WO2022102757A1 - 樹脂組成物 - Google Patents

樹脂組成物 Download PDF

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Publication number
WO2022102757A1
WO2022102757A1 PCT/JP2021/041792 JP2021041792W WO2022102757A1 WO 2022102757 A1 WO2022102757 A1 WO 2022102757A1 JP 2021041792 W JP2021041792 W JP 2021041792W WO 2022102757 A1 WO2022102757 A1 WO 2022102757A1
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Prior art keywords
resin composition
mass
resin
component
group
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PCT/JP2021/041792
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English (en)
French (fr)
Japanese (ja)
Inventor
賢司 川合
Original Assignee
味の素株式会社
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Priority to JP2022562211A priority Critical patent/JPWO2022102757A1/ja
Priority to CN202180076144.3A priority patent/CN116406332A/zh
Priority to KR1020237015905A priority patent/KR20230098808A/ko
Publication of WO2022102757A1 publication Critical patent/WO2022102757A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • 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

Definitions

  • the present invention relates to a resin composition containing a maleimide compound. Further, the present invention relates to a cured product obtained by using the resin composition, a sheet-like laminated material, a resin sheet, a printed wiring board, and a semiconductor device.
  • the insulating layer is generally formed by curing the resin composition.
  • further improvement of dielectric properties such as dielectric constant of an insulating layer and further improvement of copper adhesion have been required.
  • an insulating layer having a high glass transition temperature there is a demand for an insulating layer having a high glass transition temperature.
  • the minimum melt viscosity of the resin composition, the relative permittivity (Dk) and the dielectric constant tangent (Df) of the material, and the glass transition are so far. There was a problem with the low point (Tg).
  • Patent Document 1 maleimide compounds containing an isopropylidene group have been known.
  • the subject of the present invention is a cured product in which the minimum melt viscosity can be suppressed to a lower level, the relative permittivity (Dk) and the dielectric constant tangent (Df) are low, the glass transition point (Tg) is high, and the copper plating peel strength is excellent.
  • the present invention is to provide a resin composition capable of obtaining the above.
  • (B) an active ester compound and (C) an epoxy resin surprisingly, the minimum melt viscosity of the resin composition can be suppressed to a lower value, and the specific dielectric constant (Dk) and the dielectric tangent (Df) can be suppressed.
  • Dk specific dielectric constant
  • Df dielectric tangent
  • the component (A) is the formula (A2) :.
  • rings A and B each independently represent an aromatic ring that may have a substituent; a represents an integer of 1 or more.
  • the component (A) is the formula (A-1) :.
  • R 1 and R 2 independently represent an alkyl group or an aryl group; a represents an integer of 1 or more; x and y independently represent 0, 1, 2 or, respectively. 3 is shown.
  • the content of the component (A) is 3% by mass to 30% by mass when the non-volatile component in the resin composition is 100% by mass, according to any one of the above [1] to [4].
  • the content of the component (B) is 3% by mass to 30% by mass when the non-volatile component in the resin composition is 100% by mass, according to any one of the above [1] to [5].
  • Resin composition. [7] The above-mentioned [1] to [6], wherein the mass ratio of the component (A) to the component (B) (component (A) / component (B)) is 0.5 to 2.
  • the content of the component (C) is 1% by mass to 30% by mass when the non-volatile component in the resin composition is 100% by mass, according to any one of the above [1] to [7].
  • a semiconductor device including the printed wiring board according to the above [18].
  • the minimum melt viscosity can be suppressed to be lower, the relative permittivity (Dk) and the dielectric tangent (Df) are low, the glass transition point (Tg) is high, and the copper plating peel strength is obtained.
  • An excellent cured product can be obtained.
  • the resin composition of the present invention comprises (A) a maleimide compound having an isopropyridene group bonded to two aromatic carbon atoms of different aromatic rings (hereinafter, may be referred to as "specific maleimide compound"), and (B) an active ester. It contains a compound and (C) epoxy resin.
  • the resin composition of the present invention may further contain any component in addition to (A) the specific maleimide compound, (B) the active ester compound, and (C) the epoxy resin.
  • Optional components include, for example, (A') other maleimide compounds, (B') other curing agents, (D) inorganic fillers, (E) curing accelerators, (F) polyimide resins, (G) and others. Additives and (H) organic solvent.
  • each component contained in the resin composition will be described in detail.
  • the resin composition of the present invention contains (A) a specific maleimide compound.
  • the specific maleimide compound may be used alone or in combination of two or more at any ratio.
  • the maleimide compound means a compound having at least one maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl group) in one molecule.
  • the maleimide group in the specific maleimide compound may be bonded to an aromatic carbon atom or an aliphatic carbon atom, but preferably contains one bonded to an aromatic carbon atom (A).
  • the number of maleimide groups in one molecule of the specific maleimide compound is preferably 2 or more, more preferably 3 or more, more preferably 3 to 11, and 3 to 6. More preferred.
  • the specific maleimide compound has at least one isopropylidene group (-C (CH 3 ) 2- ) bonded to two aromatic carbon atoms of different aromatic rings in one molecule.
  • the isopropyridene group contained in the specific maleimide compound is two aromatic carbon atoms in a combination of an aromatic carbon atom in an aromatic ring having a maleimide group and an aromatic carbon atom in an aromatic ring having no maleimide group.
  • the specific maleimide compound is preferably bonded to two aromatic carbon atoms in a combination of an aromatic carbon atom in an aromatic ring having a maleimide group and an aromatic carbon atom in an aromatic ring having no maleimide group.
  • all the isopropyridene groups contained in the specific maleimide compound are an aromatic carbon atom in an aromatic ring having a maleimide group and an aromatic carbon in an aromatic ring having no maleimide group. It is an isopropylidene group bonded to two aromatic carbon atoms in combination with an atom.
  • the number of such isopropyrine groups in one molecule of the specific maleimide compound is preferably 2 or more, more preferably 4 or more, still more preferably 4 to 20, and 4 to 10. Is particularly preferable.
  • the aromatic ring means a ring according to Hückel's law in which the number of electrons contained in the ⁇ -electron system on the ring is 4p + 2 (p is a natural number).
  • the aromatic ring may be an aromatic carbocycle having a carbon atom as a ring-constituting atom, or an aromatic heterocyclic ring having a heteroatom such as an oxygen atom, a nitrogen atom, and a sulfur atom in addition to the carbon atom as the ring-constituting atom. However, in one embodiment, it is preferably an aromatic carbon ring.
  • the aromatic ring is preferably a 5- to 14-membered aromatic ring, more preferably a 5- to 10-membered aromatic ring, and even more preferably a 5- or 6-membered aromatic ring.
  • the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and the like, more preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring.
  • the specific maleimide compound is preferably the formula (A1): in one embodiment.
  • ring A, ring B and ring C each independently represent an aromatic ring which may have a substituent;
  • X is an independent single bond, —C (R x ).
  • 2- -O-, -CO-, -S-, -SO-, -SO 2- , -CONH-, or -NHCO-;
  • R x independently contains a hydrogen atom and a substituent.
  • the a unit and the c unit may be the same or different for each unit.
  • Rings A, B and C each independently represent an aromatic ring which may have a substituent, preferably an aromatic carbocycle which may have a substituent, and more preferably.
  • substituted group is not particularly limited, but for example, an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, an alkyl-oxy group, an alkenyl-oxy group, and an aryl-oxy group.
  • alkyl-carbonyl group alkenyl-carbonyl group, aryl-carbonyl group, alkyl-oxy-carbonyl group, alkenyl-oxy-carbonyl group, aryl-oxy-carbonyl group, alkyl-carbonyl-oxy group, alkenyl-carbonyl-oxy
  • Alkyl (group) means a linear, branched and / or cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, the alkyl (group) is preferably an alkyl (group) having 1 to 14 carbon atoms. Examples of the alkyl (group) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a nonyl group.
  • Alkenyl (group) means a linear, branched and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. Unless otherwise specified, the alkenyl (group) is preferably an alkenyl group having 2 to 14 carbon atoms.
  • alkenyl (group) examples include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a cyclohexenyl group and the like.
  • Aryl (group) means a monovalent aromatic hydrocarbon group. Unless otherwise specified, the aryl (group) is preferably an aryl (group) having 6 to 14 carbon atoms. Examples of the aryl (group) include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.
  • X can independently form a single bond, -C (R x ) 2- , -O-, -CO-, -S-, -SO-, -SO 2- , -CONH-, or -NHCO-. Shown, preferably single bond, -C (R x ) 2- , or -O-, more preferably single bond, or -C (R x ) 2- , and particularly preferably single bond.
  • R x independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and more preferably, a hydrogen atom, an alkyl group, or an alkyl group. It is an aryl group, more preferably a hydrogen atom or an alkyl group.
  • the specific maleimide compound includes, in one embodiment, a maleimide compound represented by the formula (A1) in which a is 1, and a maleimide compound represented by the formula (A1) in which a is 2 or more.
  • the maleimide compound represented by the formula (A1) of 2 or more is preferably contained in an amount of 1% by mass, more preferably 5% by mass, further preferably 8% by mass, and 10% by mass. Especially preferable.
  • B indicates 0 or 1 independently of each other, and is preferably 1.
  • c independently indicates 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.
  • the specific maleimide compound is more preferably the formula (A2): in one embodiment.
  • the specific maleimide compound is more preferably the formulas (A-1) to (A-6): in another embodiment.
  • R 1 and R 2 independently indicate an alkyl group or an aryl group; x and y independently indicate 0, 1, 2 or 3; other symbols are described above. Is similar to.
  • the maleimide compound represented by any of the above is contained, and in one embodiment, the compound represented by the formula (A-1) is contained, and in one embodiment, the formula (A-1a) is even more preferable.
  • a compound represented by the formula (A-1a) is particularly preferably contained.
  • R 1 and R 2 each independently represent an alkyl group or an aryl group, and are preferably an alkyl group.
  • x and y independently represent 0, 1, 2 or 3, respectively, preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.
  • the weight average molecular weight (Mw) of the specific maleimide compound is preferably 500 to 5000, more preferably 500 to 4000, and even more preferably 500 to 3000.
  • the number average molecular weight (Mn) of the specific maleimide compound is preferably 500 to 5000, more preferably 500 to 4000, and even more preferably 500 to 3000.
  • the weight average molecular weight and the number average molecular weight of the resin can be measured as polystyrene-equivalent values by the gel permeation chromatography (GPC) method.
  • the maleimide equivalent of the specific maleimide compound is preferably 100 g / eq. ⁇ 1000 g / eq. , More preferably 150 g / eq. ⁇ 400 g / eq. Is.
  • the maleimide equivalent of the (A) specific maleimide compound is the mass of the (A) specific maleimide compound per one equivalent of the maleimide group.
  • the content of the (A) specific maleimide 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, more preferably 50% by mass or less. It is 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 15% by mass or less.
  • the lower limit of the content of the (A) specific maleimide compound in the resin composition is not particularly limited, but is preferably 0.1% by mass or more when the non-volatile component in the resin composition is 100% by mass. , More preferably 1% by mass or more, still more preferably 3% by mass or more, still more preferably 5% by mass or more, and particularly preferably 7% by mass or more.
  • the resin composition of the present invention may further contain a (A') maleimide compound other than the (A) component as an optional component.
  • (A') Other maleimide compounds may be used alone or in any combination of two or more.
  • the (A') other maleimide compound is not particularly limited, and may be an aliphatic maleimide compound containing an aliphatic amine skeleton or an aromatic maleimide compound containing an aromatic amine skeleton, and may be commercially available.
  • Examples of products include "SLK-2600” manufactured by Shinetsu Chemical Industry Co., Ltd., "BMI-1500”, “BMI-1700", “BMI-3000J”, “BMI-689", and “BMI-689” manufactured by Designer Molecule's.
  • BMI-2500 maleimide compound containing dimerdiamine structure
  • BMI-6100 aromatic maleimide compound
  • MIR-3000-70MT biphenyl aralkyl type maleimide compound
  • BMI-70 and BMI-80 manufactured by KAI Kasei Co., Ltd.
  • BMI-2300 a maleimide resin
  • BMI-TMH a maleimide resin
  • the maleimide equivalent of the other maleimide compound is preferably 100 g / eq. ⁇ 20000 g / eq. , More preferably 200 g / eq. ⁇ 15000 g / eq. , More preferably 300 g / eq. ⁇ 10,000 g / eq. Is.
  • the maleimide equivalent of the (A') other maleimide compound is the mass of the (A') other maleimide compound per 1 equivalent of the maleimide group.
  • the weight average molecular weight (Mw) of the (A') other maleimide compound is preferably 500 to 50,000, more preferably 700 to 20,000.
  • the number average molecular weight (Mn) of the (A') other maleimide compound is preferably 500 to 50,000, more preferably 700 to 20,000.
  • the content of the (A') and other maleimide compounds in the resin composition is not particularly limited, but is preferably 50% by mass or less when the non-volatile component in the resin composition is 100% by mass. It is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
  • the lower limit of the content of the (A') and other maleimide compounds 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. , 0.1% by mass or more, 1% by mass or more, 2% by mass or more, and the like.
  • the content of the (A) specific maleimide compound in the resin composition is preferably 10% by mass when the total maleimide compound (total of the (A) component and the (A') component) in the resin composition is 100% by mass. % Or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 50% by mass or more.
  • the resin composition of the present invention contains (B) an active ester compound.
  • the active ester compound may be used alone or in combination of two or more at any ratio.
  • the (B) active ester compound may have a function as an epoxy resin curing agent that reacts with and cures the (C) epoxy resin.
  • ester compound generally, two or more ester groups with high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds are contained in one molecule.
  • the compound to have 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 preferable, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable.
  • the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like.
  • phenol compound or naphthol compound examples include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-.
  • the "dicyclopentadiene-type diphenol compound” refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.
  • 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 a phenol novolac acetylated product, and a phenol novolak benzoyl compound.
  • the active ester compound is preferable, and at least one selected from the dicyclopentadiene type active ester compound and the naphthalene type active ester compound is more preferable, and the dicyclopentadiene type active ester compound is further preferable.
  • the dicyclopentadiene type active ester compound an active ester compound containing a dicyclopentadiene type diphenol structure is preferable.
  • 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 the active ester compound per active ester group equivalent.
  • the content of the (B) 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, more preferably 50% by mass or less. It is 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and particularly preferably 20% by mass or less.
  • the lower limit of the content of the (B) active ester compound in the resin composition is not particularly limited, but is preferably 0.1% by mass or more when the non-volatile component in the resin composition is 100% by mass. , More preferably 1% by mass or more, still more preferably 3% by mass or more, still more preferably 5% by mass or more, still more preferably 8% by mass or more, and particularly preferably 10% by mass or more.
  • the mass ratio ((A) component / (B) component) of the (A) specific maleimide compound to the (B) active ester compound in the resin composition is preferably 0.1 or more, more preferably 0.3 or more, particularly. It is preferably 0.5 or more.
  • the upper limit of the mass ratio ((A) component / (B) component) of the (A) specific maleimide compound to the (B) active ester compound in the resin composition is preferably 5 or less, more preferably 2 or less, and particularly preferably. It is 1 or less.
  • the resin composition of the present invention may further contain a (B') curing agent other than the (B) component as an optional component.
  • (B') Other curing agents may be used alone or in any combination of two or more.
  • the (B') other curing agent may have a function as an epoxy resin curing agent that reacts with (C) an epoxy resin and cures, similarly to the (B) active ester compound.
  • the (B') other curing agent is not particularly limited, but for example, a phenol-based curing agent, a carbodiimide-based curing agent, an acid anhydride-based curing agent, an amine-based curing agent, a benzoxazine-based curing agent, and the like. Examples thereof include a cyanate ester-based curing agent and a thiol-based curing agent. It is particularly preferable that the (B') other curing agent contains a phenolic curing agent.
  • a phenolic curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the adherend, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Of these, a triazine skeleton-containing phenol novolac resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion.
  • phenolic curing agent examples include, for example, "MEH-7700”, “MEH-7810", “MEH-7851” manufactured by Meiwa Kasei Co., Ltd., “NHN”, “CBN”, and “CBN” manufactured by Nippon Kayaku Co., Ltd. GPH, "SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485”, “SN-495”, “SN-” manufactured by Nittetsu Chemical & Materials Co., Ltd. 375 “,” SN-395 “, DIC's" LA-7052 “,” LA-7054 “,” LA-3018 “,” LA-3018-50P “,” LA-1356 “,” TD2090 “,” TD-2090-60M “and the like.
  • carbodiimide-based curing agent examples include curing agents having one or more, preferably two or more carbodiimide structures in one molecule, and examples thereof include tetramethylene-bis (t-butylcarbodiimide) and cyclohexanebis (methylene-).
  • aliphatic biscarbodiimides such as t-butylcarbodiimide; biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis (kisilylcarbodiimide); polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly (methylene).
  • Aliphatic polycarbodiimides such as biscyclohexylene carbodiimide), poly (isophorone carbodiimide); poly (phenylene carbodiimide), poly (naphthylene carbodiimide), poly (trilen carbodiimide), poly (methyldiisopropylphenylene carbodiimide), poly (triethylphenylene) Carbodiimide), poly (diethylphenylene carbodiimide), poly (triisopropylphenylene carbodiimide), poly (diisopropylphenylene carbodiimide), poly (xylylene carbodiimide), poly (tetramethylxylylene carbodiimide), poly (methylenediphenylene carbodiimide), poly Examples thereof include polycarbodiimides such as aromatic polycarbodiimides such as [methylenebis (methylphenylene) carbodiimide].
  • carbodiimide-based curing agents include, for example, "carbodilite V-02B”, “carbodilite V-03”, “carbodilite V-04K”, “carbodilite V-07” and “carbodilite V-09” manufactured by Nisshinbo Chemical Co., Ltd. "; Examples thereof include” Stavaxol P “,” Stavaxol P400 “, and” High Kazil 510 “manufactured by Rheinchemy.
  • the acid anhydride-based curing agent examples include a curing agent having one or more acid anhydride groups in one molecule, and a curing agent having two or more acid anhydride groups in one molecule is preferable.
  • Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrohydride phthalic acid, methylhexahydrohydride phthalic acid, methylnadic acid anhydride, and hydride methylnadic acid.
  • acid anhydride curing agents include "HNA-100”, “MH-700”, “MTA-15”, “DDSA”, “OSA” manufactured by Shin Nihon Rika Co., Ltd., and “OSA” manufactured by Mitsubishi Chemical Corporation. "YH-306”, “YH-307”, “HN-2200”, “HN-5500” manufactured by Hitachi Chemical, "EF-30”, “EF-40”, “EF-60”, “EF” manufactured by Clay Valley. -80 "and the like.
  • the amine-based curing agent examples include curing agents having one or more, preferably two or more amino groups in one molecule, and examples thereof include aliphatic amines, polyether amines, and alicyclic amines. Aromatic amines and the like can be mentioned, and among them, aromatic amines are preferable from the viewpoint of achieving the desired effect of the present invention.
  • the amine-based curing agent is preferably a primary amine or a secondary amine, more preferably a primary amine.
  • amine-based curing agent examples include 4,4'-methylenebis (2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone.
  • amine-based curing agent for example, "SEIKACURE-S” manufactured by Seika, "KAYABOND C-200S”, “KAYABOND C-100”, and “Kayahard A-A” manufactured by Nippon Kayaku. , "Kayahard AB”, “Kayahard AS”, “Epicure W” manufactured by Mitsubishi Chemical Corporation, and the like.
  • benzoxazine-based curing agent examples include "JBZ-OP100D” and “ODA-BOZ” manufactured by JFE Chemical Co., Ltd .; “HFB2006M” manufactured by Showa High Polymer Co., Ltd .; “Pd” manufactured by Shikoku Chemicals Corporation. Examples include “FA”.
  • cyanate ester-based curing agent examples include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4, 4'-Etilidene diphenyl disyanate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-) Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, Examples thereof include polyfunctional cyanate resins derived from phenol novolac, cresol novolak and the like, and prepolymers in which these cyanate
  • cyanate ester-based curing agent examples include "PT30” and “PT60” (both are phenol novolac type polyfunctional cyanate ester resins), "BA230”, and “BA230S75” (part of bisphenol A dicyanate) manufactured by Lonza Japan.
  • PT30 and "PT60” (both are phenol novolac type polyfunctional cyanate ester resins), "BA230”, and “BA230S75” (part of bisphenol A dicyanate) manufactured by Lonza Japan.
  • a prepolymer in which the whole is triazined to become a trimer) and the like can be mentioned.
  • thiol-based curing agent examples include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), tris (3-mercaptopropyl) isocyanurate, and the like.
  • the reaction group equivalent of (B') and other curing agents is preferably 50 g / eq. ⁇ 3000 g / eq. , More preferably 100 g / eq. ⁇ 1000 g / eq. , More preferably 100 g / eq. ⁇ 500 g / eq. , Particularly preferably 100 g / eq. ⁇ 300 g / eq. Is.
  • the reaction group equivalent is the mass of the curing agent per reaction group equivalent.
  • the content of the (B') and other curing agents in the resin composition is not particularly limited, but is preferably 15% by mass or less when the non-volatile component in the resin composition is 100% by mass. 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 the (B') and other curing agents 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, 2% by mass or more, and the like.
  • the content of the (B) active ester compound in the resin composition is preferably 10% by mass when the total of the (B) active ester compound and the (B') other curing agent in the resin composition is 100% by mass. % Or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 50% by mass or more.
  • the resin composition of the present invention contains (C) an epoxy resin.
  • the epoxy resin is a curable resin having an epoxy group.
  • epoxy resin examples include bixilenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol type.
  • the resin composition preferably contains, as the (C) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule.
  • (C) The ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the non-volatile component of the epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably. Is 70% by mass or more.
  • the epoxy resin may be a liquid epoxy resin at a temperature of 20 ° C. (hereinafter sometimes referred to as “liquid epoxy resin”) or a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “solid epoxy resin”). ).
  • the resin composition of the present invention may contain only the liquid epoxy resin or only the solid epoxy resin as the epoxy resin, or may contain the liquid epoxy resin and the solid epoxy resin in combination. You may be.
  • the epoxy resin in the resin composition of the present invention is preferably a solid epoxy resin or a combination of a liquid epoxy resin and a solid epoxy resin, and more preferably a liquid epoxy resin.
  • liquid epoxy resin a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.
  • liquid epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton.
  • An alicyclic epoxy resin having an alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, and an epoxy resin having a butadiene structure are preferable.
  • liquid epoxy resin examples include “HP4032”, “HP4032D”, and “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC; “828US”, “828EL”, “jER828EL”, and “825" manufactured by Mitsubishi Chemical Co., Ltd.
  • Bisphenol F type epoxy resin mixture Bisphenol F type epoxy resin mixture
  • Nagase Chemtex's "EX-721” glycol ester type epoxy resin
  • Daicel's "Selokiside 2021P” alicyclic epoxy resin with an ester skeleton
  • PB-3600 manufactured by Nippon Soda, "JP-100", “JP-200” (epoxy resin having a butadiene structure)
  • ZX1658 "ZX1658GS” (liquid) manufactured by Nittetsu Chemical & Materials. 1,4-glycidylcyclohexane type epoxy resin) and the like. These may be used individually by 1 type, or may be used in combination of 2 or more types.
  • solid epoxy resin a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.
  • the solid epoxy resin examples include bixilenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol type epoxy resin.
  • Naftor type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol phthali Midin type epoxy resin and phenol phthalein type epoxy resin are preferable.
  • solid epoxy resin examples include "HP4032H” (naphthalene type epoxy resin) manufactured by DIC; "HP-4700” and “HP-4710” (naphthalen type tetrafunctional epoxy resin) manufactured by DIC; DIC. "N-690” (cresol novolac type epoxy resin); DIC “N-695" (cresol novolac type epoxy resin); DIC "HP-7200”, “HP-7200HH”, “HP” -7200H “,” HP-7200L “(dicyclopentadiene type epoxy resin);” EXA-7311 ",” EXA-7311-G3 ",” EXA-7311-G4 ",” EXA-7311-G4S "manufactured by DIC.
  • Epoxy resin "ESN485" (naphthol type epoxy resin) manufactured by Nittetsu Chemical &Materials; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nittetsu Chemical &Materials; "YX4000H” manufactured by Mitsubishi Chemical Co., Ltd., "YX4000", “YX4000HK”, “YL7890” (bixilenol type epoxy resin); “YL6121” (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; “YX8800” (anthracen type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; Chemical's "YX7700” (phenol aralkyl type epoxy resin); Osaka Gas Chemical's "PG-100", “CG-500”; Mitsubishi Chemical's "YL7760” (bisphenol AF type epoxy resin); Mitsubishi “YL7800” manufactured by Chemical Co., Ltd.
  • the mass ratio of the solid epoxy resin to the liquid epoxy resin is not particularly limited. However, it is preferably 10 or less, more preferably 5 or less, still more preferably 1 or less, still more preferably 0.5 or less, and particularly preferably 0.1 or less.
  • the epoxy equivalent of the epoxy resin is preferably 50 g / eq. ⁇ 5,000 g / eq. , More preferably 60 g / eq. ⁇ 2,000 g / eq. , More preferably 70 g / eq. ⁇ 1,000 g / eq. , Even more preferably 80 g / eq. ⁇ 500 g / eq. Is.
  • Epoxy equivalent is the mass of resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.
  • the weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 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 (C) 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. It is 0% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
  • the lower limit of the content of the (C) 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 0.1% by mass or more. It is more preferably 0.5% by mass or more, further preferably 1% by mass or more, still more preferably 3% by mass or more, and particularly preferably 5% by mass or more.
  • the mass ratio ((A) component / (C) component) of the (A) specific maleimide compound to the (C) epoxy resin in the resin composition is preferably 0.1 or more, more preferably 0.5 or more, and particularly preferably. Is 0.8 or more.
  • the upper limit of the mass ratio ((A) component / (C) component) of the (A) specific maleimide compound to the (C) epoxy resin in the resin composition is preferably 10 or less, more preferably 3 or less, and particularly preferably 1. It is less than 5.5.
  • the resin composition of the present invention may contain (D) an inorganic filler as an optional component.
  • (D) The inorganic filler is contained in the resin composition in the form of particles.
  • An inorganic compound is used as the material of the inorganic filler.
  • Examples of the material of the inorganic filler (D) include silica, alumina, aluminosilicate, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, and hydrotalcite.
  • Boehmite Aluminum Hydroxide, Magnesium Hydroxide, Calcium Carbonate, Magnesium Carbonide, Magnesium Oxide, Boron Nitride, Aluminum Nitride, Manganese Nitride, Aluminum Borate, Strontium Carbonate, Strontium Titanium, Calcium Titanium, Magnesium Titanium, Bismus Titanium , Titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate and the like.
  • silica or aluminosilicate is preferable, and silica is particularly preferable.
  • silica examples include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable.
  • the inorganic filler may be used alone or in combination of two or more at any ratio.
  • inorganic fillers include, for example, "UFP-30” manufactured by Denka Kagaku Kogyo Co., Ltd .; “SP60-05” and “SP507-05” manufactured by Nittetsu Chemical & Materials Co., Ltd .; manufactured by Admatex Co., Ltd.
  • the average particle size of the inorganic filler is not particularly limited, but is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, still more preferably 2 ⁇ m or less, still more preferably 1 ⁇ m or less, and particularly preferably 0. It is 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 the Mie scattering theory.
  • the inorganic filler can be measured by creating a particle size distribution of the inorganic filler on a volume basis by a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size.
  • 100 mg of an inorganic filler and 10 g of methyl ethyl ketone can be weighed in a vial and dispersed by ultrasonic waves for 10 minutes.
  • the measurement sample was measured using a laser diffraction type particle size distribution measuring device, the light source wavelengths used were blue and red, and the volume-based particle size distribution of the inorganic filler was measured by the flow cell method.
  • the average particle size was calculated as the median diameter.
  • Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by HORIBA, Ltd.
  • 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 is not particularly limited, but is preferably 100 m 2 / g or less, more preferably 70 m 2 / g or less, still more preferably 50 m 2 / g or less, and particularly preferably. Is 40 m 2 / g or less.
  • nitrogen gas is adsorbed on the sample surface using a specific surface area measuring device (Maxorb HM-1210 manufactured by Mountech) according to the BET method, and the specific surface area is calculated using the BET multipoint method. It can be obtained by.
  • a specific surface area measuring device Maxorb HM-1210 manufactured by Mountech
  • the inorganic filler may be a non-hollow inorganic filler having a porosity of 0% by volume (preferably non-hollow silica or non-hollow aluminosilicate), and a hollow inorganic filler having a porosity of more than 0% by volume. It may be (preferably hollow silica, hollow aluminosilicate) or may contain both.
  • the inorganic filler contains only a hollow inorganic filler (preferably hollow silica, hollow aluminosilicate) or a non-hollow inorganic filler (preferably non-hollow silica, non-hollow silica) from the viewpoint of suppressing the dielectric constant to be lower.
  • Hollow aluminosilicate and hollow inorganic filler are both included.
  • the porosity of the hollow inorganic filler is preferably 90% by volume or less, and more preferably 85 product% or less.
  • the lower limit of the porosity of the inorganic filler is not particularly limited, but for example, more than 0% by volume, 1% by volume or more, 5% by volume or more, 10% by volume or more, 20% by volume or more, It can be 30% by volume or more.
  • the pore ratio P (volume%) of the inorganic filler is the volume-based ratio of the total volume of one or two or more pores existing inside the particle to the total volume of the particle with respect to the outer surface of the particle (of the pores). Defined as total volume / volume of particles), for example, a measured value of the actual density of the inorganic filler DM (g / cm 3 ), and a theoretical value of the material density of the material forming the inorganic filler DT (g). It is calculated by the following formula (I) using / cm 3 ).
  • the actual density of the inorganic filler can be measured, for example, using a true density measuring device.
  • the true density measuring device include ULTRAPYCNOMETER1000 manufactured by QUANTACHROME.
  • nitrogen is used as the measurement gas.
  • the inorganic filler is preferably surface-treated with an appropriate surface treatment agent.
  • an appropriate surface treatment agent include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epyloxycyclohexyl) ethyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane.
  • Isocyanurate-based silane coupling agent such as 3-ureidopropyltrialkoxysilane
  • ureido-based silane coupling agent such as 3-ureidopropyltrialkoxysilane
  • mercapto-based silane coupling agent such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.
  • An isocyanate-based silane coupling agent such as 3-isocyanatepropyltriethoxysilane; an acid anhydride-based silane coupling agent such as 3-trimethoxysilylpropylsuccinic anhydride; a silane coupling agent such as; methyltrimethoxysilane, Dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimeth Examples thereof include alkylalkoxysilane compounds such as xysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, and tri
  • Examples of commercially available surface treatment agents include “KBM-1003” and “KBE-1003” (vinyl-based silane coupling agents) manufactured by Shin-Etsu Chemical Industry Co., Ltd .; “KBM-303", “KBM-402”, and “KBM-402”.
  • the degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler.
  • 100% by mass of the inorganic filler is preferably surface-treated with 0.2% by mass to 5% by mass of a surface treatment agent, and is surface-treated with 0.2% by mass to 3% by mass. It is more preferable that the surface is treated with 0.3% by mass to 2% by mass.
  • the degree of surface treatment with 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 0.2 mg / m 2 from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable.
  • 1.0 mg / m 2 or less is preferable, 0.8 mg / m 2 or less is more preferable, and 0.5 mg / m / More preferably, m 2 or less.
  • 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 (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. or the like can be used.
  • EMIA-320V manufactured by HORIBA, Ltd.
  • the content of the (D) inorganic filler 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 90% by mass or less, more preferably 90% by mass or less. It can be 85% by mass or less, more preferably 80% by mass or less, and particularly preferably 75% by mass or less.
  • the lower limit of the content of the (D) inorganic filler 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 and 1% by mass. % Or more, preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 50% by mass or more.
  • the mass ratio ((A) component / (D) component) of the (A) specific maleimide compound to the (D) inorganic filler in the resin composition is preferably 0.01 or more, more preferably 0.05 or more, particularly. It is preferably 0.1 or more.
  • the upper limit of the mass ratio ((A) component / (D) component) of the (A) specific maleimide compound to the (D) inorganic filler in the resin composition is preferably 1 or less, more preferably 0.5 or less, particularly. It is preferably 0.3 or less.
  • the resin composition of the present invention may contain (E) a curing accelerator as an optional component.
  • the (E) curing accelerator has a function of accelerating the curing of the (C) epoxy resin.
  • the curing accelerator examples include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, and the like. Of these, an imidazole-based curing accelerator is preferable from the viewpoint of improving the crosslinkability.
  • the curing accelerator may be used alone or in combination of two or more.
  • Examples of the phosphorus-based curing accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis (tetrabutylphosphonium) pyromeritate, and tetrabutylphosphonium hydro.
  • Alitriphenylphosphine salts such as genhexahydrophthalate, tetrabutylphosphonium 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenorate, di-tert-butyldimethylphosphonium tetraphenylphosphine; Methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-triltriphenylphosphoniumtetra-p-trilborate, tetraphenyl Triphenylphosphinephosphine, tetraphenylphosphinetetrap-trilborate, triphenylethylphosphoniumtetraphenylborate, tri
  • Arophenylphosphine / quinone addition reactants such as addition reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl-).
  • 2-Butenyl) phosphine tricyclophenylphosphine and other aliphatic phosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclophosphine, triphenylphosphine, tri-o -Triphenylphosphine, tri-m-triphenylphosphine, tri-p-tri Luphosphine, Tris (4-ethylphenyl) phosphine, Tris (4-propylphenyl) phosphine, Tris (4-isopropylphenyl) phosphine, Tris (4-butylphenyl) phosphine, Tris (4-tert-butylphenyl) phosphine, Tris (2,4-di
  • urea-based curing accelerator examples include 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-dimethylurea, 3- (4-) Methoxyphenyl) -1,1-dimethylurea, 3- (4-nitrophenyl) -1,1-dimethylurea, 3- [4- (4-methoxyphenoxy) phen
  • guanidine-based curing accelerator examples include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, and trimethylguanidine.
  • imidazole-based curing accelerator examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and the like.
  • imidazole-based curing accelerator a commercially available product may be used, for example, "1B2PZ”, “2MZA-PW”, “2PHZ-PW” manufactured by Shikoku Chemicals Corporation, and "P200-H50” manufactured by Mitsubishi Chemical Corporation. And so on.
  • the metal-based curing accelerator examples include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin.
  • organic metal complex examples include an organic cobalt complex such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, an organic copper complex 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, and organic manganese complexes such as manganese (II) acetylacetonate.
  • organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.
  • amine-based curing accelerator examples include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo. (5, 4, 0) -Undesen and the like can be mentioned.
  • amine-based curing accelerator a commercially available product may be used, and examples thereof include "MY-25” manufactured by Ajinomoto Fine-Techno Co., Ltd.
  • the content of the (E) 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 15% by mass or less, more preferably. It is 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 1% by mass or less.
  • the lower limit of the content of the (E) 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 001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.2% by mass or more, and the like.
  • the resin composition of the present invention may contain (F) polyimide resin as an optional component.
  • the polyimide resin is a resin having an imide bond in the repeating unit.
  • the polyimide resin also includes a modified polyimide resin such as a siloxane modified polyimide resin.
  • the (F) polyimide resin preferably contains an aromatic polyimide resin having no fat chain in the main chain.
  • the (F) polyimide resin is more preferably the formula (F1): in one embodiment.
  • X 1 , Y 1 and Y 2 are independently single-bonded, -CR 2- , -O-, -CO-, -S-, -SO-, -SO 2- , -CONH-, or-.
  • the xa unit may be the same or different for each unit.
  • the ya unit may be the same or different for each unit.
  • X 1 , Y 1 and Y 2 are independently single-bonded, -CR 2- , -O-, -CO-, -S-, -SO-, -SO 2- , -CONH-, or-. Shows NHCO-; preferably -CR 2- , -O-, or -CO-; more preferably -CR 2- , or -O-.
  • R independently represents a hydrogen atom and an alkyl group; preferably a hydrogen atom and a methyl group; more preferably a methyl group.
  • Ring X a , ring X b , and ring Y a each independently represent an aromatic ring which may have a substituent; preferably a group selected from an alkyl group, an alkenyl group, and an aryl group. It is a benzene ring which may be substituted, or a naphthalene ring which may be substituted with a group selected from an alkyl group, an alkenyl group, and an aryl group; more preferably, it is selected from an alkyl group, an alkenyl group, and an aryl group. It is a benzene ring which may be substituted with a group; more preferably a benzene ring which may be substituted with an alkyl group; particularly preferably a (unsubstituted) benzene ring.
  • Each R y1 independently represents a substituent; preferably an alkyl group, an alkenyl group, or an aryl group; more preferably an alkyl group.
  • Y1 independently indicates 0, 1, 2 or 3; preferably 0, 1 or 2; more preferably 0 or 1; particularly preferably 0.
  • xa indicates 0, 1, 2, 3, 4 or 5; preferably 1, 2, 3, 4 or 5; more preferably 2, 3, 4 or 5; even more preferably 3 4 or 5; particularly preferably 4.
  • ya indicates 0, 1, 2, 3, 4 or 5; preferably 0, 1, 2, 3 or 4; more preferably 0, 1, 2 or 3; even more preferably. 1, 2 or 3; particularly preferably 2.
  • yb indicates 0 or 1; preferably 1.
  • the (F) polyimide resin is more preferably of the formulas (F2-1) to (F2-4) :.
  • X 11 , X 12 , X 13 , X 14 , Y 11 , Y 12 and Y 2 are independently single-bonded, -CR 2- , -O-, -CO-, -S-, -SO-, respectively. , -SO 2- , -CONH-, or -NHCO-; Ring X a1 , ring X a2 , ring X a3 , ring X a4 , ring X b , ring Y a1 and ring Y a2 each independently represent an aromatic ring which may have a substituent; Other symbols are as described above.
  • It contains a resin having a repeating unit represented by, and more preferably, it contains a resin having a repeating unit represented by the formula (F2-1).
  • X 11 , X 12 , X 13 and X 14 are independently single-bonded, -CR 2- , -O-, -CO-, -S-, -SO-, -SO 2- , -CONH- , Or -NHCO-; preferably -CR 2- , -O-, or -CO-; more preferably -CR 2- , or -O-; even more preferably X 11 and.
  • X 14 is -O- and X 12 and X 13 are -CR 2- .
  • Y 11 , Y 12 and Y 2 are independently single-bonded, -CR 2- , -O-, -CO-, -S-, -SO-, -SO 2- , -CONH-, or-. Shows NHCO-; preferably -CR 2- , -O-, or -CO-; more preferably -CR 2- , or -O-; even more preferably Y 11 and Y 2 . -O- and Y 12 is -CR 2- .
  • Ring X a1 , ring X a2 , ring X a3 , ring X a4 , ring X b , ring Y a1 and ring Y a2 each independently represent an aromatic ring which may have a substituent; preferably.
  • the (F) polyimide resin is more preferably the formula (F3): in one embodiment.
  • R x1 and Ry2 each independently indicate a substituent; x1 and y2 independently indicate 0, 1, 2, 3 or 4; Other symbols are as described above. ] Includes resins with repeating units represented by.
  • R x1 and Ry2 each independently indicate a substituent; preferably an alkyl group, an alkenyl group, or an aryl group; more preferably an alkyl group.
  • x1 and y2 independently indicate 0, 1, 2, 3 or 4; preferably 0, 1, 2 or 3; more preferably 0, 1 or 2; even more preferably. , 0 or 1; particularly preferably 0.
  • the (F) polyimide resin is not particularly limited, but is known, for example, an imidization reaction between a diamine compound and a tetracarboxylic acid anhydride, an imidization reaction between a diisocyanate compound and a tetracarboxylic acid anhydride, and the like. Can be obtained by law.
  • the (F) polyimide resin a commercially available product may be used, and examples of the (F) commercially available polyimide resin include “Ricacoat SN20” and “Ricacoat PN20” manufactured by Shin Nihon Rika Co., Ltd.
  • the weight average molecular weight of the (F) polyimide resin is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, still more preferably 3000 or more, and particularly preferably 4000 or more.
  • the upper limit of the weight average molecular weight of the (F) polyimide resin is not particularly limited, but is preferably 200,000 or less, more preferably 150,000 or less, particularly preferably 100,000 or less, and particularly preferably 75,000 or less.
  • the weight average molecular weight here may be a value measured by a gel permeation chromatography (GPC) method (polystyrene conversion).
  • the glass transition temperature of the (F) polyimide resin is not particularly limited, but is preferably 50 ° C. to 400 ° C., more preferably 75 ° C. to 350 ° C., still more preferably 100 ° C. to 300 ° C., and particularly preferably 125 ° C.
  • the temperature is from ° C to 250 ° C.
  • the content of the (F) polyimide 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 15% by mass or less, more preferably 10. It is mass% or less, more preferably 5% by mass or less, and particularly preferably 1% by mass or less.
  • the lower limit of the content of the (F) polyimide resin 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 001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.2% by mass or more, and the like.
  • the resin composition of the present invention may further contain any additive as a non-volatile component.
  • additives include thermoplastic resins such as phenoxy resin, polyvinyl acetal resin, polyolefin resin, polysulfone resin, polyether sulfone resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, and polyester resin; rubber.
  • Organic fillers such as particles; Organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; Colorants such as phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, crystal violet, titanium oxide, and carbon black; Polymerization prohibiting agents such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as Benton and montmorillonite; silicone-based defoaming agents, acrylic defoaming agents, and fluorine.
  • Organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds
  • Colorants such as phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, crystal violet, titanium oxide, and carbon black
  • Polymerization prohibiting agents such as hydroquinone, catechol, pyrogallol, and phenothiazine
  • leveling agents such
  • Defoaming agents such as defoaming agents and vinyl resin defoaming agents; UV absorbers such as benzotriazole-based UV absorbers; Adhesive improvers such as ureasilane; Triazole-based adhesion-imparting agents and tetrazole-based adhesion-imparting agents Adhesion-imparting agents such as agents and triazine-based adhesion-imparting agents; Antioxidants such as hindered phenol-based antioxidants; Fluorescent whitening agents such as stylben derivatives; Fluorine-based surfactants, silicone-based surfactants, etc.
  • Phosphorus-based flame retardants eg phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus
  • nitrogen-based flame retardants eg melamine sulfate
  • halogen-based flame retardants eg antimony trioxide
  • phosphoric acid ester-based dispersants polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, cationic dispersants and other dispersants
  • borate-based stabilizers titanates.
  • stabilizers such as system stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers.
  • system stabilizers aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers.
  • aluminate-based stabilizers such as system stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers.
  • the resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the above-mentioned non-volatile component.
  • an arbitrary organic solvent as a volatile component in addition to the above-mentioned non-volatile component.
  • the (H) organic solvent a known solvent can be appropriately used, and the type thereof is not particularly limited.
  • the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate and ⁇ -.
  • 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 anisol; alcohol-based solvents such as methanol, ethanol, propanol, butanol and ethylene glycol Solvents: 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 lactate, 2-hydroxyiso Ester alcohol solvent such as methyl butyrate; ether alcohol solvent such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol
  • the above-mentioned aliphatic hydrocarbon-based solvent; aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene can be mentioned.
  • the organic solvent may be used alone or in combination of two or more at any ratio.
  • the content of the (H) organic solvent is not particularly limited, but when all the components in the resin composition are 100% by mass, for example, 60% by mass or less and 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 can be, for example, in an arbitrary preparation container with (A) a specific maleimide compound, (B) an active ester compound, (C) an epoxy resin, and if necessary, (A') another maleimide compound, if necessary. (B') Other curing agents as needed, (D) Inorganic filler as needed, (E) Hardening accelerator as needed, (F) Epoxy resin as needed, (G) as needed It can be produced by adding and mixing other additives and, if necessary, (H) an organic solvent in any order and / or partially or all at the same time.
  • the temperature can be appropriately set, and heating and / or cooling may be performed temporarily or from beginning to end.
  • the resin composition may be uniformly dispersed by stirring or shaking using, for example, a stirring device such as a mixer or a shaking device in the process of adding and mixing, or thereafter. Further, at the same time as stirring or shaking, defoaming may be performed under low pressure conditions such as under vacuum.
  • the resin composition of the present invention contains (A) a specific maleimide compound, (B) an active ester compound, and (C) an epoxy resin.
  • the cured product of the resin composition of the present invention may have a feature of having a high glass transition point (Tg). Therefore, in one embodiment, the glass transition temperature (Tg) measured as in Test Example 4 below is preferably 110 ° C. or higher, more preferably 130 ° C. or higher, still more preferably 140 ° C. or higher, and particularly preferably 150 ° C. or higher. Can be above ° C.
  • the cured product of the resin composition of the present invention may have a feature of being excellent in copper plating peel strength. Therefore, in one embodiment, the copper plating peel strength calculated from the load when the copper-plated conductor layer is formed on the cured product and the copper-plated conductor layer is peeled off in the vertical direction as in Test Example 2 below is preferable.
  • the upper limit is not particularly limited, but may be, for example, 10 kgf / cm or less.
  • the cured product of the resin composition of the present invention may have a feature of low dielectric loss tangent (Df). Therefore, in one embodiment, the dielectric positive contact (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 0.020 or less and 0.010 or less. , More preferably 0.009 or less, 0.008 or less, still more preferably 0.007 or less, 0.006 or less, particularly preferably 0.005 or less, 0.0045 or less, 0.004 or less.
  • the cured product of the resin composition of the present invention may have a feature of having a low relative permittivity (Dk). Therefore, in one embodiment, the relative permittivity (Dk) 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 5.0 or less, more preferably. It can be 4.0 or less, more preferably 3.5 or less, particularly preferably 3.2 or less, 3.0 or less.
  • the resin composition of the present invention may have a feature that the minimum melt viscosity is low. Therefore, in one embodiment, using a dynamic viscoelasticity measuring device as in Test Example 5 below, the frequency is 1 Hz, the strain is 5 degrees, the load is 100 g, the heating rate is 5 ° C / min, and the temperature range is 60 ° C to 180 ° C.
  • the minimum melt viscosity when measured can be preferably 4000 poise or less, 3000 poise or less, more preferably 2000 poise or less, 1700 poise or less, still more preferably 1500 poise or less, 1300 poise or less, and particularly preferably 1100 poise or less.
  • the cured product of the resin composition of the present invention may have a feature that the arithmetic average roughness (Ra) of the surface after the roughening treatment is low. Therefore, in one embodiment, the arithmetic average roughness (Ra) of the surface of the cured product after the roughening treatment measured as in Test Example 3 below is preferably 300 nm or less, more preferably 200 nm or less, still more preferably 150 nm. Below, it can be even more preferably 100 nm or less, and particularly preferably 70 nm or less. The lower limit is not particularly limited and may be, for example, 1 nm or more and 2 nm or more.
  • the resin composition of the present invention can be suitably used as a resin composition for insulating use, particularly as a resin composition for forming an insulating layer.
  • a resin composition for forming the insulating layer for forming the conductor layer (including the rewiring layer) formed on the insulating layer (resin for forming the insulating layer for forming the conductor layer). It can be suitably used as a composition).
  • a printed wiring board described later it can be suitably used as 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 requires a resin composition such as a resin sheet, a sheet-like laminated material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, and a component embedding resin.
  • a resin composition such as a resin sheet, a sheet-like laminated material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, and a component embedding resin.
  • a resin composition such as a resin sheet, a sheet-like laminated material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, and a component embedding resin.
  • the resin composition of the present invention is for a rewiring forming layer as an insulating layer for forming the rewiring layer.
  • a rewiring layer may be further formed on the sealing layer.
  • Step of laminating a temporary fixing film on a base material (2) A process of temporarily fixing a semiconductor chip on a temporary fixing film, (3) Step of forming a sealing layer on a semiconductor chip, (4) Step of peeling the base material and the temporary fixing film from the semiconductor chip, (5) A step of forming a rewiring forming layer as an insulating layer on the surface from which the base material and the temporary fixing film of the semiconductor chip are peeled off, and (6) a rewiring layer as a conductor layer is formed on the rewiring forming layer.
  • the resin composition of the present invention provides an insulating layer having good component embedding property, it can be suitably used even when the printed wiring board is a component built-in circuit board.
  • the resin composition of the present invention can be applied and used in a varnished state, but industrially, it is generally preferable to use the resin composition in the form of a sheet-like laminated material containing the resin composition.
  • the following resin sheets and prepregs 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 from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product having excellent insulating properties even if the cured product of the resin composition is a thin film. It is preferably 40 ⁇ m or less.
  • the lower limit of the thickness of the resin composition layer is not particularly limited, but may 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.
  • the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET”) or polyethylene naphthalate (hereinafter abbreviated as “PEN”).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • acrylics such as polymethylmethacrylate (PMMA)
  • PMMA polymethylmethacrylate
  • TAC triacetylcellulose
  • PES polyethersulfide
  • polyethers examples thereof include ketones and polyimides.
  • polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.
  • the metal foil When a metal foil is used as the support, examples of the metal foil include copper foil, aluminum foil, and the like, and copper foil is preferable.
  • the copper foil a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it.
  • the support may be matted, corona-treated, or antistatic-treated on the surface to be joined to the resin composition layer.
  • a support with a release layer having a release layer on the surface to be joined to the resin composition layer may be used.
  • the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. ..
  • a commercially available product may be used.
  • “SK-1” and “SK-1” manufactured by Lintec Corporation which are PET films having a release layer containing an alkyd resin-based mold release agent as a main component. Examples include “AL-5", “AL-7", “Lumilar T60” manufactured by Toray Industries, “Purex” manufactured by Teijin Ltd., and “Unipee” manufactured by Unitika Ltd.
  • the thickness of the support is not particularly limited, but is preferably in the range of 5 ⁇ m to 75 ⁇ m, and more preferably in the range of 10 ⁇ m to 60 ⁇ m.
  • the thickness of the entire support with a release layer is preferably in the above range.
  • the resin sheet may further contain any layer, if necessary.
  • an arbitrary layer include a protective film similar to the support provided on a surface of the resin composition layer that is not bonded to the support (that is, a surface opposite to the support). Be done.
  • the thickness of the protective film is not particularly limited, but is, for example, 1 ⁇ m to 40 ⁇ m.
  • a resin varnish prepared by dissolving the resin composition as it is in a liquid resin composition or in an organic solvent is applied onto a support using a die coater or the like, and further dried. It can be produced by forming a resin composition layer.
  • organic solvent examples include the same organic solvents as those described as the components of the resin composition.
  • the organic solvent may be used alone or in combination of two or more.
  • Drying may be carried out by a known method such as heating or 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
  • the resin composition layer can be formed by drying for a minute.
  • the resin sheet can be rolled up and stored. If 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 the base material for the prepreg such as glass cloth, aramid non-woven fabric, and liquid crystal polymer non-woven fabric can be used.
  • the thickness of the sheet-shaped 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-shaped fiber base material is not particularly limited. Usually, it is 10 ⁇ m or more.
  • the prepreg can be produced 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 above-mentioned resin sheet.
  • the sheet-shaped 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 (printed). It can be more preferably used for the interlayer insulating layer of the wiring board).
  • 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.
  • the printed wiring board can be manufactured, for example, by using the above-mentioned resin sheet by a method including the following steps (I) and (II).
  • (I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate
  • (II) The resin composition layer is cured (for example, thermosetting) to form an insulating layer.
  • the “inner layer substrate” used in the step (I) is a member that becomes a substrate of a printed wiring board, and is, 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. And so on. Further, the substrate may have a conductor layer on one side or both sides thereof, and the conductor layer may be patterned. An inner layer board in which a conductor layer (circuit) is formed on one side or both sides of the board may be referred to as an "inner layer circuit board".
  • an intermediate product in which an insulating layer and / or a conductor layer should be formed when the printed wiring board is manufactured is also included in the "inner layer substrate" in the present invention.
  • the printed wiring board is a circuit board with built-in components
  • an inner layer board containing built-in components may be used.
  • the inner layer substrate and the resin sheet can be laminated, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side.
  • the member for heat-pressing the resin sheet to the inner layer substrate include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). It is preferable not to press the heat-bonded member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.
  • the inner layer substrate and the resin sheet may be laminated by the vacuum laminating method.
  • the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C.
  • the heat crimping pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of .29 MPa to 1.47 MPa
  • the heat crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds.
  • Lamination can be carried out under reduced pressure conditions preferably with a pressure of 26.7 hPa or less.
  • Lamination can be performed by a commercially available vacuum laminator.
  • the commercially available vacuum laminator include a vacuum pressurizing laminator manufactured by Meiki Co., Ltd., a vacuum applicator manufactured by Nikko Materials, and a batch type vacuum pressurizing laminator.
  • the laminated resin sheet may be smoothed by pressing under normal pressure (under atmospheric pressure), for example, from the support side.
  • the press conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above-mentioned lamination.
  • the smoothing process can be performed by a commercially available laminator.
  • the laminating and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.
  • the support may be removed between steps (I) and step (II), or may be removed after step (II).
  • step (II) the resin composition layer is cured (for example, thermosetting) to form an insulating layer made of a cured product of the resin composition.
  • the curing conditions of the resin composition layer are not particularly limited, and the conditions usually adopted when forming the insulating layer of the printed wiring board may be used.
  • the thermosetting conditions of the resin composition layer differ depending on the type of the resin composition and the like, but in one embodiment, the curing temperature is preferably 120 ° C. to 240 ° C., more preferably 150 ° C. to 220 ° C., still more preferable. Is 170 ° C to 210 ° C.
  • the curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.
  • the resin composition layer Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is heated 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. Preheating may be preferably 5 to 150 minutes, more preferably 15 to 120 minutes, still more preferably 15 to 100 minutes.
  • steps (III) to (V) may be carried out according to various methods known to those skilled in the art used for manufacturing a printed wiring board.
  • the support is removed after the step (II)
  • the support may be removed between the steps (II) and the step (III), between the steps (III) and the step (IV), or the step ( It may be carried out between IV) and step (V).
  • the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board.
  • the printed wiring board of the present invention can be manufactured by using the above-mentioned prepreg.
  • the manufacturing method is basically the same as when a resin sheet is used.
  • 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.
  • the step (III) may be carried out by using, for example, a drill, a laser, a plasma, or the like, depending on the composition of the resin composition used for forming 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 removal is also performed.
  • the procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions usually used for forming the insulating layer of the printed wiring board can be adopted.
  • the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.
  • the swelling solution used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, preferably an alkaline solution, and the alkaline solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. preferable.
  • Examples of commercially available swelling liquids include "Swelling Dip Security Guns P" and "Swelling Dip Security Guns 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 ° C. to 90 ° C. for 1 minute 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 to 15 minutes.
  • the oxidizing agent used for the roughening treatment is not particularly limited, and examples thereof 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 performed by immersing the insulating layer in an oxidizing agent solution heated to 60 ° C. to 100 ° C. for 10 to 30 minutes.
  • the concentration of permanganate 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 "Dozing Solution Security P" manufactured by Atotech Japan.
  • the neutralizing solution used for the roughening treatment is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Security P” manufactured by Atotech Japan.
  • the treatment with a neutralizing solution can be performed by immersing the treated surface that has been roughened with an oxidizing agent in a neutralizing solution at 30 ° C to 80 ° C for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object roughened with an oxidizing agent in a neutralizing solution at 40 ° C to 70 ° C for 5 to 20 minutes is preferable.
  • the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, still more preferably 300 nm or less.
  • the lower limit is not particularly limited and may be, for example, 1 nm or more and 2 nm or more.
  • the root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.
  • Step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer.
  • the conductor material used for the conductor layer is not particularly limited.
  • the conductor layer is 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, nickel-chromium alloy, copper, etc.). Examples include layers formed from nickel alloys and copper-titanium alloys).
  • Nickel alloys, copper-titanium alloy alloy layers are preferred, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal layers, or nickel-chromium alloy alloy layers are more preferred, copper singles.
  • a metal layer is more preferred.
  • the conductor layer may have a single-layer structure, a single metal layer made of different types of metals or alloys, or a multi-layer structure in which two or more alloy layers 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 depends on the desired design of the printed wiring board, but is generally 3 ⁇ m to 35 ⁇ m, preferably 5 ⁇ m to 30 ⁇ m.
  • the conductor layer may be formed by plating.
  • the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern, and the semi-additive can be manufactured from the viewpoint of ease of manufacture. It is preferably formed by the method.
  • a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern
  • the semi-additive can be manufactured from the viewpoint of ease of manufacture. It is preferably formed by the method.
  • an example of forming the conductor layer by the semi-additive method will be shown.
  • a plating seed layer is formed on the surface of the insulating layer by electroless plating.
  • a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer.
  • the mask pattern is removed.
  • the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.
  • the conductor layer may be formed using a metal leaf.
  • the step (V) is carried out between the steps (I) and the step (II).
  • the support is removed and a metal leaf is laminated on the surface of the exposed resin composition layer.
  • the laminating of the resin composition layer and the metal foil may be carried out by a vacuum laminating method.
  • the laminating conditions may be the same as the conditions described for step (I).
  • step (II) is carried out to form an insulating layer.
  • the metal foil on the insulating layer can be used to form a conductor layer having a desired wiring pattern by a conventionally known technique such as a subtractive method or a modified semi-additive method.
  • the metal foil can be manufactured by a known method such as an electrolysis method or a rolling method.
  • Examples of commercially available metal foils include HLP foils and JXUT-III foils manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foils and TP-III foils manufactured by Mitsui Mining & Smelting Co., Ltd.
  • the 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 by using the printed wiring board of the present invention.
  • semiconductor devices examples include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.).
  • Example 1 23 parts of an isopropyridene group-containing maleimide compound (“MIR-5000-60T” manufactured by Nippon Kayaku Co., Ltd., a toluene solution of 60% by mass of a non-volatile component, a main component (non-volatile component): a maleimide compound represented by the following formula (A)) , Liquid naphthalene skeleton-containing epoxy resin (DIC's "HP-4032-SS", epoxy equivalent 144 g / eq.) 10 parts, active ester curing agent containing dicyclopentadiene type diphenol structure (DIC's "HPC-" 8000-65T ”, a toluene solution of 65% by mass of the non-volatile component, 30 parts of active ester group equivalent 223 g / eq.), And an inorganic filler (amine-based epoxysilane compound (“KBM573 ”manufactured by Shinetsu Chemical Industry Co.
  • Example 2 Instead of the active ester curing agent containing a dicyclopentadiene type diphenol structure (“HPC-8000-65T” manufactured by DIC), the active ester compound containing a naphthalene structure (“HPC-8150-62T” manufactured by DIC), a non-volatile component.
  • a resin composition (resin varnish) was obtained in the same manner as in Example 1 except that a 62 mass% toluene solution and 30 parts of an active ester group equivalent of 229 g / eq.) Were used.
  • Example 3 The amount of the isopropyridene group-containing maleimide compound (“MIR-5000-60T” manufactured by Nippon Kayaku Co., Ltd.) was changed from 23 parts to 18 parts, and an active ester curing agent containing a dicyclopentadiene-type diphenol structure (manufactured by DIC Co., Ltd.) was changed.
  • MIR-5000-60T manufactured by Nippon Kayaku Co., Ltd.
  • Example 4 The amount of the isopropyridene group-containing maleimide compound (“MIR-5000-60T” manufactured by Nippon Kayaku Co., Ltd.) was changed from 23 parts to 21 parts, and the active ester curing agent containing a dicyclopentadiene type diphenol structure (manufactured by DIC Co., Ltd.) was changed.
  • Example 5 Instead of the active ester curing agent containing a dicyclopentadiene type diphenol structure (“HPC-8000-65T” manufactured by DIC), the active ester compound containing a naphthalene structure (“HPC-8150-62T” manufactured by DIC), a non-volatile component. Using 62 parts by mass of a toluene solution and 25 parts of active ester group equivalent 229 g / eq. Except for the fact that 5 parts of a triazine skeleton-containing cresol novolac-based curing agent (“LA-3018-50P” manufactured by DIC, hydroxyl group equivalent: about 151, 2-methoxypropanol solution containing 50% non-volatile components) was used. A resin composition (resin varnish) was obtained in the same manner as in Example 1.
  • Example 6 A resin composition (resin varnish) was obtained in the same manner as in Example 5 except that two parts of the polyimide resin 1 obtained in Synthesis Example 1 were added.
  • Example 7 The amount of "SO-C2" manufactured by Admatex was changed from 80 parts to 60 parts, and instead, an inorganic filler having a hollow part (amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was used on the surface.
  • the resin composition (same as in Example 5) except that 20 parts of spherical silica having a treated hollow portion (“BA-S” manufactured by JGC Catalysts and Chemicals, Inc., average particle size 2.6 ⁇ m) was used. Resin varnish) was obtained.
  • Example 2 The same as in Example 1 except that 30 parts of the active ester compound (“HPC-8150-62T” manufactured by DIC, a toluene solution containing 62% by mass of the non-volatile component, and an active ester group equivalent of 229 g / eq.) was used. , A resin composition (resin varnish) was obtained.
  • a resin composition (resin varnish) was obtained in the same manner as in Example 1 except that "-62T", a toluene solution containing 62% by mass of the non-volatile component, and 30 parts of an active ester group equivalent (229 g / eq.) Were used.
  • ⁇ Test Example 1 Measurement of Relative Permittivity (Dk) and Dielectric Dissipation Factor (Df)>
  • Dk Relative Permittivity
  • Df Dielectric Dissipation Factor
  • A5 polyethylene terephthalate film
  • the resin compositions (resin varnishes) obtained in Examples and Comparative Examples were uniformly applied onto the release layer of this support so that the thickness of the resin composition layer after drying was 40 ⁇ m. Then, the resin composition was dried at 80 ° C. to 100 ° C. (average 90 ° C.) for 4 minutes to obtain a resin sheet containing a support and a resin composition layer.
  • the obtained resin sheet was heated at 190 ° C. for 90 minutes to heat-cure the resin composition layer. Then, 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 relative permittivity (Dk) and the dielectric loss tangent (Df) of the test piece were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using “HP8632B” manufactured by Azilent Technologies. Measurements were made for three test pieces, and the average values are shown in Table 1 below.
  • the laminated substrate was immersed in a neutralizing solution (reduction sholusin securigant P (aqueous solution of sulfuric acid) manufactured by Atotech Japan) at 40 ° C. for 5 minutes, and then the laminated substrate was dried at 80 ° C. for 30 minutes. Then, "evaluation substrate A" was obtained.
  • a neutralizing solution reduction sholusin securigant P (aqueous solution of sulfuric acid) manufactured by Atotech Japan
  • the evaluation substrate 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. Then, it was heated at 150 ° C. for 30 minutes to perform annealing treatment. After that, an etching resist was formed, and a pattern was formed by etching. Then, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 20 ⁇ m. Next, the annealing treatment was performed at 190 ° C. for 60 minutes to obtain "evaluation substrate B".
  • a notch was formed in the conductor layer of the evaluation substrate B to surround a rectangular portion having a width of 10 mm and a length of 100 mm.
  • One end of the rectangular part was peeled off and grasped with a gripping tool (autocom type testing machine "AC-50C-SL" manufactured by TSE Co., Ltd.). With a gripper, the rectangular part was peeled off in the vertical direction at a speed of 50 mm / min at room temperature, and the load (kgf / cm) when the 35 mm was peeled off was measured as the copper plating peel strength, and the following was measured. It is shown in Table 1.
  • ⁇ Test Example 3 Measurement of Surface Roughness Ra> The arithmetic average roughness Ra of the surface of the insulating layer of the evaluation substrate A produced in Test Example 2 (4) was measured. The measurement was carried out using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Becoin Sturments) with a VSI mode and a 50x lens, and the measurement range was 121 ⁇ m ⁇ 92 ⁇ m. This measurement was performed at 10 measurement points, and the average value is shown in Table 1 below.
  • WYKO NT3300 manufactured by Becoin Sturments
  • Tg> The resin sheet obtained in Test Example 1 was heated in an oven at 190 ° C. for 90 minutes to cure the resin composition layer. Then, the support was peeled off to obtain a cured product of the resin composition layer. This cured product was cut into a length of 20 mm and a width of 6 mm to obtain a cured product for evaluation.
  • the first TMA curve was obtained at a heating rate of 5 ° C / min from 25 ° C to 250 ° C by a tensile weighting method using a thermomechanical analyzer (TMA) manufactured by Rigaku. Then, the same measurement was performed on the same cured product for evaluation, and a second TMA curve was obtained. From the TMA curve obtained the second time, the value of the glass transition temperature Tg (° C.) was obtained and shown in Table 1 below.
  • Test Example 5 Measurement of minimum melt viscosity> The resin sheet obtained in Test Example 1 was peeled off from the support film, and the frequency was 1 Hz, the strain was 5 degrees, the load was 100 g, the temperature rise rate was 5 ° C / min, and the temperature was measured by the dynamic viscoelasticity measuring device G-3000 manufactured by UBM. Measurements were made in the range of 60 ° C to 180 ° C.
  • Table 1 below shows the amounts of raw materials used, the content of non-volatile components, and the measurement results of the test examples of the resin compositions of Examples and Comparative Examples.

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US20240110098A1 (en) * 2022-09-13 2024-04-04 Government Of The United States, As Represented By The Secretary Of The Air Force Highly aromatic and liquid-crystalline co-polyimides endcapped with aromatic groups and crosslinked products therefrom

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013234328A (ja) * 2013-06-18 2013-11-21 Ajinomoto Co Inc エポキシ樹脂組成物
JP2019044128A (ja) * 2017-09-06 2019-03-22 味の素株式会社 樹脂組成物
WO2020054526A1 (ja) * 2018-09-12 2020-03-19 日本化薬株式会社 マレイミド樹脂、硬化性樹脂組成物およびその硬化物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013234328A (ja) * 2013-06-18 2013-11-21 Ajinomoto Co Inc エポキシ樹脂組成物
JP2019044128A (ja) * 2017-09-06 2019-03-22 味の素株式会社 樹脂組成物
WO2020054526A1 (ja) * 2018-09-12 2020-03-19 日本化薬株式会社 マレイミド樹脂、硬化性樹脂組成物およびその硬化物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20240110098A1 (en) * 2022-09-13 2024-04-04 Government Of The United States, As Represented By The Secretary Of The Air Force Highly aromatic and liquid-crystalline co-polyimides endcapped with aromatic groups and crosslinked products therefrom
US11976231B2 (en) * 2022-09-13 2024-05-07 United States Of America As Represented By The Secretary Of The Air Force Highly aromatic and liquid-crystalline co- polyimides endcapped with aromatic groups and crosslinked products therefrom

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