugated diene polymer (D2) with other resins and suppression of gelation of the product during the reaction.
• the styrene-based elastomer (D3) is not particularly limited as long as it is an elastomer having a structural unit derived from a styrene-based compound.
• the resin composition of the present embodiment tends to have better dielectric properties by containing the styrene-based elastomer (D3).
• the styrene-based elastomer (D3) may be used alone or in combination of two or more kinds.
• styrene-based elastomer (D3) one having a structural unit derived from a styrene-based compound represented by the following general formula (D3-1) is preferred.
• R d1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
• R d2 is an alkyl group having 1 to 5 carbon atoms
• n d1 is an integer of 0 to 5.
• Examples of the alkyl group having 1 to 5 carbon atoms represented by R d1 and R d2 in the above general formula (D3-1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group.
• the alkyl group having 1 to 5 carbon atoms may be either linear or branched. Among these, an alkyl group having 1 to 3 carbon atoms is preferred, an alkyl group having 1 or 2 carbon atoms is more preferred, and a methyl group is even more preferred.
• n d1 is an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
• the styrene-based elastomer (D3) may contain structural units other than the structural units derived from the styrene-based compound.
• Examples of structural units other than the structural units derived from a styrene-based compound that may be contained in the styrene-based elastomer (D3) include a structural unit derived from butadiene, a structural unit derived from isoprene, a structural unit derived from maleic acid, and a structural unit derived from maleic anhydride.
• the butadiene-derived structural unit and the isoprene-derived structural unit may be hydrogenated. When hydrogenated, the butadiene-derived structural unit is a structural unit having a mixture of ethylene units and butylene units, and the isoprene-derived structural unit is a structural unit having a mixture of ethylene units and propylene units.
• Examples of the styrene-based elastomer (D3) include hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene-styrene block copolymers, and styrene-maleic anhydride copolymers.
• Examples of hydrogenated styrene-butadiene-styrene block copolymers include SEBS obtained by completely hydrogenating the carbon-carbon double bonds in the butadiene block, and SBBS obtained by partially hydrogenating the carbon-carbon double bonds at the 1,2-bond sites in the butadiene block.
• the completely hydrogenated SEBS usually means 90% or more, 95% or more, 99% or more, or 100% of the total carbon-carbon double bonds.
• the partial hydrogenation rate in SBBS is, for example, 60 to 85% of the total carbon-carbon double bonds.
• the hydrogenated styrene-isoprene-styrene block copolymer is obtained as SEPS by hydrogenating the polyisoprene portion.
• SEBS and SEPS are preferred, and SEBS is more preferred.
• the content of structural units derived from styrene-based compounds (hereinafter sometimes referred to as the "styrene content”) is not particularly limited, but is preferably 5 to 60% by mass, more preferably 7 to 40% by mass, and even more preferably 10 to 20% by mass.
• the number average molecular weight of the styrene-based elastomer (D3) is not particularly limited, but is preferably 10,000 to 500,000, more preferably 50,000 to 350,000, and even more preferably 100,000 to 200,000.
• Examples of the (D) elastomer other than the conjugated diene polymer (D1), modified conjugated diene polymer (D2), and styrene-based elastomer (D3) include polyolefin-based resins, polyphenylene ether-based resins, polyester-based resins, polyamide-based resins, polyacrylic-based resins, etc.
• the content of the elastomer (D) is not particularly limited, but is preferably 10 to 80 mass%, more preferably 30 to 70 mass%, and even more preferably 50 to 60 mass%, relative to the total amount (100 mass%) of the resin components in the resin composition of the present embodiment.
• the content of the elastomer (D) is equal to or greater than the lower limit, better dielectric properties tend to be obtained.
• the content of the elastomer (D) is equal to or less than the upper limit, better heat resistance tends to be obtained.
• the total content of one or more selected from the group consisting of conjugated diene polymer (D1), modified conjugated diene polymer (D2) and styrene-based elastomer (D3) is not particularly limited, but from the viewpoint of dielectric properties and conductor adhesion, it is preferably 60 to 100 mass%, more preferably 80 to 100 mass%, and even more preferably 90 to 100 mass% relative to the total amount (100 mass%) of the elastomer (D).
• the (D) elastomer preferably contains one or more selected from the group consisting of conjugated diene polymers (D1) and modified conjugated diene polymers (D2), and a styrene-based elastomer (D3).
• the (D) elastomer contains one or more selected from the group consisting of a conjugated diene polymer (D1) and a modified conjugated diene polymer (D2), and a styrene-based elastomer (D3)
• the ratio of the total content of the conjugated diene polymer (D1) and the modified conjugated diene polymer (D2) to the content of the styrene-based elastomer (D3), [[(D1)+(D2)]/(D3)] is not particularly limited, but is preferably 0.1 to 5, more preferably 0.2 to 1, and even more preferably 0.3 to 0.7, from the viewpoints of dielectric properties and compatibility.
• the resin composition of the present embodiment preferably further contains (E) a curing accelerator.
• E curing accelerator
• the curing accelerator (E) may be used alone or in combination of two or more kinds.
• the (E) curing accelerator contains a radical polymerization initiator.
• the radical polymerization initiator acts as a polymerization initiator for radical polymerization, and decomposes into a compound having an unpaired electron when exposed to energy such as light or heat.
• Examples of the radical polymerization initiator include organic peroxides, inorganic peroxides, and azo compounds described below, with organic peroxides being preferred.
• curing accelerator (E) examples include acid catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, pyridine, tributylamine, and dicyandiamide; imidazole compounds such as methylimidazole, phenylimidazole, and 1-cyanoethyl-2-phenylimidazole; isocyanate mask imidazole compounds such as an addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole; tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; dicumyl peroxide, 2,5-dimethyl-2,5-bis(2,4-dimethylphenyl)-2,5-diisocyanate; Examples of peroxides include organic peroxides such as (t-butylperoxy)hexyne-3, 2,5-dimethyl-2,
• imidazole compounds from the viewpoints of the curing acceleration effect and storage stability, imidazole compounds, isocyanate-masked imidazole compounds, organic peroxides, and carboxylates are preferred, and isocyanate-masked imidazole compounds and organic peroxides are more preferred.
• the content of the curing accelerator (E) is not particularly limited, but is preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 4 to 8 parts by mass relative to the total amount (100 parts by mass) of the thermosetting resin (A) and the reactive liquid compound (B).
• the content of the curing accelerator (E) is equal to or more than the lower limit, a sufficient curing acceleration effect tends to be easily obtained, and when the content of the curing accelerator (E) is equal to or less than the upper limit, storage stability tends to be improved.
• the content of the radical polymerization initiator is not particularly limited, but is preferably 0.05 to 7 parts by mass, more preferably 0.5 to 5 parts by mass, and even more preferably 2 to 4 parts by mass relative to the total amount (100 parts by mass) of the thermosetting resin (A) and the reactive liquid compound (B).
• the content of the radical polymerization initiator is equal to or more than the lower limit, a sufficient curing acceleration effect is easily obtained, and the generation of volatile components tends to be more easily suppressed.
• the content of the radical polymerization initiator is equal to or less than the upper limit, the storage stability tends to be better.
• the resin composition of the present embodiment may further contain, as necessary, one or more optional components selected from the group consisting of resin materials other than the above-mentioned components, flame retardants, antioxidants, heat stabilizers, antistatic agents, UV absorbers, pigments, colorants, lubricants, organic solvents, and other additives.
• the above-mentioned optional components may each be used alone or in combination of two or more.
• the content of the above-mentioned optional components in the resin composition of the present embodiment is not particularly limited, and may be used as necessary within a range that does not impair the effects of the present embodiment.
• the resin composition of the present embodiment may not contain the above-mentioned optional components depending on the desired performance.
• the thickness of the resin film is not particularly limited, but from the viewpoint of effectively expressing the characteristic of the supported resin film of this embodiment, namely, excellent flexibility, the thickness is preferably 10 ⁇ m or more, more preferably 80 ⁇ m or more, even more preferably 100 ⁇ m or more, still more preferably 130 ⁇ m or more, and particularly preferably 150 ⁇ m or more. Furthermore, the thickness of the resin film in the supported resin film of the present embodiment is not particularly limited, but is preferably 1,000 ⁇ m or less, more preferably 700 ⁇ m or less, and even more preferably 500 ⁇ m or less.
• the content of the organic solvent in the resin film is preferably 2 mass % or less, more preferably 1 mass % or less, and even more preferably 0.5 mass % or less, relative to the total amount (100 mass %) of the resin film, and may be 0 mass %.
• the content of the organic solvent in the resin film is within the above range, the amount of the organic solvent that volatilizes during heat curing tends to be sufficiently suppressed.
• the resin film has a mass reduction rate when heated and dried at 170° C. for 30 minutes in an air atmosphere (hereinafter, may be referred to as "170° C. mass reduction rate").
• the mass reduction rate is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1.0% by mass or less, and may be 0% by mass.
• the mass loss rate at 170° C. can be measured by the method described in the examples.
• the dielectric constant (Dk) at 10 GHz of the cured resin film may be less than 3.0, less than 2.9, or less than 2.8.
• the dielectric loss tangent (Df) at 10 GHz of the cured resin film may be less than 0.0030, less than 0.0025, or less than 0.0015.
• the resin film is preferably a resin film having a thickness of 150 ⁇ m or more, and a cured product of the resin film preferably has a relative dielectric constant (Dk) of less than 2.8 and a dielectric loss tangent (Df) of less than 0.0030 at 10 GHz.
• the relative dielectric constant (Dk) and the dielectric loss tangent (Df) are values based on the cavity resonator perturbation method, and more specifically, are values measured by the method described in the examples.
• the support of the supported resin film of the present embodiment has an arithmetic mean roughness Ra of the surface on the resin film side of 0.06 ⁇ m or more, whereby the cured resin film has excellent plating peel strength on the surface in contact with the support.
• the arithmetic mean roughness Ra of the surface of the support facing the resin film is preferably 0.07 ⁇ m or more, more preferably 0.15 ⁇ m or more, and even more preferably 0.2 ⁇ m or more.
• the ten-point average roughness Rz of the surface of the support on the resin film side of the support of the support-attached resin film of this embodiment is not particularly limited, but is preferably 0.7 to 10.0 ⁇ m, more preferably 1.0 to 7.0 ⁇ m, and even more preferably 2.0 to 5.0 ⁇ m.
• the ten-point average roughness Rz is equal to or greater than the lower limit, the cured resin film tends to have excellent plating peel strength on the surface in contact with the support, and when the ten-point average roughness Rz is equal to or less than the upper limit, the cured resin film tends to have improved fine wiring properties.
• the ten-point average roughness Rz of the support can be measured by the method described in the examples.
• Examples of the support include plastic films, metal foils, release papers, etc. Among these, one or more types selected from the group consisting of plastic films and metal foils are preferred.
• plastic films include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride; polyester films such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate; polycarbonate films, polyimide films, etc.
• PET polyethylene terephthalate
• polyethylene terephthalate films are preferred from the viewpoints of economy and ease of handling.
• Examples of the metal foil include copper foil and aluminum foil. When copper foil is used as the support, the copper foil itself can be used as a conductor layer to form a circuit.
• rolled copper foil, electrolytic copper foil, etc. can be used as the copper foil.
• a copper foil with a carrier may be used from the viewpoint of improving workability.
• the support may be subjected to a surface treatment such as a matte treatment or a corona treatment in order to adjust the arithmetic mean roughness Ra of the surface to the above range.
• the support may also be subjected to a release treatment using a silicone resin-based release agent, an alkyd resin-based release agent, a fluororesin-based release agent, or the like.
• the thickness of the support is not particularly limited, but from the viewpoints of ease of handling and economy, it is preferably 10 to 150 ⁇ m, more preferably 20 to 100 ⁇ m, and even more preferably 30 to 70 ⁇ m.
• the resin film with a support of this embodiment is suitable, for example, as a resin film with a support for forming an insulating layer in a printed wiring board such as a multilayer printed wiring board, or as a resin film with a support for sealing semiconductors in a semiconductor package.
• a coating device for coating the resin varnish for example, a coating device known to those skilled in the art, such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, a die coater, etc. These coating devices may be appropriately selected depending on the film thickness to be formed.
• the drying conditions after the resin varnish is applied may be appropriately determined depending on the content, boiling point, etc. of the organic solvent, and are not particularly limited.
• a conductor layer is formed by plating on the roughened surface of the insulating layer.
• the plating method include electroless plating and electrolytic plating.
• the metal for plating include copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and alloys containing at least one of these metal elements. Among these, copper and nickel are preferred, and copper is more preferred.
• Silica Spherical silica treated with aminosilane coupling agent, average particle size 0.5 ⁇ m
• Alumina Alumina 1 (average particle size 18 ⁇ m, polyhedral spherical), Alumina 2 (average particle size 3 ⁇ m, polyhedral spherical), Alumina 3 (average particle size 0.4 ⁇ m, polyhedral spherical) mixed in a mass ratio of 66:24:10

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• 2023
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