Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
  • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W70/00—Package substrates; Interposers; Redistribution layers [RDL]
  • H10W70/60—Insulating or insulated package substrates; Interposers; Redistribution layers
  • H10W70/67—Insulating or insulated package substrates; Interposers; Redistribution layers characterised by their insulating layers or insulating parts
  • H10W70/69—Insulating materials thereof

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.
• a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked is known.
• 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.
• Df dielectric loss tangent
• Patent Document 1 maleimide compounds containing an isopropylidene group have been known.
• An object of the present invention is to provide a resin composition capable of suppressing the minimum melt viscosity to a lower level, obtaining a cured product having a low dielectric loss tangent (Df) and excellent copper plating peel strength.
• a resin having (B) vinylphenyl group and / or (meth) acryloyl group surprisingly, the minimum melt viscosity of the resin composition can be suppressed to a lower value, and the dielectric positive contact (Df) can be reduced. It has been found that a cured product having a low copper plating peel strength and excellent in copper plating peel strength can be obtained, and the present invention has been completed.
• 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 component (B) is a resin selected from a modified polyphenylene ether resin having a vinylphenyl group and / or a (meth) acryloyl group, and a modified polystyrene resin having a vinylphenyl group and / or a (meth) acryloyl group.
• the resin composition according to any one of the above [1] to [5].
• the content of the component (A) is 5% 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 [6]. Resin composition.
• the content of the component (B) is 5% by mass to 40% 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].
• Resin composition. [9] The above-mentioned [1] to [8], wherein the mass ratio of the component (A) to the component (B) (component (A) / component (B)) is 0.3 to 3.
• Resin composition. The resin composition according to any one of the above [1] to [9], further comprising (C) an inorganic filler.
• the resin composition according to the above [10] wherein the content of the component (C) is 40% by mass or more when the non-volatile component in the resin composition is 100% by mass.
• a semiconductor device including the printed wiring board according to the above [18].
• the minimum melt viscosity can be suppressed to a lower level, and a cured product having a low dielectric loss tangent (Df) and excellent copper plating peel strength 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) vinyl. Includes resins with phenyl and / or (meth) acryloyl groups.
• the resin composition of the present invention may further contain any component in addition to (A) the specific maleimide compound and (B) the resin having a vinylphenyl group and / or (meth) acryloyl group.
• Optional components include, for example, (A') other maleimide compounds, (C) inorganic fillers, (D) radical polymerization initiators, (E) thermoplastic resins, (F) elastomers, (G) and other additions.
• Agents and (H) organic solvents can be mentioned.
• 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 25% by mass or less, and particularly preferably 20% 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 5% by mass or more, still more preferably 8% by mass or more, and particularly preferably 10% 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 the product 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
• Nippon Kayaku Co., Ltd. Compound and the like.
• a maleimide resin maleimide compound containing an indane ring skeleton
• Publication No. 2020-500211 of the Japan Institute of Invention and Innovation may be used.
• 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) a resin having a vinyl phenyl group and / or (meth) acryloyl group.
• the (meth) acryloyl group means an acryloyl group or a methacryloyl group.
• the vinylphenyl group includes a 2-vinylphenyl group, a 3-vinylphenyl group, a 4-vinylphenyl group, or a group in which these aromatic carbon atoms are further substituted with one or more alkyl groups.
• the component (B) is usually a resin having two or more vinyl phenyl groups and / or (meth) acryloyl groups in one molecule.
• each molecule can react with the molecule of the component (B) or with the molecule of the component (A) or the component (A').
• the component (B) is preferably a thermoplastic resin having a vinylphenyl group and / or a (meth) acryloyl group.
• the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polystyrene resin, polyethylene resin, polypropylene resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, and polyphenylene ether resin.
• Polycarbonate resin, polyether ether ketone resin, polyester resin and the like, and the component (B) can be a modified resin having a vinylphenyl group and / or (meth) acryloyl group of these resins.
• the component (B) is more preferably a modified polyphenylene ether resin having a vinylphenyl group and / or a (meth) acryloyl group (hereinafter sometimes abbreviated as "modified polyphenylene ether resin"), and a vinylphenyl group and / or (. Meta)
• modified polystyrene resin A resin selected from modified polystyrene resins having an acryloyl group (hereinafter, may be abbreviated as "modified polystyrene resin”).
• the modified polyphenylene ether resin is preferably the formula (B-1) :.
• R 11 and R 12 each independently indicate an alkyl group
• R 13 , R 14 , R 21 , R 22 , R 23 and R 24 are independent hydrogen atoms or alkyl, respectively. Groups are indicated
• R 31 and R 32 each independently indicate a vinylphenyl group or a (meth) acryloyl group
• Y is a single bond, -C (R y ) 2- , -O-, -CO-. , -S-, -SO-, or -SO 2-
• Ry indicates a hydrogen atom or an alkyl group, respectively
• Z indicates a single bond or an alkylene group
• n and m indicate , Independently indicate an integer of 1 or more
• p indicates 0 or 1.
• the n unit and the m unit may be the same or different for each unit.
• R 11 and R 12 each independently represent an alkyl group, preferably a methyl group.
• R 13 and R 14 each independently represent a hydrogen atom or an alkyl group, and are preferably a hydrogen atom.
• R 21 and R 22 each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
• R 23 and R 24 independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and more preferably one of R 23 and R 24 is a methyl group. And the other is a hydrogen atom.
• R 31 and R 32 independently represent a vinylphenyl group or a (meth) acryloyl group, and Z represents a single bond or an alkylene group.
• the alkylene group means a linear, branched or cyclic divalent saturated hydrocarbon group.
• the alkylene group is preferably an alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group include -CH 2- , -CH 2 -CH 2- , -CH (CH 3 )-, -CH 2 -CH 2 -CH 2- , -CH 2 -CH (CH 3 )-, -CH (CH 3 ) -CH 2- , -C (CH 3 ) 2- and the like can be mentioned.
• R 31 and R 32 are vinylphenyl groups and Z is an alkylene group (particularly preferably ⁇ CH2- ), or R 31 and R 32 are (meth) acryloyl groups. And Z is a single bond.
• Y represents a single bond, -C (R y ) 2- , -O-, -CO-, -S-, -SO-, or -SO 2- , preferably a single bond, -C (R y) . ) 2 -or -O-, more preferably a single bond.
• Ry independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom or a methyl group.
• n and m each independently indicate an integer of 1 or more, preferably an integer of 1 to 200, and more preferably an integer of 1 to 100.
• p represents 0 or 1, preferably 1.
• modified polyphenylene ether resin examples include, for example, "OPE-2St 1200” and “OPE-2St 2200” (vinyl benzyl modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Company; "SA9000” manufactured by SABIC Innovative Plastics Co., Ltd. , "SA9000-111” (methacryl-modified polyphenylene ether resin) and the like.
• the modified polystyrene resin is preferably of the formula (B-2a) :.
• R 41 , R 42 and R 43 each independently represent a hydrogen atom or an alkyl group; R 44 each independently represents an alkyl group; s is an integer of 0 to 3. show.
• R 51 , R 52 and R 53 each independently represent a hydrogen atom or an alkyl group; R 54 each independently represents an alkyl group; t is an integer of 0 to 3. show.
• It is a resin having a repeating unit represented by.
• the repeating unit of the formula (B-2a) and the repeating unit of the formula (B-2b) may be the same or different for each unit.
• R 41 , R 42 , R 43 , R 51 , R 52 and R 53 each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
• R 44 and R 54 each independently represent an alkyl group, preferably an ethyl group or a methyl group.
• s represents an integer of 0 to 3, preferably 0 or 1, and more preferably 0.
• t represents an integer of 0 to 3, preferably 0 or 1.
• the molar content of the repeating unit of the formula (B-2a) is 8 mol% to 54 mol, assuming that the total of the repeating unit of the formula (B-2a) and the repeating unit of the formula (B-2b) is 100 mol%. % Is preferable.
• modified polystyrene resins examples include “ODV-XET (X03)”, “ODV-XET (X04)”, and “ODV-XET (X05)” (styrene-divinylbenzene) manufactured by Nittetsu Chemical & Materials Co., Ltd. Copolymer) and the like.
• the functional group equivalent of the component (B) is preferably 250 g / eq. ⁇ 2500 g / eq. , More preferably 300 g / eq. ⁇ 1500 g / eq. Is.
• the functional group equivalent of the component (B) represents the mass of the resin per equivalent of vinylphenyl group or (meth) acryloyl group.
• the weight average molecular weight (Mw) of the component (B) is preferably 1000 to 40,000, more preferably 1000 to 10000, and particularly preferably 1000 to 5000.
• the number average molecular weight (Mn) of the component (B) is preferably 1000 to 40,000, more preferably 1000 to 10000, and particularly preferably 1000 to 5000.
• 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 content of the component (B) 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 50% by mass. % Or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 25% by mass or less.
• the lower limit of the content of the component (B) 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 preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and particularly preferably 15% by mass or more.
• the mass ratio ((A) component / (B) component) of the (A) specific maleimide compound to the (B) component in the resin composition is preferably 0.1 or more, more preferably 0.3 or more, and particularly preferably. It is 0.5 or more.
• the upper limit of the mass ratio ((A) component / (B) component) of the (A) specific maleimide compound to the (B) component in the resin composition is preferably 5 or less, more preferably 3 or less, and particularly preferably 1. It is 5 or less.
• the resin composition of the present invention may contain (C) an inorganic filler as an optional component.
• (C) The inorganic filler is contained in the resin composition in the form of particles.
• An inorganic compound is used as the material of the inorganic filler.
• Examples of the material of the inorganic filler (C) 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 inorganic filler after the surface treatment 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 (C) 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 80% by mass or less, more preferably 75% by mass or less, and particularly preferably 70% by mass or less.
• the lower limit of the content of the (C) 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 30% by mass or more, still more preferably 40% by mass or more, still more preferably 50% by mass or more, and particularly preferably 60% by mass or more.
• the mass ratio ((A) component / (C) component) of the (A) specific maleimide compound to the (C) inorganic filler in the resin composition is preferably 0.05 or more, more preferably 0.1 or more, particularly. It is preferably 0.2 or more.
• the upper limit of the mass ratio ((A) component / (C) component) of the (A) specific maleimide compound to the (C) inorganic filler in the resin composition is preferably 2 or less, more preferably 1 or less, and particularly preferably 1. It is 0.5 or less.
• the resin composition of the present invention may further contain (D) a radical polymerization initiator as an optional component.
• the radical polymerization initiator may be, for example, a thermal polymerization initiator that generates free radicals when heated.
• the radical polymerization initiator (D) may be a polymerization initiator of a radically polymerizable component containing the components (A) to (B) described above.
• the radical polymerization initiator may be used alone or in any combination of two or more.
• Examples of the (D) radical polymerization initiator include peroxide-based radical polymerization initiators, azo-based radical polymerization initiators, and the like. Of these, a peroxide-based radical polymerization initiator is preferable.
• peroxide radical polymerization initiator examples include hydroperoxide compounds such as 1,1,3,3-tetramethylbutylhydroperoxide; tert-butylcumyl peroxide, di-tert-butyl peroxide, and di.
• -Tert-Hexyl peroxide dicumyl peroxide, 1,4-bis (1-tert-butylperoxy-1-methylethyl) benzene, 2,5-dimethyl-2,5-bis (tert-butylperoxy) )
• Dialkyl peroxide compounds such as hexane; diacyl peroxide compounds such as dilauroyl peroxide, didecanoyl peroxide, dicyclohexylperoxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate; tert-butylper.
• azo-based radical polymerization initiator examples include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2. '-Azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methyl) Azobisisobuty compound such as ethyl) azo] formamide, 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile; 2,2'-azobis [2-methyl-N- [1,1-bis (hydroxymethyl)) -2-Hydroxyethyl] propionamide], 2,2'-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide], 2,2'-azobis [2-methyl- N- [2- (1-Hydr
• Examples of commercially available products of the radical polymerization initiator (D) include “Perbutyl C”, “Perbutyl A”, “Perbutyl P”, “Perbutyl L”, “Perbutyl O”, and “Perbutyl ND” manufactured by NOF CORPORATION.
• “Perbutyl Z”, “Perbutyl I”, “Park Mill P”, “Park Mill D”, “Perhexyl D”, “Perhexyl A”, “Perhexyl I”, “Perhexyl Z”, “Perhexyl ND”, “Perhexyl O” Examples thereof include “perhexyl PV” and “perhexyl O”.
• the content of the (D) radical polymerization initiator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 5% by mass or less, more preferably. Can be 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.8% by mass or less.
• the lower limit of the content of the (D) radical polymerization initiator 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.
• 0.0001% by mass or more preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, in particular. It may be preferably 0.3% by mass or more.
• the resin composition of the present invention may further contain (E) a thermoplastic resin as an optional component.
• the (E) thermoplastic resin described here is a component other than those corresponding to the components (A) to (B) described above.
• thermoplastic resin as the component (E) examples include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, and polyphenylene ether resin. , Polycarbonate resin, polyether ether ketone resin, polyester resin and the like. Above all, from the viewpoint of remarkably obtaining the effect of the present invention, it is preferable that the (E) thermoplastic resin contains a resin selected from a phenoxy resin and a polyimide resin. Further, the thermoplastic resin may be used alone or in combination of two or more.
• phenoxy resin examples include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantan skeleton, and terpene.
• the terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.
• phenoxy resin examples include "1256” and “4250” manufactured by Mitsubishi Chemical Co., Ltd. (both are bisphenol A skeleton-containing phenoxy resins); “YX8100” manufactured by Mitsubishi Chemical Co., Ltd. (bisphenol S skeleton-containing phenoxy resin); “YX6954” (bisphenol acetophenone skeleton-containing phenoxy resin); “FX280” and “FX293” manufactured by Nippon Steel & Sumitomo Metal Corporation; "YL7500BH30", “YX6954BH30", “YX7553”, “YX7553BH30” manufactured by Mitsubishi Chemical Co., Ltd. Examples thereof include “YL7769BH30", “YL6794", "YL7213", “YL7290", “YL7482” and “YL7891T30”;
• polyvinyl acetal resin examples include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferable.
• Specific examples of the polyvinyl acetal resin include "Electrified Butyral 4000-2", “Electrified Butyral 5000-A”, “Electrified Butyral 6000-C”, and “Electrified Butyral 6000-EP” manufactured by Sekisui Chemical Co., Ltd .; Sekisui Chemical Co., Ltd.
• polystyrene resin examples include ethylene-based copolymers such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer.
• Resin Polyethylene, polyethylene-propylene block copolymers and other polyolefin-based polymers can be mentioned.
• polyamide-imide resin examples include "Vilomax HR11NN” and “Vilomax HR16NN” manufactured by Toyobo Co., Ltd.
• polyamide-imide resin examples include modified polyamide-imides such as “KS9100” and “KS9300” (polysiloxane skeleton-containing polyamide-imide) manufactured by Hitachi Chemical Co., Ltd.
• polyether sulfone resin examples include "PES5003P” manufactured by Sumitomo Chemical Co., Ltd.
• polysulfone resin examples include polysulfones “P1700” and “P3500” manufactured by Solvay Advanced Polymers.
• polyester resin examples include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethylterephthalate resin and the like.
• the polyimide resin also includes a modified polyimide resin such as a siloxane modified polyimide resin.
• the polyimide resin preferably contains an aromatic polyimide resin having no fat chain in the main chain.
• the polyimide resin is more preferably the formula (E1): 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 polyimide resin is more preferably represented by the formulas (E2-1) to (E2-4) :.
• 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 (E2-1).
• 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 polyimide resin is more preferably the formula (E3): 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 polyimide resin is not particularly limited, but is obtained by a known synthetic method such as an imidization reaction between a diamine compound and a tetracarboxylic acid anhydride, or an imidization reaction between a diisocyanate compound and a tetracarboxylic acid anhydride. be able to.
• a commercially available product may be used as the polyimide resin, and examples of the commercially available polyimide resin include "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin Nihon Rika Co., Ltd.
• 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 weight average molecular weight (Mw) of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, and particularly preferably 20,000 or more, from the viewpoint of remarkably obtaining the effect of the present invention. It is preferably 70,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less.
• the content of the (E) thermoplastic resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, the desired effect of the present invention is remarkably obtained. From the viewpoint, it may be preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, still more preferably 7% by mass or less, and particularly preferably 5% by mass or less.
• the lower limit of the content of the (E) thermoplastic 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.
• 0.01% by mass or more 0.05% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, still more preferably 2% by mass or more. , Particularly preferably 3% by mass or more.
• the resin composition of the present invention may further contain (F) an elastomer as an optional component.
• the (F) elastomer described here is a component other than those corresponding to the components (A) to (B) described above.
• the elastomer as the component (F) is a resin having flexibility, preferably a resin having rubber elasticity or a resin polymerizing with other components to exhibit rubber elasticity.
• the rubber elasticity include a resin that conforms to the Japanese Industrial Standards (JIS K7161) and exhibits an elastic modulus of 1 GPa or less when a tensile test is performed at a temperature of 25 ° C. and a humidity of 40% RH.
• the (F) elastomer has a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisobutylene structure, a polyisobutylene structure, a polycarbonate structure, and polystyrene in the molecule. It is preferable that the resin has one or more structures selected from the structures. "(Meta) acrylate” refers to methacrylate and acrylate.
• the (F) elastomer is preferably one or more selected from a resin having a glass transition temperature (Tg) of 25 ° C. or lower and a resin having a glass transition temperature (Tg) of 25 ° C. or lower and being liquid.
• the glass transition temperature of the resin having a glass transition temperature (Tg) of 25 ° C. or lower is preferably 20 ° C. or lower, more preferably 15 ° C. or lower.
• the lower limit of the glass transition temperature is not particularly limited, but may be usually ⁇ 15 ° C. or higher.
• the resin that is liquid at 25 ° C. is preferably a resin that is liquid at 20 ° C. or lower, and more preferably a resin that is liquid at 15 ° C. or lower.
• the glass transition temperature can be measured by DSC (Differential Scanning Calorimetry).
• (F) Elastomer is usually an amorphous resin component that can be dissolved in an organic solvent.
• this (F) elastomer one type may be used alone, or two or more types may be used in combination at any ratio.
• Examples of the (F) elastomer include a resin containing a polybutadiene structure.
• the polybutadiene structure may be contained in the main chain or the side chain. Further, the polybutadiene structure may be partially or wholly hydrogenated.
• a resin containing a polybutadiene structure may be referred to as a "polybutadiene resin".
• Specific examples of the polybutadiene resin include "Ricon 130MA8", “Ricon 130MA13", “Ricon 130MA20”, “Ricon 131MA5", "Ricon 131MA10", “Ricon 131MA17”, “Ricon 131MA20", and “Ricon” manufactured by Clay Valley.
• the polybutadiene resin a linear polyimide using a hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride as raw materials (Japanese Patent Laid-Open No. 2006-37083, International Publication No. 2008/153208). ), Phenolic hydroxyl group-containing butadiene and the like.
• the content of the butadiene structure of the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass.
• JP-A-2006-37083 and International Publication No. 2008/153208 can be referred to, and the contents thereof are incorporated in the present specification.
• Examples of the (F) elastomer include a resin containing a poly (meth) acrylate structure.
• a resin containing a poly (meth) acrylate structure may be referred to as a "poly (meth) acrylic resin".
• Specific examples of the poly (meth) acrylic resin include Teisan resin manufactured by Nagase ChemteX, "ME-2000", “W-116.3”, “W-197C", and "KG-25” manufactured by Negami Kogyo. , "KG-3000” and the like.
• Examples of the (F) elastomer include a resin containing a polycarbonate structure.
• a resin containing a polycarbonate structure may be referred to as a "polycarbonate resin".
• Specific examples of the polycarbonate resin include “T6002" and “T6001” (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and “C-1090", “C-2090” and “C-3090” (polycarbonate diol) manufactured by Kuraray. And so on.
• a linear polyimide made from a hydroxyl group-terminated polycarbonate, a diisocyanate compound and a tetrabasic acid anhydride can also be used.
• the content of the carbonate structure of the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass.
• the details of the polyimide resin can be referred to in International Publication No. 2016/129541, which is incorporated herein by reference.
• Examples of the (F) elastomer include a resin containing a polysiloxane structure.
• a resin containing a polysiloxane structure may be referred to as a "siloxane resin".
• Specific examples of the siloxane resin include "SMP-2006”, “SMP-2003PGMEA”, “SMP-5005PGMEA” manufactured by Shinetsu Silicone Co., Ltd., an amine group-terminated polysiloxane, and a linear polyimide made from tetrabasic acid anhydride.
• International Publication No. 2010/053185, JP-A-2002-12667, JP-A-2000-31386, etc.) and the like can be mentioned.
• Examples of the (F) elastomer include a resin containing a polyalkylene structure or a polyalkylene oxy structure.
• a resin containing a polyalkylene structure may be referred to as an "alkylene resin”.
• a resin containing a polyalkylene oxy structure may be referred to as an "alkylene oxy resin”.
• As the polyalkylene oxy structure a polyalkylene oxy structure having 2 to 15 carbon atoms is preferable, a polyalkylene oxy structure having 3 to 10 carbon atoms is more preferable, and a polyalkylene oxy structure having 5 to 6 carbon atoms is particularly preferable.
• Specific examples of the alkylene resin and the alkyleneoxy resin include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers Corporation.
• Examples of the (F) elastomer include a resin containing a polyisoprene structure.
• a resin containing a polyisoprene structure may be referred to as "isoprene resin".
• Specific examples of the isoprene resin include "KL-610" and "KL613" manufactured by Kuraray.
• Examples of the (F) elastomer include a resin containing a polyisobutylene structure.
• a resin containing a polyisobutylene structure may be referred to as "isobutylene resin".
• Specific examples of the isobutylene resin include "SIBSTAR-073T” (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D” (styrene-isobutyrene block copolymer) manufactured by Kaneka.
• Examples of the (F) elastomer include a resin containing a polystyrene structure.
• a resin containing a polystyrene structure may be referred to as "styrene resin”.
• Examples of the styrene resin include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), and styrene-.
• SEPS Ethylene-propylene-styrene block copolymer
• SEEPS styrene-ethylene-ethylene-propylene-styrene block copolymer
• SBBS styrene-butadiene-butylene-styrene block copolymer
• SEPS Ethylene-propylene-styrene block copolymer
• SEEPS styrene-ethylene-ethylene-propylene-styrene block copolymer
• SBBS styrene-butadiene-butylene-styrene block copolymer
• styrene-butadiene diblock examples thereof include a copolymer, a hydride styrene-butadiene block copolymer, a hydride styrene-isoprene block copolymer, and a hydride styrene-butadiene random copo
• styrene resin examples include hydrogenated styrene-based thermoplastic elastomers "H1041”, “Toughtech H1043”, “Toughtech P2000”, and “Toughtech MP10” (manufactured by Asahi Kasei Co., Ltd.); epoxidized styrene-butadiene thermoplastic elastomer "Epofriend”.
• the number average molecular weight (Mn) of the elastomer is preferably 1,000 or more, more preferably 1500 or more, still more preferably 3000 or more, particularly preferably 5000 or more, and preferably 1,000,000 or less. It is preferably 900,000 or less.
• the number average molecular weight (Mn) can be measured in terms of polystyrene using GPC (gel permeation chromatography).
• the content of the (F) elastomer in the resin composition is not particularly limited, but from the viewpoint of significantly obtaining the desired effect of the present invention when the non-volatile component in the resin composition is 100% by mass. It can be preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, still more preferably 7% by mass or less, and particularly preferably 5% by mass or less.
• the lower limit of the content of the (F) elastomer 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.
• 0.05% by mass or more preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, still more preferably 2% by mass or more, particularly. It may be preferably 3% by mass or more.
• the resin composition of the present invention may further contain any additive as a non-volatile component.
• additives include heat of epoxy resin, epoxy acrylate resin, urethane acrylate resin, urethane resin, cyanate resin, polyimide resin, benzoxazine resin, unsaturated polyester resin, phenol resin, melamine resin, silicone resin and the like.
• Curing resin Curing accelerators such as imidazole-based curing accelerators, phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators; phenol-based curing agents, Naftor-based curing agents, acid anhydride-based curing agents, thiol-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, carbodiimide-based curing agents, imidazole-based curing agents, curing agents such as active ester compounds; rubber particles, etc.
• Curing accelerators such as imidazole-based curing accelerators, phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators; phenol-based curing agents, Naftor-based curing agents, acid anhydride
• Organic fillers organic metal compounds such as organic copper compounds, organic zinc compounds, organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, crystal violet, titanium oxide, carbon black; hydroquinone, Anti-polymerization agents such as catechol, pyrogallol, phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as Benton and montmorillonite; Defoaming agents such as foaming agents and vinyl resin-based defoaming agents; UV absorbers such as benzotriazole-based ultraviolet absorbers; Adhesive improvers such as ureasilane; Triazole-based adhesion-imparting agents, Tetrazole-based adhesion-imparting agents, Adhesion-imparting agents such as triazine-based adhesion-imparting agents; Antioxidants such as hindered phenol-based antioxidants and hindered
• stabilizers such as stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers.
• stabilizers such as stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers.
• one type may be used alone, or two or more types may be used in combination at any ratio.
• the content of other additives can be appropriately set by those skilled in the art.
• the resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the 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 may be, for example, a resin having (A) a specific maleimide compound, (B) a vinylphenyl group and / or a (meth) acryloyl group in an arbitrary preparation container, and (A') or the like, if necessary.
• 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, and (B) a resin having a vinylphenyl group and / or a (meth) acryloyl group.
• A a specific maleimide compound
• B a resin having a vinylphenyl group and / or a (meth) acryloyl group.
• 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, 0.005 or less, particularly preferably 0.004 or less, 0.0035 or less, 0.003 or less. obtain.
• Df dielectric positive contact
• the resin composition of the present invention may have a feature that the minimum melt viscosity is low. Therefore, in one embodiment, the frequency is 1 Hz, the strain is 5 degrees, the load is 100 g, the temperature rise rate is 5 ° C./min, and the temperature range is 60 ° C. to 180 ° C. using a dynamic viscoelasticity measuring device as in Test Example 4 below.
• the minimum melt viscosity as measured can be preferably 2500 poise or less, more preferably 2000 poise or less, still more preferably 1800 poise 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 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 may be even more preferably 130 nm or less, and particularly preferably 110 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 further 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 the neutralizing solution can be performed by immersing the treated surface that has been roughened with the oxidizing agent in the neutralizing solution at 30 ° C to 80 ° C for 5 to 30 minutes. From the viewpoint of workability 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 containing 60% by mass of a non-volatile component, a main component (non-volatile component): a maleimide compound represented by the following formula (A)) , Vinyl benzyl-modified polyphenylene ether resin ("OPE-2St 1200” manufactured by Mitsubishi Gas Chemicals, Inc., toluene solution with number average molecular weight of 1200, non-volatile content of 65% by mass), polymerization initiator (peroxide manufactured by Nichiyu Co., Ltd.
• Perbutyl (registered trademark) C ) 0.5 part, spherical silica surface-treated with an inorganic filler (amine-based alkoxysilane compound ("KBM573 "manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (" SO-C2 "manufactured by Admatex), Average particle size 0.5 ⁇ m, specific surface area 5.8 m 2 / g)) 50 parts, and ester-type phenoxy resin (“YL7891T30” manufactured by Mitsubishi Chemical Co., Ltd., 1: 1 solution of MEK and cyclohexanone with a solid content of 30% by mass) 10 parts were mixed and uniformly dispersed using a high-speed rotary mixer to obtain a resin composition (resin varnish).
• an inorganic filler amine-based alkoxysilane compound
• SO-C2 manufactured by Admatex
• Average particle size 0.5 ⁇ m, specific surface area 5.8 m 2 / g
• Example 2 Instead of 20 parts of vinylbenzyl-modified polyphenylene ether resin (Mitsubishi Gas Chemicals "OPE-2St 1200"), styrene-divinylbenzene copolymer (Nittetsu Chemical & Materials “ODV-XET (X04)", weight A resin composition (resin varnish) was obtained in the same manner as in Example 1 except that 20 parts (average molecular weight 3110, vinyl group equivalent 380 g / eq., 65 mass% solution) was used.
• OPE-2St 1200 styrene-divinylbenzene copolymer
• ODV-XET (X04) weight A resin composition (resin varnish) was obtained in the same manner as in Example 1 except that 20 parts (average molecular weight 3110, vinyl group equivalent 380 g / eq., 65 mass% solution) was used.
• Example 3 Instead of 20 parts of vinylbenzyl-modified polyphenylene ether resin (Mitsubishi Gas Chemical Company "OPE-2St 1200"), 20 parts of methacrylic-modified polyphenylene ether resin (SABIC "SA9000-111", number average molecular weight 1850 to 1950) A resin composition (resin varnish) was obtained in the same manner as in Example 1 except that it was used.
• Example 4 The amount of the isopropyridene group-containing maleimide compound (“MIR-5000-60T” manufactured by Nippon Kayaku Co., Ltd.) has been changed from 23 parts to 18 parts, and the biphenyl aralkyl type maleimide compound (“MIR-3000” manufactured by Nippon Kayaku Co., Ltd.) has been changed.
• a resin composition (resin varnish) was obtained in the same manner as in Example 1 except that 5 parts of MEK / toluene mixed solution having a non-volatile content of 70% was used.
• Example 5 The amount of the isopropyridene group-containing maleimide compound (“MIR-5000-60T” manufactured by Nippon Kayaku Co., Ltd.) has been changed from 23 parts to 21 parts, and the liquid aliphatic maleimide compound (“BMI” manufactured by Designer Moleculars Co., Ltd.) has been changed.
• a resin composition (resin varnish) was obtained in the same manner as in Example 1 except that 2 parts were used.
• Example 6 Instead of 10 parts of an ester-type phenoxy resin (Mitsubishi Chemical's "YL7891T30", a 1: 1 solution of MEK and cyclohexanone with a solid content of 30% by mass), an elastomer (styrene-ethylene / butylene-styrene block co-weight manufactured by Kraton) A resin composition (resin varnish) was obtained in the same manner as in Example 1 except that 3 parts of the coalesced "FG1924") were used.
• an ester-type phenoxy resin Mitsubishi Chemical's "YL7891T30"
• MEK cyclohexanone with a solid content of 30% by mass
• elastomer styrene-ethylene / butylene-styrene block co-weight manufactured by Kraton
• Example 7 The amount of the ester-type phenoxy resin (“YL7891T30” manufactured by Mitsubishi Chemical Co., Ltd., a 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass) was changed from 10 parts to 5 parts, and the polyimide resin obtained in Synthesis Example 1 was used. A resin composition (resin varnish) was obtained in the same manner as in Example 1 except that 7 parts of 1 were added.
• YL7891T30 manufactured by Mitsubishi Chemical Co., Ltd., a 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass
• Example 8> The amount of "SO-C2" manufactured by Admatex was changed from 50 parts to 40 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 6) except that 10 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.
• ⁇ 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
• ⁇ Test Example 4 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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• 2021
  • 2021-11-11 TW TW110142075A patent/TW202233705A/zh unknown
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