Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
• • 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
  • 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
  • C08L51/04—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 grafted on to rubbers
• • 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
• • 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
  • H10W74/40—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

Definitions

• the present invention relates to a resin composition containing an epoxy resin. Furthermore, it relates to a cured product, a sheet-like laminated material, a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition.
• the insulating layer is generally formed by curing a resin composition.
• further improvements in dielectric properties such as the dielectric constant of insulating layers and further improvements in copper adhesion have been demanded.
• Df dielectric loss tangent
• Patent Document 1 the dielectric loss tangent of the insulating layer has been lowered by using an epoxy resin composition containing an active ester compound instead of a general phenol-based curing agent as the resin composition for forming the insulating layer. It is known that it can be suppressed (Patent Document 1).
• Patent Document 2 A characteristic epoxy resin has been known so far (Patent Document 2).
• An object of the present invention is to provide a resin composition capable of suppressing the dielectric loss tangent to a lower level, suppressing the occurrence of cracks after desmear treatment, and obtaining a cured product having excellent copper plating peel strength. That's what it is.
• an epoxy resin composition containing an active ester compound further includes (A-1) represented by formula (1) described below.
• the epoxy equivalent weight applied is 1000 g/eq. ⁇ 5000g/eq. and (A-2) an epoxy equivalent of 200 g/eq.
• a resin composition containing (A) an epoxy resin and (B) an active ester compound, (A) component is (A-1) Formula (1):
• Each R 1 is independently a hydrogen atom, an optionally substituted alkyl-carbonyl group, an optionally substituted alkenyl-carbonyl group, or an optionally substituted an aryl-carbonyl group, and at least one of R 1 is an optionally substituted alkyl-carbonyl group, an optionally substituted alkenyl-carbonyl group, and a substituted a group selected from an aryl-carbonyl group which may be
• Each Ar is independently represented by formula (X):
• R 2 and R 3 each independently represent a substituent; X represents a single bond or an organic group; a and b each independently represent 0, 1, 2, 3, or 4; * indicates the binding site. ) showing a group represented by; n is an integer of 1 or more and indicates the number of repeating units.
• the epoxy equivalent represented by is 1000 g/eq. ⁇ 5000g/eq. and (A-2) an epoxy equivalent of 200 g/eq.
• Ar is each independently represented by formula (X-1):
• R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represent a hydrogen atom or an alkyl group, and at least one of them is an alkyl is a group;
• X 1 represents a single bond, -C(R x ) 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH- or -NHCO-;
• Each R x independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. or two R x on the same carbon atom are joined together to form an optionally substituted non-aromatic ring; * indicates the binding site.
• X 2 represents a single bond, -C(R x ) 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH- or -NHCO-;
• Each R x independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. or two R x on the same carbon atom are joined together to form an optionally substituted non-aromatic ring; * indicates the binding site.
• the dielectric loss tangent can be suppressed to a lower level, the occurrence of cracks after desmear treatment can be suppressed, and a cured product with excellent copper plating peel strength can be obtained.
• the resin composition of the present invention comprises (A) an epoxy resin and (B) an active ester compound, wherein component (A) has (A-1) an epoxy equivalent represented by formula (1) described below. 1000 g/eq. ⁇ 5000g/eq. (hereinafter sometimes referred to as “specific epoxy resin”), and (A-2) an epoxy equivalent of 200 g / eq.
• specific epoxy resin an epoxy equivalent represented by formula (1) described below. 1000 g/eq. ⁇ 5000g/eq.
• the resin composition of the present invention may further contain optional components in addition to (A) the epoxy resin and (B) the active ester compound.
• Optional components include, for example, (B') other curing agents, (C) inorganic fillers, (D) organic fillers, (E) curing accelerators, (F) other additives, and (G) An organic solvent is mentioned.
• B' other curing agents
• C inorganic fillers
• D organic fillers
• E curing accelerators
• F other additives
• G An organic solvent is mentioned.
• the resin composition of the present invention contains (A) an epoxy resin.
• (A) Epoxy resin is a curable resin having an epoxy group.
• (A) epoxy resin has (A-1) formula (1):
• Each R 1 is independently a hydrogen atom, an optionally substituted alkyl-carbonyl group, an optionally substituted alkenyl-carbonyl group, or an optionally substituted an aryl-carbonyl group, and at least one of R 1 is an optionally substituted alkyl-carbonyl group, an optionally substituted alkenyl-carbonyl group, and a substituted a group selected from an aryl-carbonyl group which may be
• Each Ar is independently represented by formula (X):
• R 2 and R 3 each independently represent a substituent; X represents a single bond or an organic group; a and b each independently represent 0, 1, 2, 3, or 4; * indicates the binding site. ) showing a group represented by; n is an integer of 1 or more and indicates the number of repeating units.
• the epoxy equivalent represented by is 1000 g/eq. ⁇ 5000g/eq. of epoxy resin (specific epoxy resin).
• Each R 1 is independently a hydrogen atom, an optionally substituted alkyl-carbonyl group, an optionally substituted alkenyl-carbonyl group, or an optionally substituted an aryl-carbonyl group, and at least one of R 1 is an optionally substituted alkyl-carbonyl group, an optionally substituted alkenyl-carbonyl group, and a substituted It is a group selected from aryl-carbonyl groups which may be substituted.
• the substituents are not particularly limited, but examples include halogen atoms, alkyl groups, alkenyl groups, aryl groups, aryl-alkyl groups (alkyl groups substituted with aryl groups), alkyl- Aryl group (aryl group substituted with an alkyl group), halogen-substituted alkyl group (alkyl group substituted with a halogen atom), halogen-substituted alkenyl group (alkenyl group substituted with a halogen atom), halogen-substituted aryl group (halogen atom aryl group substituted with), alkyl-oxy group, alkenyl-oxy group, aryl-oxy group, alkyl-carbonyl group, alkenyl-carbonyl group, aryl-carbonyl group, alkyl-oxy-carbonyl group, alkenyl-oxy-carbonyl groups, aryl-oxy-carbonyl groups, alkyl-
• a halogen atom means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and among them, a fluorine atom is preferable.
• Alkyl (group) means a linear, branched and/or cyclic monovalent saturated aliphatic hydrocarbon group. Unless otherwise specified, the alkyl (group) is preferably an alkyl (group) having 1 to 14 carbon atoms, more preferably an alkyl (group) having 1 to 10 carbon atoms, an alkyl (group) having 1 to 6 carbon atoms ( group) is more preferred.
• Alkyl (group) includes, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl decyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,2,4-trimethylcyclohexyl group, cyclopentylmethyl group, cyclohexylmethyl group and the like.
• Alkenyl (group) means a linear, branched and/or cyclic monovalent unsaturated aliphatic hydrocarbon group having at least one carbon-carbon double bond.
• Alkenyl (group) is preferably an alkenyl (group) having 2 to 14 carbon atoms, more preferably an alkenyl (group) having 2 to 10 carbon atoms, and an alkenyl group having 2 to 6 carbon atoms, unless otherwise specified. is more preferred.
• alkenyl (group) examples include vinyl group, propenyl group (allyl group, 1-propenyl group, isopropenyl group), butenyl group (1-butenyl group, crotyl group, methallyl group, isocrotyl group, etc.), pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, cyclohexenyl group and the like.
• Aryl (group) means a monovalent aromatic hydrocarbon group from which one hydrogen atom is removed from an aromatic carbocyclic ring.
• the aryl (group) is preferably an aryl (group) having 6 to 14 carbon atoms, particularly preferably an aryl (group) having 6 to 10 carbon atoms, unless otherwise specified.
• Aryl (group) includes, for example, phenyl group, 1-naphthyl group, 2-naphthyl group and the like.
• Each R 1 is independently a hydrogen atom, an optionally substituted alkyl-carbonyl group, an optionally substituted alkenyl-carbonyl group, or an optionally substituted represents an aryl-carbonyl group, and in one embodiment, is preferably a hydrogen atom, an alkyl-carbonyl group, an alkenyl-carbonyl group, or an aryl-carbonyl group, more preferably a hydrogen atom or an alkyl-carbonyl group , more preferably a hydrogen atom, an acetyl group, a propanoyl group, a butanoyl group or a 2-methylpropanoyl group, particularly preferably a hydrogen atom or an acetyl group.
• At least one of R 1 is other than a hydrogen atom (that is, an optionally substituted alkyl-carbonyl group, an optionally substituted alkenyl-carbonyl group, and a substituted a group selected from aryl-carbonyl groups which may be present).
• R 1 is preferably 5 mol% or more, more preferably 20 mol% or more, still more preferably 40 mol% or more, particularly preferably 60 mol% or more or 80 mol%
• the above are atoms other than hydrogen atoms.
• R 2 and R 3 each independently represent a substituent, and in one embodiment, preferably alkyl group, alkenyl group, aryl group, aryl-alkyl group, alkyl-aryl group, alkyl-oxy group, alkenyl -oxy group or aryl-oxy group, more preferably an alkyl group, an alkenyl group or an aryl group, still more preferably an alkyl group, and particularly preferably a methyl group.
• X represents a single bond or an organic group, in one embodiment preferably a single bond, —C(R x ) 2 —, —O—, —CO—, —S—, —SO—, —SO 2 -, -CONH- or -NHCO-, more preferably a single bond, -C(R x ) 2 -, -O-, -CO-, -S- or -SO 2 -, A single bond, —C(R x ) 2 —, or —O— is more preferred, and a single bond is particularly preferred.
• the organic group is not particularly limited, but in one embodiment, for example, one or more selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms (eg, 1 to 100, preferably 1 to 50, particularly preferably 1 to 20) skeletal atoms, which may contain a linear structure, a branched chain structure and/or a cyclic structure, and which does not contain an aromatic ring. or a group containing an aromatic ring.
• Each R x independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. or two R x on the same carbon atom are joined together to form an optionally substituted non-aromatic ring.
• each R x is independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, an alkyl-aryl group, a halogen-substituted alkyl group, a halogen-substituted alkenyl group, or a halogen-substituted aryl group, or two R x on the same carbon atom bonded together to form a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, an alkyl-aryl group, and an oxo group to form a non-aromatic ring optionally substituted with a group.
• each R x is independently a hydrogen atom, an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group, or two R x on the same carbon atom together come together to form a non-aromatic carbocycle. More preferably, each R x is independently a hydrogen atom, an alkyl group, or a halogen-substituted alkyl group.
• a non-aromatic ring means a ring other than an aromatic ring having aromaticity throughout the ring.
• An aromatic ring having aromaticity over the entire ring means a ring having 4p+2 (p is a natural number) electrons contained in the ⁇ electron system on the ring and conforming to Hückel's rule.
• a non-aromatic ring is a non-aromatic carbocyclic ring having only carbon atoms as ring-constituting atoms, or a non-aromatic heterocyclic ring having heteroatoms such as oxygen, nitrogen and sulfur atoms in addition to carbon atoms as ring-constituting atoms.
• the non-aromatic ring may be a non-aromatic saturated ring consisting only of a single bond, or a non-aromatic unsaturated ring having at least one of a double bond and a triple bond.
• the non-aromatic ring may be a monocyclic non-aromatic ring, or may be a polycyclic non-aromatic ring such as a bicyclic, tricyclic, tetracyclic, or pentacyclic ring system.
• an aromatic ring (benzene ring, naphthalene ring) may be condensed.
• the non-aromatic ring is preferably a non-aromatic ring having 3 to 21 carbon atoms, more preferably a non-aromatic ring having 4 to 17 carbon atoms, and even more preferably a non-aromatic ring having 5 to 14 carbon atoms.
• a and b each independently represent 0, 1, 2, 3, or 4, and in one embodiment, preferably 0, 1, 2, or 3, more preferably 0, 1, or 2, and particularly preferably 0 or 1.
• n is an integer of 1 or more and indicates the number of repeating units.
• the average value of n is not particularly limited, but is preferably 1 or more, more preferably 5 or more, still more preferably 8 or more, and particularly preferably 10 or more, from the viewpoint of handleability of the resin composition,
• the upper limit is preferably 500 or less, more preferably 300 or less, still more preferably 200 or less, and particularly preferably 100 or less.
• each Ar preferably independently represents formula (X-1):
• R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represent a hydrogen atom or an alkyl group, and at least one of them is an alkyl is a group;
• X 1 represents a single bond, -C(R x ) 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH- or -NHCO-;
• Each R x independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. or two R x on the same carbon atom are joined together to form an optionally substituted non-aromatic ring; * indicates the binding site.
• X 2 represents a single bond, -C(R x ) 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH- or -NHCO-;
• Each R x independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. or two R x on the same carbon atom are joined together to form an optionally substituted non-aromatic ring; * indicates the binding site.
• Ar which is a group represented by formula (X-1) and Ar which is a group represented by formula (X-2).
• R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represent a hydrogen atom or an alkyl group, and at least one of them is an alkyl is the base.
• R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 are each independently a hydrogen atom or an alkyl group
• R At least one of 11 , R 12 , R 13 and R 14 and at least one of R 15 , R 16 , R 17 and R 18 are each independently an alkyl group.
• R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently a hydrogen atom or an alkyl group, and R 11 and R 12 and at least one of R 15 and R 16 are each independently an alkyl group. More preferably, R 11 , R 12 , R 15 and R 16 are each independently an alkyl group, and R 13 , R 14 , R 17 and R 18 are each independently a hydrogen atom , or an alkyl group.
• R 11 , R 12 , R 15 and R 16 are each independently methyl, ethyl, propyl or isopropyl
• R 13 , R 14 , R 17 and R 18 are each independently a hydrogen atom, a methyl group, an ethyl group, a propyl group, or an isopropyl group.
• X 1 represents a single bond, -C(R x ) 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH- or -NHCO-;
• the form is preferably a single bond, -C(R x ) 2 -, -O-, -CO-, -S-, or -SO 2 -, more preferably a single bond, -C(R x ) 2 — or —O—, particularly preferably a single bond.
• X 2 represents a single bond, -C(R x ) 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH- or -NHCO-;
• the form is preferably a single bond, -C(R x ) 2 -, -O-, -CO-, -S-, or -SO 2 -, more preferably a single bond, -C(R x ) 2 — or —O—, particularly preferably a single bond.
• the group represented by formula (X-1) is particularly preferably represented by formulas (X-1-1) to (X-1-8):
• the group represented by formula (X-2) is particularly preferably represented by formula (X-2-1):
• Ar includes at least one Ar group represented by formula (X-1) and at least one Ar group represented by formula (X-2).
• the proportion of Ar which is the group represented by formula (X-1) in Ar is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more, especially Preferably, it is 20 mol % or more.
• the proportion of Ar which is the group represented by formula (X-2) in Ar is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more, especially Preferably, it is 20 mol % or more.
• units in which Ar is a group represented by formula (X-1) and units in which Ar is a group represented by formula (X-2) are arranged alternately. They may be arranged in blocks, or randomly, but in one embodiment, they are preferably staggered.
• Epoxy equivalent weight is the mass of resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.
• the weight average molecular weight (Mw) of the specific epoxy resin is not particularly limited. It is preferably 40,000 or less, and its lower limit is preferably 1,000 or more, more preferably 2,500 or more, and even more preferably 3,000 or more.
• the weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.
• the number average molecular weight (Mn) of the specific epoxy resin is not particularly limited. It is preferably 15,000 or less, and its lower limit is preferably 1,000 or more, more preferably 1,500 or more, and even more preferably 2,000 or more.
• the number average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).
• the polydispersity (Mw/Mn) of the specific epoxy resin is not particularly limited, but in one embodiment, it is preferably in the range of 1.1 to 10.0. A range of 5 to 5.0 is more preferred, and a range of 2.0 to 3.0 is particularly preferred.
• the specific epoxy resin is not particularly limited, but in one embodiment, for example, one or more bifunctional epoxy resins corresponding to Ar (biphenol diglycidyl ether and/or glycidyl ether) and one or more diester compounds corresponding to Ar (biphenol ester and/or bisphenol ester), if necessary, in the presence of a catalyst.
• a specific method for example, the method described in JP-A-2016-89165 or a method based thereon can be used.
• the content of the (A-1) specific epoxy resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 20% by mass or less, or more.
• the content is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1.5% by mass or less.
• the lower limit of the content of the specific epoxy resin (A-1) in the resin composition is not particularly limited, but from the viewpoint of obtaining the desired effects of the present invention more remarkably, the non-volatile component in the resin composition is 100% by mass, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, particularly preferably is 0.8% by mass or more.
• the content of the (A-1) specific epoxy resin in the (A) epoxy resin is not particularly limited, but is preferably 50% when the (A) epoxy resin in the resin composition is 100% by mass. % by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less.
• the lower limit of the content of (A-1) specific epoxy resin in (A) epoxy resin is not particularly limited, but from the viewpoint of obtaining the desired effect of the present invention more remarkably, (A) When the epoxy resin is 100% by mass, preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, even more preferably 5% by mass or more, particularly preferably It is 8% by mass or more.
• (A-2) epoxy equivalent is 200 g/eq.
• the following epoxy resins preferably contain epoxy resins having two or more epoxy groups in one molecule.
• the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably It is 70% by mass or more.
• epoxy resins include, but are not limited to, naphthalene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, trisphenol type epoxy resin, Glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, glycyrrol type epoxy resin, dicyclopentadiene type epoxy resin, cyclohexane type epoxy resin, bixylenol type epoxy resin, anthracene type epoxy resin and the like.
• epoxy resin (A-2) epoxy equivalent of 200 g/eq.
• epoxy resins include "HP4032D” (epoxy equivalent: 136 to 148 g/eq.) and “HP4032SS” (epoxy equivalent: 144 g/eq.) (naphthalene-type epoxy resin) manufactured by DIC; "828US” (epoxy equivalent weight 184-194g/eq.), “828EL” (epoxy equivalent weight 184-194g/eq.), “jER828EL” (epoxy equivalent weight 184-194g/eq.), "825" (epoxy equivalent weight 170 ⁇ 180 g / eq.) (bisphenol A type epoxy resin); Mitsubishi Chemical "jER807” (epoxy equivalent 160 to 175 g / eq.), “1750” (epoxy equivalent 156 to 163 g / eq.) (bisphenol F type epoxy resin); "jER152” manufactured by Mitsubishi Chemical Corporation (epoxy equivalent 176
• the epoxy equivalent of the following epoxy resins is preferably 190 g/eq. Below, more preferably 180 g/eq. or less, and the lower limit thereof is preferably 80 g/eq. above, more preferably 100 g/eq. above, more preferably 120 g/eq. above, particularly preferably 130 g/eq. It can be more than Epoxy equivalent weight is the mass of resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.
• the weight average molecular weight (Mw) of the following epoxy resins is preferably 100 to 5,000, more preferably 200 to 3,000, still more preferably 250 to 1,500.
• the weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.
• the content of the following epoxy resin is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably is 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less.
• the lower limit of the content of the following epoxy resin is not particularly limited, but from the viewpoint of obtaining the desired effect of the present invention more remarkably, when the nonvolatile component in the resin composition is 100% by mass, it is preferable is 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, even more preferably 3% by mass or more, and particularly preferably 5% by mass or more.
• the content of the following epoxy resin is not particularly limited, but when the (A) epoxy resin in the resin composition is 100% by mass, it is preferably 98% by mass or less, more preferably 95% by mass or less. , and particularly preferably 92% by mass or less.
• the lower limit of the content of the following epoxy resin is not particularly limited, but from the viewpoint of obtaining the desired effect of the present invention more remarkably, the epoxy resin (A) in the resin composition was set to 100% by mass. is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 60% by mass or more.
• the mass ratio ((A-1) component/(A-2) component) of the (A-1) specific epoxy resin to the following epoxy resin is not particularly limited, but is preferably 0.005 or more, more It is preferably 0.01 or more, particularly preferably 0.05 or more.
• the upper limit of the mass ratio ((A-1) component/(A-2) component) of the specific epoxy resin (A-1) to the following epoxy resin is not particularly limited, but is preferably 5 or less, more It is preferably 1 or less, particularly preferably 0.5 or less.
• the epoxy resin may further contain (A-3) other epoxy resins that do not correspond to the components (A-1) and (A-2) as optional components. good.
• epoxy resins preferably include epoxy resins having two or more epoxy groups in one molecule.
• the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass, relative to 100% by mass of the non-volatile components of the other epoxy resin. above, and particularly preferably at least 70% by mass.
• epoxy resins include, but are not limited to, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, naphthylene ether type epoxy resin, naphthol novolac type epoxy resin, biphenyl type epoxy resin. resins, naphthalene-type epoxy resins, naphthol-type epoxy resins, phenol aralkyl-type epoxy resins, fluorene-type epoxy resins, epoxy resins having a butadiene structure, ester-type epoxy resins, and the like.
• epoxy resins include "N-690” (epoxy equivalent: 209 to 219 g/eq.) (cresol novolac type epoxy resin) manufactured by DIC; "N-695" manufactured by DIC. ” (epoxy equivalent weight 209-219 g / eq.) (cresol novolak type epoxy resin); / eq.), "HP-7200H” (epoxy equivalent weight 272-284 g/eq.), “HP-7200L” (epoxy equivalent weight 242-252 g/eq.) (dicyclopentadiene type epoxy resin); EXA-7311" (epoxy equivalent 277 g / eq.) (naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd.
• NC7000L (epoxy equivalent 230 g / eq.) (naphthol novolac type epoxy resin); Nippon Kayaku Co., Ltd.
• NC3000H (epoxy equivalent weight 291g/eq.), "NC3000” (epoxy equivalent weight 280g/eq.), “NC3000L” (epoxy equivalent weight 270g/eq.), “NC3100” (epoxy equivalent weight 258g/eq.) ( biphenyl-type epoxy resin);
• ESN475V (epoxy equivalent: 330 g/eq.) (naphthalene-type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "ESN485" (epoxy equivalent: 270 g/eq.) manufactured by Nippon Steel Chemical &Materials; ) (naphthol-type epoxy resin); Mitsubishi Chemical Co., Ltd.
• YX7700 260 to 285 g / eq.
• PG-100 epoxy equivalent 260 g / eq.
• CG-500 epoxy equivalent 310 g / eq.
• JP-200 manufactured by Nippon Soda Co., Ltd.
• Epoxy equivalent weight is the mass of resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.
• the weight average molecular weight (Mw) of other epoxy resins is preferably 100 to 50,000, more preferably 200 to 30,000, still more preferably 300 to 10,000.
• the weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.
• the content of (A-3) other epoxy resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably less than 50% by mass, It is more preferably 30% by mass or less, still more preferably 20% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less, and the lower limit thereof is, for example, 0% by mass or more and 0.1% by mass. or more, 1% by mass or more, and the like.
• the content of (A-3) other epoxy resin in (A) epoxy resin is not particularly limited, but when (A) epoxy resin in the resin composition is 100% by mass, it is preferably 80% by mass or less, more preferably 50% by mass or less, particularly preferably 30% by mass or less, and the lower limits thereof are, for example, 0% by mass or more, 0.1% by mass or more, 1% by mass or more, 10% by mass or more, etc. can be
• the content of (A) the epoxy resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 60% by mass or less, more preferably 40% by mass. % by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less.
• the lower limit of the content of (A) the epoxy resin in the resin composition is not particularly limited, but from the viewpoint of obtaining the desired effect of the present invention more remarkably, the non-volatile component in the resin composition is 100 mass. %, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, even more preferably 5% by mass or more, and particularly preferably 10% by mass or more. .
• the resin composition of the present invention contains (B) an active ester compound.
• the active ester compound may be used singly or in combination of two or more at any ratio.
• the active ester compound may function as an epoxy resin curing agent that reacts with (A) the epoxy resin to cure it.
• the active ester compound generally has two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. is preferably used.
• the active ester compound is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound.
• an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred.
• carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
• phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol no
• the (B) active ester compound includes a dicyclopentadiene-type active ester compound, a naphthalene-type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolak, and a benzoylated product of phenol novolak.
• Active ester compounds are preferred, among which at least one selected from dicyclopentadiene-type active ester compounds and naphthalene-type active ester compounds is more preferred, and dicyclopentadiene-type active ester compounds are even more preferred.
• the dicyclopentadiene-type active ester compound an active ester compound containing a dicyclopentadiene-type diphenol structure is preferable.
• active ester compounds include "EXB9451”, “EXB9460”, “EXB9460S”, “EXB-8000L” and “EXB-8000L-65M” as active ester compounds containing a dicyclopentadiene type diphenol structure.
• the active ester group equivalent of the active ester compound is preferably 50 g/eq. ⁇ 500 g/eq. , more preferably 50 g/eq. ⁇ 400 g/eq. , more preferably 100 g/eq. ⁇ 300 g/eq. is.
• the active ester group equivalent is the mass of active ester compound per equivalent of active ester group.
• the content of (B) the active ester compound in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably, when the non-volatile component in the resin composition is 100% by mass. is 5% by mass or more, particularly preferably 10% by mass or more.
• the upper limit of the content of (B) the active ester compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less, or more. It is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less.
• the mass ratio of (B) active ester compound to (A) epoxy resin in the resin composition ((B) component/(A) component) is preferably 0.1 or more, more preferably 0.5 or more, and particularly preferably is greater than or equal to 1.0.
• the upper limit of the mass ratio ((B) component/(A) component) of the active ester compound (B) to the epoxy resin (A) in the resin composition is preferably 5.0 or less, more preferably 3.0 or less. Especially preferably, it is 2.0 or less.
• the resin composition of the present invention may further contain (B′) other curing agents than the (B) component as optional components.
• B′ other curing agents may be used singly or in any combination of two or more.
• B') Other curing agents can function as epoxy resin curing agents that react with (A) epoxy resins to cure them, similarly to (B) active ester compounds.
• (B') Other curing agents include, but are not limited to, phenol-based curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, benzoxazine-based curing agents, Examples include cyanate ester-based curing agents and thiol-based curing agents.
• the resin composition of the present invention preferably contains a curing agent selected from phenolic curing agents and carbodiimide curing agents, and particularly preferably contains a phenolic curing agent.
• a phenolic curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance.
• a nitrogen-containing phenolic curing agent is preferred, and a triazine skeleton-containing phenolic curing agent is more preferred.
• a triazine skeleton-containing phenol novolak resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion.
• Specific examples of the phenol-based curing agent include, for example, Meiwa Chemical Co., Ltd. "MEH-7700", “MEH-7810", “MEH-7851”, Nippon Kayaku Co., Ltd.
• carbodiimide-based curing agents include curing agents having one or more, preferably two or more carbodiimide structures in one molecule.
• biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylene biscyclohexylenecarbodiimide), poly(isophoronecarbodiimide) and other aliphatic polycarbodiimides; poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylene carbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide),
• carbodiimide curing agents examples include “Carbodilite V-02B”, “Carbodilite V-03”, “Carbodilite V-04K”, “Carbodilite V-07” and “Carbodilite V-09” manufactured by Nisshinbo Chemical Co., Ltd. "Stabaxol P”, “Stabaxol P400”, and “Hykasil 510” manufactured by Rhein Chemie.
• the acid anhydride curing agent includes curing agents having one or more acid anhydride groups in one molecule, preferably curing agents having two or more acid anhydride groups in one molecule.
• Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid.
• acid anhydride-based curing agents include “HNA-100”, “MH-700”, “MTA-15”, “DDSA” and “OSA” manufactured by Shin Nippon Rika Co., Ltd., and " YH-306", “YH-307”, Hitachi Chemical "HN-2200”, “HN-5500”, Clay Valley “EF-30”, “EF-40” “EF-60”, “EF -80” and the like.
• Amine-based curing agents include curing agents having one or more, preferably two or more amino groups in one molecule. Examples include aliphatic amines, polyether amines, alicyclic amines, Aromatic amines and the like can be mentioned, and among them, aromatic amines are preferable from the viewpoint of achieving the desired effects of the present invention. Amine-based curing agents are preferably primary amines or secondary amines, more preferably primary amines.
• amine curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone.
• amine-based curing agents may be used, for example, "SEIKACURE-S” manufactured by Seika, "KAYABOND C-200S”, “KAYABOND C-100” and “Kayahard AA” manufactured by Nippon Kayaku. , “Kayahard AB”, “Kayahard AS”, “Epicure W” manufactured by Mitsubishi Chemical Corporation, and the like.
• benzoxazine-based curing agents include “JBZ-OP100D” and “ODA-BOZ” manufactured by JFE Chemical Co., Ltd.; “HFB2006M” manufactured by Showa Polymer Co., Ltd.; Examples include “Fa”.
• cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate (oligo(3-methylene-1,5-phenylenecyanate)), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4, 4′-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5- Difunctional cyanate resins such as dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, Polyfunctional cyanate resins derived from phenol novolak, cresol novolak, etc., and prepolymers obtained by partially triazine-forming these cyan
• cyanate ester curing agents include “PT30” and “PT60” (both phenol novolac type polyfunctional cyanate ester resins), “BA230” and “BA230S75” (part of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. or a prepolymer that is entirely triazined to form a trimer), and the like.
• thiol-based curing agents examples include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), tris (3-mercaptopropyl) isocyanurate, and the like.
• the reactive group equivalent of other curing agents is preferably 50 g/eq. ⁇ 3000g/eq. , more preferably 100 g/eq. ⁇ 1000g/eq. , more preferably 100 g/eq. ⁇ 500 g/eq. , particularly preferably 100 g/eq. ⁇ 300 g/eq. is.
• Reactive group equivalent weight is the mass of curing agent per equivalent of reactive group.
• the content of (B') other curing agent in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 15% by mass or less, or more. It is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less.
• the lower limit of the content of (B′) other curing agent in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more , 0.01% by mass or more, 0.1% by mass or more, 1% by mass or more, 1.5% by mass or more, and the like.
• the content of (B) the active ester compound in the resin composition is preferably 10 mass when the sum of (B) the active ester compound and (B') other curing agent in the resin composition is 100 mass%. % or more, more preferably 30 mass % or more, still more preferably 40 mass % or more, and particularly preferably 50 mass % or more.
• the resin composition of the present invention may further contain (C) an inorganic filler as an optional component.
• (C) The inorganic filler is contained in the resin composition in the form of particles.
• An inorganic compound is used as the material for the inorganic filler.
• inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water.
• silica is particularly suitable.
• examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As silica, spherical silica is preferable.
• Inorganic fillers may be used singly or in combination of two or more at any ratio.
• inorganic fillers include, for example, “UFP-30” manufactured by Denka Kagaku Kogyo; “SP60-05” and “SP507-05” manufactured by Nippon Steel & Sumikin Materials; “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C”; “UFP-30” manufactured by Denka; 5N”; “SC2500SQ”, “SO-C4”, “SO-C2” and “SO-C1” manufactured by Admatechs; “DAW-03” and “FB-105FD” manufactured by Denka.
• the average particle size of the inorganic filler (C) is not particularly limited, but is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, even more preferably 2 ⁇ m or less, even more preferably 1 ⁇ m or less, and particularly preferably 0.001 ⁇ m or less. 7 ⁇ m or less.
• the lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, still more preferably 0.1 ⁇ m or more, and particularly preferably 0 .2 ⁇ m or more.
• the average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement.
• a measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes.
• a measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, the volume-based particle size distribution of the inorganic filler is measured by the flow cell method, and from the obtained particle size distribution The average particle diameter was calculated as the median diameter.
• the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.
• the specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m 2 /g or more, more preferably 0.5 m 2 /g or more, still more preferably 1 m 2 /g or more, Particularly preferably, it is 3 m 2 /g or more.
• the upper limit of the specific surface area of the inorganic filler (C) is not particularly limited, it is preferably 100 m 2 /g or less, more preferably 70 m 2 /g or less, even more preferably 50 m 2 /g or less, and particularly preferably is 40 m 2 /g or less.
• the specific surface area of the inorganic filler is determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and calculating the specific surface area using the BET multipoint method. obtained by
• the inorganic filler is preferably treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility.
• surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate compounds.
• a coupling agent etc. are mentioned.
• one type of surface treatment agent may be used alone, or two or more types may be used in combination.
• Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Industry Co., Ltd. "KBE903” (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573” (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.
• the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% to 5% by mass, and is surface-treated with 0.2% to 3% by mass. more preferably 0.3 mass % to 2 mass % of the surface treatment.
• the degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler.
• the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and more preferably 0.2 mg/m 2 from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable.
• it is preferably 1.0 mg/m 2 or less, more preferably 0.8 mg/m 2 or less, and 0.5 mg/m 2 or less. More preferred are:
• the amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (eg, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.
• EMIA-320V manufactured by Horiba Ltd.
• the content of (C) the inorganic filler in the resin composition is not particularly limited. It is 90% by mass or less, more preferably 85% by mass or less, and particularly preferably 80% by mass or less.
• the lower limit of the content of the inorganic filler (C) in the resin composition is not particularly limited. It can be at least 10% by mass, at least 10% by mass, at least 20% by mass, preferably at least 30% by mass, more preferably at least 40% by mass, even more preferably at least 50% by mass, even more preferably at least 60% by mass, especially Preferably, it is 70% by mass or more.
• the mass ratio of the inorganic filler (C) to the epoxy resin (A) in the resin composition ((C) component/(A) component) is preferably 1 or more, more preferably 3 or more, and particularly preferably 5 or more. be.
• the upper limit of the mass ratio (component (C)/component (A)) of the inorganic filler (C) to the epoxy resin (A) in the resin composition is preferably 30 or less, more preferably 20 or less, and particularly preferably 10. It is below.
• the resin composition of the present invention may further contain (D) an organic filler as an optional component.
• the organic filler exists in a particulate form in the resin composition.
• the (D) organic filler it is preferable to use rubber particles from the viewpoint of significantly obtaining the desired effects of the present invention.
• Organic fillers may be used singly or in combination of two or more at any ratio.
• rubber components contained in the rubber particles include silicone elastomers such as polydimethylsiloxane; polybutadiene, polyisoprene, polychlorobutadiene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer; coalescence, styrene-isobutylene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, isobutylene-butadiene copolymer, ethylene-propylene-diene terpolymer, ethylene-propylene-butene terpolymer Olefinic thermoplastic elastomers such as coalescing; thermal acrylic thermoplastic elastomers such as poly(meth)acrylate, poly(meth)butyl acrylate, poly(meth)acrylate cyclohexyl
• the rubber component may be mixed with silicone rubber such as polyorganosiloxane rubber.
• the rubber component contained in the rubber particles has a glass transition temperature of, for example, 0° C. or lower, preferably ⁇ 10° C. or lower, more preferably ⁇ 20° C. or lower, and even more preferably ⁇ 30° C. or lower.
• the organic filler preferably contains core-shell type rubber particles from the viewpoint of significantly obtaining the desired effects of the present invention.
• the core-shell type rubber particles are particulate organic fillers composed of core particles containing the above-described rubber component and one or more layers of shell covering the core particles.
• the core-shell type rubber particles are composed of a core particle containing the above-mentioned rubber component and a shell part obtained by graft copolymerization of a monomer component copolymerizable with the rubber component contained in the core particle.
• Shell-type graft copolymer rubber particles are preferred.
• the term "core-shell type" as used herein does not necessarily refer only to particles in which the core particle and the shell part can be clearly distinguished, and includes particles in which the boundary between the core particle and the shell part is unclear. It does not have to be completely covered with parts.
• the content of the rubber component in the core-shell type rubber particles is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more.
• the upper limit of the content of the rubber component in the core-shell type rubber particles is not particularly limited, but from the viewpoint of sufficiently covering the core particles with the shell portion, for example, 95% by mass or less, 90% by mass. Preferably.
• Examples of the monomer component forming the shell portion of the core-shell type rubber particles include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, and (meth)acryl.
• (Meth)acrylic acid esters such as octyl acid and glycidyl (meth)acrylate; (meth)acrylic acid; N-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; maleimide; ⁇ such as maleic acid and itaconic acid , ⁇ -unsaturated carboxylic acid; aromatic vinyl compounds such as styrene, 4-vinyltoluene, and ⁇ -methylstyrene; ) methyl acrylate.
• Examples of commercially available core-shell type rubber particles include “CHT” manufactured by Cheil Industries; “B602” manufactured by UMGABS; “Paraloid EXL-2602” and “Paraloid EXL-2603” manufactured by Dow Chemical Japan. ”, “Paraloid EXL-2655”, “Paraloid EXL-2311”, “Paraloid-EXL2313”, “Paraloid EXL-2315”, “Paraloid KM-330”, “Paraloid KM-336P”, “Paraloid KCZ-201”, Mitsubishi Rayon's “Metabrene C-223A”, “Metabrene E-901", “Metabrene S-2001”, “Metabrene W-450A”, “Metabrene SRK-200”, Kaneka's "Kane Ace M-511", “Kane Ace M-600”, “Kane Ace M-400", “Kane Ace M-580", “Kane Ace MR-01” and the like.
• the average particle size (average primary particle size) of the organic filler is not particularly limited, but is preferably 20 nm or more, more preferably 30 nm or more, and still more preferably 50 nm or more.
• the upper limit of the average particle size (average primary particle size) of the organic filler is not particularly limited, but is preferably 5,000 nm or less, more preferably 2,000 nm or less, and still more preferably 1,000 nm. It is below.
• the average particle size (average primary particle size) of the organic filler can be measured using a zeta potential particle size distribution analyzer or the like.
• the content of the (D) organic filler in the resin composition is not particularly limited. It is 5% by mass or less, more preferably 2% by mass or less.
• the lower limit of the content of the (D) organic filler in the resin composition is not particularly limited. 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 0.5% by weight or more.
• the resin composition of the present invention may further contain (E) a curing accelerator as an optional component.
• the curing accelerator has a function of accelerating the curing of (A) the epoxy resin.
• curing accelerators examples include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators.
• the resin composition of the present invention preferably contains an amine curing accelerator or an imidazole curing accelerator, and particularly preferably contains an amine curing accelerator.
• the curing accelerator may be used singly or in combination of two or more.
• Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydro Aliphatic phosphonium salts such as genhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphospho
• Urea-based curing accelerators include, for example, 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3- Aliphatic dimethylurea such as cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl )-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4- methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethyl
• Guanidine curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and
• imidazole curing accelerators examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-d
• imidazole-based curing accelerator a commercially available product may be used, for example, "1B2PZ”, “2MZA-PW”, “2PHZ-PW” manufactured by Shikoku Kasei Co., Ltd., "P200-H50” manufactured by Mitsubishi Chemical Corporation. etc.
• metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin.
• organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate.
• organic zinc complexes such as iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate;
• organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
• amine curing accelerators examples include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo (5,4,0)-undecene and the like.
• amine-based curing accelerator a commercially available product may be used, such as "MY-25” manufactured by Ajinomoto Fine-Techno Co., Ltd., and the like.
• the content of (E) the curing accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 5% by mass or less, more preferably It is 1% by mass or less, more preferably 0.7% by mass or less, and particularly preferably 0.5% by mass or less.
• the lower limit of the content of (E) the curing accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 0 It can be 0.001 wt% or more, 0.01 wt% or more, 0.1 wt% or more, and the like.
• the resin composition of the present invention may further contain optional additives as non-volatile components.
• additives include radically polymerizable compounds having a vinylphenyl group, (meth)acryloyl group, maleimide group, etc.; radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; Agent; thermosetting resin such as epoxy acrylate resin, urethane acrylate resin, urethane resin, cyanate resin, benzoxazine resin, unsaturated polyester resin, phenol resin, melamine resin, silicone resin, epoxy resin; polyvinyl acetal resin, polyolefin resin, Thermoplastic resins such as polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins; Organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds;
• melamine sulfate melamine sulfate
• halogen flame retardants e.g. antimony trioxide
• phosphate ester dispersants polyoxyalkylene dispersants, acetylene dispersants, silicone dispersants Dispersants such as agents, anionic dispersants, cationic dispersants; borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, carboxylic acid stabilizers Examples include stabilizers such as anhydride-based stabilizers.
• Other additives may be used singly or in combination of two or more at any ratio.
• the content of other additives can be appropriately set by those skilled in the art.
• the resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the non-volatile components described above.
• an arbitrary organic solvent as a known one can be used as appropriate, and the type thereof is not particularly limited.
• organic solvents examples include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ester-based solvents such as butyrolactone; Ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; Alcohol-based solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol Solvent; Ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, ⁇ -butyrolactone, methyl methoxypropionate; methyl lactate, ethyl
• the content of the (G) organic solvent is not particularly limited, but when all components in the resin composition are 100% by mass, for example, 60% by mass or less, 40% by mass or less , 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, and the like.
• the resin composition of the present invention for example, in any preparation container (A) epoxy resin, (B) active ester compound, optionally (B') other curing agent, optionally (C) inorganic filling material, optionally (D) organic filler, optionally (E) curing accelerator, optionally (F) other additives, and optionally (G) organic solvent, any It can be prepared by adding them sequentially and/or by adding them partly or wholly at the same time and mixing. Also, during the process of adding and mixing each component, the temperature can be set appropriately, and heating and/or cooling may be performed temporarily or over time.
• the resin composition may be stirred or shaken using a stirring or shaking device such as a mixer to uniformly disperse.
• a stirring or shaking device such as a mixer to uniformly disperse.
• defoaming may be performed under low pressure conditions such as vacuum.
• the resin composition of the present invention contains (A) an epoxy resin and (B) an active ester compound, and (A) the epoxy resin has an epoxy equivalent represented by (A-1) formula (1) of 1000 g/eq. . ⁇ 5000g/eq. and (A-2) an epoxy equivalent of 200 g/eq.
• a cured product of the resin composition of the present invention may have a low dielectric loss tangent (Df). Therefore, in one embodiment, for example, the dielectric loss tangent (Df) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. as in Test Example 1 below is preferably 0.0200 or less and 0.0200 or less. 0100 or less, more preferably 0.0080 or less, 0.0070 or less, 0.0060 or less, more preferably 0.0050 or less, 0.0040 or less, 0.0035 or less, particularly preferably 0.0032 or less, 0.0030 can be:
• the cured product of the resin composition of the present invention can have a feature of being excellent in copper plating peel strength. Therefore, in one embodiment, for example, a copper-plated conductor layer is formed on a cured product as in Test Example 2 below, and the copper-plated peel strength calculated from the load when the copper-plated conductor layer is peeled off in the vertical direction is , preferably 0.2 kgf/cm or more, more preferably 0.25 kgf/cm or more, still more preferably 0.3 kgf/cm or more and 0.35 kgf/cm or more, particularly preferably 0.4 kgf/cm or more and 0.45 kgf /cm or more.
• the upper limit is not particularly limited, it may be, for example, 10 kgf/cm or less.
• the cured product of the resin composition of the present invention can have the characteristic of being able to suppress the occurrence of cracks after desmear treatment. Therefore, in one embodiment, after fabricating and desmearing a circuit board as in Test Example 3 below, when 100 copper pad portions of the circuit board are observed, the number of cracks may preferably be 10 or less.
• the resin composition of the present invention can be suitably used as a resin composition for insulation, particularly as a resin composition for forming an insulation layer.
• a resin composition for forming an insulating layer for forming a conductor layer (including a rewiring layer) formed on an insulating layer (resin for forming an insulating layer for forming a conductor layer composition).
• a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board).
• the resin composition of the present invention also includes resin sheets, sheet laminate materials such as prepreg, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, and the like. It can be used in a wide range of applications.
• the resin composition of the present invention is used as an insulating layer for forming a rewiring layer.
• a resin composition for forming a rewiring layer and a resin composition for sealing a semiconductor chip (a resin composition for semiconductor chip sealing).
• a rewiring layer may be further formed on the encapsulation layer when the semiconductor chip package is manufactured.
• the resin composition of the present invention provides an insulating layer with good part-embedding properties, it can be suitably used when the printed wiring board is a component-embedded circuit board.
• the resin composition of the present invention can be applied in the form of a varnish, it is industrially preferably used in the form of a sheet-like laminated material containing the resin composition.
• the resin sheets and prepregs shown below are preferable.
• the resin sheet comprises a support and a resin composition layer provided on the support, and the resin composition layer is formed from the resin composition of the present invention.
• the thickness of the resin composition layer is preferably 50 ⁇ m or less, more It is preferably 40 ⁇ m or less.
• the lower limit of the thickness of the resin composition layer is not particularly limited, it can be usually 5 ⁇ m or more, 10 ⁇ m or more, or the like.
• the support examples include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.
• plastic material examples include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET”) and polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”).
• PET polyethylene terephthalate
• PEN polyethylene naphthalate
• PC polycarbonate
• acrylic such as polymethyl methacrylate (PMMA)
• PMMA polymethyl methacrylate
• TAC triacetyl cellulose
• PES polyether sulfide
• polyether ketones polyimides, and the like.
• polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.
• examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred.
• a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.
• the support may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface to be bonded to the resin composition layer.
• a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used.
• the release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins.
• a commercially available product may be used, for example, "SK-1” manufactured by Lintec Co., Ltd., “SK-1", “ AL-5”, “AL-7”, Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel”.
• the thickness of the support is not particularly limited, it is preferably in the range of 5 ⁇ m to 75 ⁇ m, more preferably in the range of 10 ⁇ m to 60 ⁇ m.
• the thickness of the release layer-attached support as a whole is preferably within the above range.
• the resin sheet may further contain any layer as necessary.
• an optional layer include a protective film conforming to the support provided on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). be done.
• the thickness of the protective film is not particularly limited, it is, for example, 1 ⁇ m to 40 ⁇ m.
• the resin sheet is produced by, for example, using a liquid resin composition as it is or preparing a resin varnish by dissolving the resin composition in an organic solvent, coating it on a support using a die coater or the like, and drying it. It can be produced by forming a resin composition layer.
• organic solvent examples include the same organic solvents as those described as components of the resin composition.
• An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
• Drying may be carried out by known methods such as heating and blowing hot air.
• the drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less.
• the temperature is 50° C. to 150° C. for 3 minutes to 10 minutes.
• a resin composition layer can be formed by drying for minutes.
• the resin sheet can be rolled up and stored.
• the resin sheet has a protective film, it can be used by peeling off the protective film.
• the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.
• the sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as prepreg base materials such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used.
• the thickness of the sheet-like fiber base material is preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, still more preferably 30 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
• the lower limit of the thickness of the sheet-like fiber base material is not particularly limited. Usually, it is 10 ⁇ m or more.
• a prepreg can be manufactured by a known method such as a hot melt method or a solvent method.
• the thickness of the prepreg can be in the same range as the resin composition layer in the resin sheet described above.
• the sheet-like laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (for a printed wiring board). for interlayer insulating layers of wiring boards).
• the printed wiring board of the present invention includes an insulating layer made of a cured product obtained by curing the resin composition of the present invention.
• a printed wiring board can be manufactured, for example, using the resin sheet described above by a method including the following steps (I) and (II).
• (I) A step of laminating a resin sheet on the inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate
• (II) Curing (for example, thermosetting) the resin composition layer to form an insulating layer process
• the “inner layer substrate” used in step (I) is a member that serves as a printed wiring board substrate, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc.
• the substrate may also have a conductor layer on one or both sides thereof, and the conductor layer may be patterned.
• An inner layer substrate having conductor layers (circuits) formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board.”
• an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing a printed wiring board is also included in the "inner layer substrate" as used in the present invention.
• an inner layer board with built-in components may be used.
• Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side.
• the member for thermocompression bonding the resin sheet to the inner layer substrate include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls).
• thermocompression bonding member instead of pressing the thermocompression member directly onto the resin sheet, it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the uneven surface of the inner layer substrate.
• Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method.
• the thermocompression temperature is preferably in the range of 60° C. to 160° C., more preferably 80° C. to 140° C.
• the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. .29 MPa to 1.47 MPa
• the heat pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds.
• Lamination can be carried out under reduced pressure conditions, preferably at a pressure of 26.7 hPa or less.
• Lamination can be done with a commercially available vacuum laminator.
• Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch vacuum pressurized laminator, and the like.
• the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side.
• the pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above.
• Smoothing treatment can be performed with a commercially available laminator. Lamination and smoothing may be performed continuously using the above-mentioned commercially available vacuum laminator.
• the support may be removed between step (I) and step (II), or may be removed after step (II).
• step (II) the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of the cured resin composition.
• Curing conditions for the resin composition layer are not particularly limited, and conditions that are usually employed when forming an insulating layer of a printed wiring board may be used.
• the thermosetting conditions for the resin composition layer vary depending on the type of resin composition, etc., but in one embodiment, the curing temperature is preferably 120° C. to 240° C., more preferably 150° C. to 220° C., and even more preferably 150° C. to 220° C. is between 170°C and 210°C.
• the curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, even more preferably 15 minutes to 100 minutes.
• the resin composition layer may be preheated at a temperature lower than the curing temperature before thermosetting the resin composition layer.
• the resin composition layer is cured at a temperature of 50° C. to 120° C., preferably 60° C. to 115° C., more preferably 70° C. to 110° C. for 5 minutes or more, It may be preheated for preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, even more preferably 15 minutes to 100 minutes.
• steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards.
• the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or step ( It may be carried out between IV) and step (V). If necessary, the steps (II) to (V) of forming the insulating layer and the conductor layer may be repeated to form a multilayer wiring board.
• the printed wiring board of the present invention can be manufactured using the prepreg described above.
• the manufacturing method is basically the same as in the case of using a resin sheet.
• the step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer.
• Step (III) may be performed using, for example, a drill, laser, plasma, or the like, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.
• Step (IV) is a step of roughening the insulating layer. Smear is usually also removed in this step (IV).
• the procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are commonly used in forming insulating layers of printed wiring boards can be employed.
• the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order.
• the swelling liquid used in the roughening treatment is not particularly limited, but examples thereof include alkaline solutions, surfactant solutions, etc., preferably alkaline solutions, more preferably sodium hydroxide solutions and potassium hydroxide solutions. preferable.
• Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU” manufactured by Atotech Japan.
• the swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30.degree. C. to 90.degree. C. for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes.
• the oxidizing agent used for the roughening treatment is not particularly limited, but examples include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide.
• the roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 100° C. for 10 to 30 minutes.
• the permanganate concentration in the alkaline permanganate solution is preferably 5% by mass to 10% by mass.
• Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan.
• an acidic aqueous solution is preferable, and commercially available products include, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan.
• the treatment with the neutralizing solution can be performed by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From the viewpoint of workability, etc., a method of immersing an object roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferable.
• the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is not particularly limited, but is preferably 500 nm or less, more preferably 400 nm or less, and still more preferably 300 nm or less. .
• the lower limit is not particularly limited, it is preferably 0.5 nm or more, more preferably 1 nm or more.
• the root-mean-square roughness (Rq) of the insulating layer surface after roughening is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less.
• the lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more.
• the arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.
• the step (V) is a step of forming a conductor layer, and forms the conductor layer on the insulating layer.
• the conductor material used for the conductor layer is not particularly limited.
• the conductor layer contains one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal.
• the conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper- nickel alloys and copper-titanium alloys).
• single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, nickel-chromium alloys, copper- Nickel alloys and copper/titanium alloy alloy layers are preferred, and single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium alloy alloy layers are more preferred, and copper single metal layers are preferred.
• a metal layer is more preferred.
• the conductor layer may have a single layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated.
• the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.
• the thickness of the conductor layer is generally 3 ⁇ m to 35 ⁇ m, preferably 5 ⁇ m to 30 ⁇ m, depending on the desired printed wiring board design.
• the conductor layer may be formed by plating.
• a conductive layer having a desired wiring pattern can be formed by plating the surface of an insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. It is preferably formed by a method.
• a semi-additive method is shown below.
• a plating seed layer is formed on the surface of the insulating layer by electroless plating.
• a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to a desired wiring pattern.
• the mask pattern is removed. After that, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.
• the conductor layer may be formed using metal foil.
• step (V) is preferably performed between step (I) and step (II).
• step (I) the support is removed and a metal foil is laminated on the exposed surface of the resin composition layer.
• Lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I).
• step (II) is performed to form an insulating layer.
• a conductor layer having a desired wiring pattern can be formed by conventional known techniques such as the subtractive method and the modified semi-additive method.
• a metal foil can be manufactured by a known method such as an electrolysis method or a rolling method.
• Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Mining Co., Ltd., and the like.
• a semiconductor device of the present invention includes the printed wiring board of the present invention.
• the semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.
• semiconductor devices examples include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, televisions, etc.) and vehicles (such as motorcycles, automobiles, trains, ships, aircraft, etc.).
• the main component of epoxy resin A is an epoxy resin represented by formula (1), wherein Ar is a group represented by formula (X-1-1) or represented by formula (X-2-1) and Ar, which is a group represented by the formula (X-1-1), and Ar, which is a group represented by the formula (X-2-1).
• Equivalent weight is 1900 g/eq. is.
• Epoxy resin A (epoxy equivalent 1900 g / eq.) 1 part, bisphenol type epoxy resin (manufactured by Nippon Steel Chemical & Materials "ZX-1059", a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent 170 g / eq.) 5 parts, naphthalene skeleton epoxy resin (manufactured by DIC "HP-4032-SS”, epoxy equivalent 144 g / eq.) 5 parts, active ester curing agent (manufactured by DIC "HPC-8150-62T", non-volatile components 62 mass% toluene solution, active ester group equivalent 234 g / eq.) 26 parts, inorganic filler (amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) surface-treated spherical silica (manufactured by Admatechs Co., Ltd.) surface-treated
• Example 2 The amount of bisphenol type epoxy resin ("ZX-1059” manufactured by Nippon Steel Chemical & Materials Co., Ltd.) was changed from 5 parts to 3 parts, and the amount of naphthalene skeleton epoxy resin ("HP-4032-SS” manufactured by DIC) used. was changed from 5 parts to 4 parts, and a biphenyl skeleton epoxy resin ("NC-3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 270 g / eq.) was added in the same manner as in Example 1, except that 3 parts were added. A resin composition (resin varnish) was prepared.
• Example 3 The amount of bisphenol type epoxy resin ("ZX-1059” manufactured by Nippon Steel Chemical & Materials Co., Ltd.) was changed from 5 parts to 3 parts, and the amount of naphthalene skeleton epoxy resin ("HP-4032-SS” manufactured by DIC) used. was changed from 5 parts to 4 parts, and 3 parts of naphthol aralkyl skeleton epoxy resin ("ESN-475V” manufactured by Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent 330 g / eq.) was added. Then, a resin composition (resin varnish) was prepared.
• Example 4 The amount of bisphenol type epoxy resin ("ZX-1059” manufactured by Nippon Steel Chemical & Materials Co., Ltd.) was changed from 5 parts to 3 parts, and the amount of naphthalene skeleton epoxy resin ("HP-4032-SS” manufactured by DIC) used.
• Example 5 The amount of bisphenol type epoxy resin ("ZX-1059” manufactured by Nippon Steel Chemical & Materials Co., Ltd.) was changed from 5 parts to 3 parts, and the amount of naphthalene skeleton epoxy resin ("HP-4032-SS” manufactured by DIC) used.
• naphthalene skeleton epoxy resin (“HP-4032-SS” manufactured by DIC) was changed from 5 parts to 8 parts, and 5 parts of biphenyl skeleton epoxy resin ("NC-3000L” manufactured by Nippon Kayaku Co., Ltd.) was added.
• no active ester curing agent (“HPC-8150-62T” manufactured by DIC) was used, and a cresol novolak resin (“LA-3018-50P” manufactured by DIC, hydroxyl equivalent 151, non-volatile content 50% 1 -Methoxy-2-propanol solution) was added in the same manner as in Example 1 to prepare a resin composition (resin varnish).
• ⁇ Test Example 1 Measurement of dielectric loss tangent (Df)>
• a polyethylene terephthalate film (“AL5” manufactured by Lintec Corporation, thickness 38 ⁇ m) provided with a release layer was prepared.
• the resin composition (resin varnish) prepared in Examples and Comparative Examples was uniformly coated on the release layer of this support so that the thickness of the resin composition layer after drying was 40 ⁇ m. Thereafter, the resin composition was dried at 80° C. to 100° C. (average 90° C.) for 4 minutes to obtain a resin sheet including a support and a resin composition layer.
• the obtained resin sheet was heated at 190°C for 90 minutes to thermally cure the resin composition layer. After that, the support was peeled off to obtain a cured product of the resin composition. This cured product was cut into test pieces having a width of 2 mm and a length of 80 mm.
• the dielectric loss tangent (Df) of the test piece was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by the cavity resonance perturbation method using “HP8362B” manufactured by Agilent Technologies. Measurements were made on three specimens.
• ⁇ Test Example 2 Measurement of copper plating peel strength> (1) Surface treatment of inner layer circuit board As an inner layer circuit board, a glass cloth base epoxy resin double-sided copper clad laminate (copper foil thickness 18 ⁇ m, substrate thickness 0.4 mm, Panasonic company "R1515A”) was prepared. Both surfaces of the inner layer circuit board were etched by 1 ⁇ m with “CZ8101” manufactured by MEC Co., Ltd. to roughen the copper surface.
• the laminated substrate is soaked in a swelling liquid (Swelling Dip Securigant P containing diethylene glycol monobutyl ether manufactured by Atotech Japan (aqueous solution of glycol ethers and sodium hydroxide)) at 60°C for 10 minutes. Soaked.
• a swelling liquid Silicone Gel P containing diethylene glycol monobutyl ether manufactured by Atotech Japan (aqueous solution of glycol ethers and sodium hydroxide)
• a roughening liquid Atotech Japan Concentrate Compact P (KMnO 4 : 60 g/L, NaOH: 40 g/L aqueous solution) at 80° C. for 20 minutes.
• the laminated substrate was immersed in a neutralizing solution (Reduction Shoryusin Securigant P (sulfuric acid aqueous solution) manufactured by Atotech Japan Co., Ltd.) for 5 minutes at 40° C. After that, the laminated substrate was dried at 80° C. for 30 minutes. Thus, "evaluation substrate A" was obtained.
• a neutralizing solution Reduction Shoryusin Securigant P (sulfuric acid aqueous solution) manufactured by Atotech Japan Co., Ltd.
• Plating by Semi-Additive Method Evaluation board A was immersed in an electroless plating solution containing PdCl 2 at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes. After that, it was annealed by heating at 150° C. for 30 minutes. After that, an etching resist was formed, and pattern formation was performed by etching. Thereafter, copper sulfate electroplating was performed to form a conductor layer with a thickness of 20 ⁇ m. Next, an annealing treatment was performed at 190° C. for 60 minutes to obtain an “evaluation substrate B”.
• a cut was formed in the conductor layer of the evaluation substrate B to surround a rectangular portion with a width of 10 mm and a length of 100 mm.
• One end of the rectangular portion was peeled off and gripped with a gripper (Autocom type testing machine "AC-50C-SL" manufactured by TSE Co., Ltd.).
• a gripper Autocom type testing machine "AC-50C-SL” manufactured by TSE Co., Ltd.
• the rectangular portion was peeled off vertically at a speed of 50 mm/min at room temperature, and the load (kgf/cm) when 35 mm was peeled off was measured as the copper plating peel strength.
• ⁇ Test Example 3 Evaluation of cracks after desmearing>
• a polyethylene terephthalate film (“AL5” manufactured by Lintec Corporation, thickness 38 ⁇ m) provided with a release layer was prepared.
• the resin composition (resin varnish) prepared in Examples and Comparative Examples was uniformly coated on the release layer of this support so that the thickness of the resin composition layer after drying was 25 ⁇ m. Thereafter, the resin varnish was dried at 80° C. to 100° C. (average 90° C.) for 2.5 minutes to obtain a resin sheet including the support and the resin composition layer.
• a core material (manufactured by Hitachi Chemical Co., Ltd.) is obtained by forming circular copper pads (thickness of copper: 35 ⁇ m) with a diameter of 350 ⁇ m in a grid pattern at intervals of 400 ⁇ m so that the resin sheet with a thickness of 25 ⁇ m obtained above has a residual copper rate of 60%.
• "E705GR”, thickness 400 ⁇ m) on both sides using a batch-type vacuum pressure laminator (2-stage build-up laminator "CVP700” manufactured by Nikko Materials Co., Ltd.) so that the resin composition layer is bonded to the inner layer substrate. Then, it was laminated on both sides of the inner layer substrate. This lamination was carried out by pressure bonding for 30 seconds at a temperature of 100° C.
• Table 1 below shows the content of non-volatile components in the resin compositions of Examples and Comparative Examples, and the measurement results and evaluation results of Test Examples.
• Comparative Example 4 which contains (A-1) the specific epoxy resin but does not contain (B) the active ester compound, has a relatively high dielectric loss tangent.
• Comparative Example 3 using (A-1) the specific epoxy resin and (B) the active ester compound, although the dielectric loss tangent is suppressed, cracks tend to occur easily.
• Comparative Example 2 in which a high epoxy equivalent weight epoxy resin having a structure represented by formula (1) was used in place of (A-1) the specific epoxy resin together with the following epoxy resin and (B) an active ester compound, cracks Although the occurrence of is suppressed, the copper plating pole strength is low. Further, (A-2) the epoxy equivalent is 200 g/eq.

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