WO2022004756A1 - Composition de résine - Google Patents

Composition de résine Download PDF

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Publication number
WO2022004756A1
WO2022004756A1 PCT/JP2021/024644 JP2021024644W WO2022004756A1 WO 2022004756 A1 WO2022004756 A1 WO 2022004756A1 JP 2021024644 W JP2021024644 W JP 2021024644W WO 2022004756 A1 WO2022004756 A1 WO 2022004756A1
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Prior art keywords
group
resin composition
resin
curing agent
mass
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PCT/JP2021/024644
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English (en)
Japanese (ja)
Inventor
奈那 滑方
正和 中沢
嘉生 西村
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味の素株式会社
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Application filed by 味の素株式会社 filed Critical 味の素株式会社
Priority to JP2022534065A priority Critical patent/JP7414143B2/ja
Priority to CN202180042093.2A priority patent/CN115698188A/zh
Publication of WO2022004756A1 publication Critical patent/WO2022004756A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits

Definitions

  • the present invention relates to a resin composition. Further, the present invention relates to a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition.
  • Patent Document 1 discloses a resin composition.
  • an insulating layer used for a wiring board provided with an embedded wiring layer is required to suppress the occurrence of warpage and to have excellent dielectric properties and adhesion with a copper foil.
  • An object of the present invention is a resin composition capable of suppressing the occurrence of warpage and obtaining a cured product having excellent dielectric properties and adhesion between copper foils (copper foil adhesion); a resin containing the resin composition.
  • Sheet A printed wiring board having an insulating layer formed by using the resin composition, and a semiconductor device.
  • the present invention includes the following contents.
  • (B) a liquid curing agent and (C) an inorganic filler [2] The resin composition according to [1], wherein the weight average molecular weight of the component (A) is 1000 or more and 15,000 or less.
  • the vinyl equivalent of the component (A) is 250 g / eq. More than 3000 g / eq.
  • the component (A) has a multi-branched structure in which a structure derived from a trifunctional or higher functional compound and a structure derived from a bifunctional compound are alternately bonded, according to any one of [1] to [3].
  • Resin composition [5] The resin composition according to any one of [1] to [4], wherein the component (A) contains a cyclic structure.
  • the resin composition according to [4], wherein the structure derived from the trifunctional or higher functional compound comprises a cyclic structure.
  • the resin composition according to [6], wherein the cyclic structure contains a nitrogen atom.
  • the resin composition according to [4], wherein the structure derived from the bifunctional compound includes a cyclic structure.
  • the content of the component (A) is 5% by mass or more and 40% by mass or less when the non-volatile component in the resin composition is 100% by mass, according to any one of [1] to [8].
  • Resin composition. [10]
  • the component (B) is at least one selected from an allyl-based liquid curing agent, a maleimide-based liquid curing agent, a (meth) acrylic-based liquid curing agent, and a butadiene-based liquid curing agent, [1] to [ 9]
  • the resin composition according to any one of. [11] The resin composition according to any one of [1] to [10], further comprising (D) a polymerization initiator.
  • a resin sheet comprising a support and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [15].
  • a printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [15].
  • a semiconductor device including the printed wiring board according to [17].
  • a resin composition capable of suppressing the occurrence of warpage and obtaining a cured product having excellent dielectric properties and copper foil adhesion; a resin sheet containing the resin composition; using the resin composition.
  • a printed wiring board having a formed insulating layer and a semiconductor device can be provided.
  • FIG. 1 is a schematic side view showing an example of two test tubes used for determining the liquid state and the solid state of the curing agent.
  • the resin composition of the present invention contains (A) a vinyl resin having a hyperbranched structure, (B) a liquid curing agent, and (C) an inorganic filler.
  • A a vinyl resin having a hyperbranched structure
  • B a liquid curing agent
  • C an inorganic filler.
  • the occurrence of warpage is suppressed, and a cured product having excellent dielectric properties and copper foil adhesion can be obtained. Further, usually, according to the cured product of the resin composition of the present invention, the occurrence of warpage can be suppressed.
  • the resin composition may further contain any component in combination with the components (A) to (C).
  • the optional component include (D) a polymerization initiator, (E) an epoxy resin, (F) an epoxy curing agent, (G) a curing accelerator, and (H) other additives.
  • D a polymerization initiator
  • E an epoxy resin
  • F an epoxy curing agent
  • G a curing accelerator
  • H other additives.
  • the resin composition contains (A) a vinyl resin having a hyperbranched structure as a component (A).
  • the component (A) may be used alone or in combination of two or more.
  • a vinyl resin having a hyperbranched structure preferably has a vinyl group at the end having 4 or more (preferably 6 or more, more preferably 8 or more) branched chains, and a vinyl group at all the ends of the branched chain. Is particularly preferred.
  • the vinyl resin having a hyperbranched structure has a multi-branched structure in which a structure derived from a trifunctional or higher functional compound and a structure derived from a bifunctional compound are alternately bonded, and has a vinyl group at the terminal. Refers to resin.
  • the vinyl resin having such a preferable hyperbranched structure can be obtained by reacting a trifunctional or higher functional compound which is the center of the molecular structure with a bifunctional compound. Further, the vinyl resin having a hyperbranched structure may be obtained by further reacting a monofunctional compound in addition to the trifunctional or higher functional compound and the bifunctional compound from the viewpoint of suppressing the elongation of the hyperbranched structure. Since the vinyl resin having a hyperbranched structure probably has a branched structure, it may have a free space around the branched portion. By having a free space, even if the resin composition is cured, it is less likely to shrink and stress is less likely to occur, and as a result, it is considered that the occurrence of warpage is suppressed.
  • any of the groups represented by the formulas (b) to (f) is preferable, and the group represented by the formula (b) and the group represented by the formula (f) are used. Is more preferable, and the group represented by the formula (f) is even more preferable.
  • the vinyl group is bonded to any of the ortho-position, the meta-position and the para-position, and it is more preferable that the vinyl group is bonded to the para-position.
  • the component (A) preferably contains a cyclic structure, and the cyclic structure preferably contains an aromatic structure, from the viewpoint of remarkably obtaining the effect of the present invention.
  • the aromatic structure is a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles.
  • Examples of the cyclic structure include a heterocyclic skeleton, a bisphenol skeleton, a phenylene skeleton, a naphthylene skeleton, a dimethylmethylene biscyclohexylene skeleton, an anthracene skeleton, and the like, and a heterocyclic skeleton and a bisphenol skeleton are preferable.
  • Examples of the heterocyclic skeleton include a heterocyclic skeleton containing a nitrogen atom such as a triazine ring and a pyridine ring, and a triazine ring is preferable.
  • the bisphenol skeleton includes bisphenol A skeleton, bisphenol F skeleton, bisphenol AP skeleton, bisphenol AF skeleton, bisphenol B skeleton, bisphenol BP skeleton, bisphenol S skeleton, bisphenol Z skeleton, bisphenol C skeleton, bisphenol TMC skeleton, bisphenol AF skeleton, bisphenol.
  • Examples thereof include E skeleton, bisphenol G skeleton, bisphenol M skeleton, bisphenol PH skeleton, and bisphenol TMC and bisphenol AF skeleton are preferable.
  • the cyclic structure is preferably contained in any one of a structure derived from a trifunctional or higher functional compound, a structure derived from a bifunctional compound, and a structure derived from a monofunctional compound, a structure derived from a trifunctional or higher functional compound, and a bifunctional compound. It is more preferably contained in the derived structure, and further preferably contained in the structure derived from a trifunctional or higher functional compound, the structure derived from a bifunctional compound, and the structure derived from a monofunctional compound.
  • the ring in the cyclic structure may have a substituent.
  • substituents include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an arylalkyl group having 7 to 12 carbon atoms, a silyl group and an acyl group.
  • acyloxy group examples include an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group and an oxo group.
  • the trifunctional or higher functional compound is a compound that can be the core of the hyperbranched structure, and has a functional group that can react with the bifunctional compound and the monofunctional compound.
  • the trifunctional or higher functional compound has a structure derived from the trifunctional or higher functional compound in the hyperbranched structure.
  • the trifunctional or higher functional compound is preferably a trifunctional compound or a tetrafunctional compound, and more preferably a trifunctional compound.
  • Examples of the functional group of the trifunctional or higher functional compound include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; OH group (including phenolic hydroxyl group); amino group; epoxy group; glycidyl ether group and the like. However, a halogen atom is preferable.
  • the trifunctional or higher functional compound preferably contains a cyclic structure from the viewpoint of remarkably obtaining the effect of the present invention.
  • the cyclic structure preferably contains an aromatic structure, preferably contains an aromatic heterocycle, and more preferably an aromatic heterocycle containing a nitrogen atom.
  • the number of nitrogen atoms contained in the aromatic heterocycle containing nitrogen atoms is preferably 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 5 or less, and particularly preferably 3 or less. Is.
  • trifunctional or higher functional compound examples include cyanuric chloride, 2,4,6-trichloropyrimidine, 2,4,6-trichloropyridine and the like. Among them, cyanuric chloride is preferable as the trifunctional or higher functional compound.
  • the bifunctional compound is a compound that can be bonded to any of the functional groups of the trifunctional or higher-functional compound and the functional group of the monofunctional compound, and has a functional group that can react with the functional group of the trifunctional or higher-functional compound.
  • the bifunctional compound has a structure derived from the bifunctional compound in the hyperbranched structure.
  • Examples of the functional group of the bifunctional compound include an OH group (including a phenolic hydroxyl group), an epoxy group, a glycidyl ether group, an amino group and the like, and an OH group is preferable.
  • the bifunctional compound preferably contains a cyclic structure, more preferably contains an aromatic structure, and further preferably has a bisphenol skeleton. Further, the bifunctional compound may contain a siloxane bond (—Si—O—Si—) from the viewpoint of further improving the dielectric loss tangent.
  • the bifunctional compound containing a siloxane bond preferably has a cage-like silsesquioxane (POSS) structure.
  • bifunctional compound examples include compounds represented by the following formulas (1) to (37).
  • formula (32) X represents a phenyl group and Y represents a methyl group.
  • equations (33) to (37) n represents an integer of 1 to 300, and in equation (37), m represents an integer of 1 to 300.
  • bifunctional compound a compound obtained by reacting a trifunctional compound with a monofunctional compound described later may be used.
  • examples of such a bifunctional compound include compounds represented by the following formulas (38) to (45).
  • R represents an isopropyl group.
  • the bifunctional compound the compounds represented by the formulas (24) and (31) to (37) are preferable.
  • bifunctional compound a commercially available product may be used.
  • examples of commercially available products include “KF-2201” and “KF-8010” manufactured by Shin-Etsu Silicone Co., Ltd.
  • the monofunctional compound is a compound that can be bonded to either a functional group of a trifunctional or higher-functional compound or a functional group of a bifunctional or higher-functional compound, and is a functional group of a trifunctional or higher-functional compound or a functional group of a bifunctional compound. It has a functional group that can react.
  • Examples of the functional group of the monofunctional compound include an amino group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an OH group (including a phenolic hydroxyl group); an amino group; an epoxy group; a glycidyl ether group. Etc., and amino groups and OH groups are preferable.
  • the monofunctional compound preferably contains a cyclic structure from the viewpoint of remarkably obtaining the effect of the present invention. Further, the monofunctional compound may contain a siloxane bond (—Si—O—) from the viewpoint of remarkably obtaining the effect of the present invention.
  • the monofunctional compound containing a siloxane bond preferably has a cage-like silsesquioxane (POSS) structure.
  • the monofunctional compound examples include compounds represented by the following formulas (1-1) to (1-21). Among them, the compound represented by the formula (1-1), the compound represented by the formula (1-6), the compound represented by the formula (1-17), and the compound represented by the formula (1-18). Is preferable, and the compound represented by the formula (1-17) and the compound represented by the formula (1-18) are more preferable.
  • R represents an isopropyl group.
  • n represents an integer of 1 to 300.
  • a commercially available product may be used as the monofunctional compound.
  • examples of commercially available products include “X-22-170BX” and “X-22-170DX” manufactured by Shin-Etsu Silicone Co., Ltd., "KBM903", “KBE903” and “KBM603” manufactured by Shin-Etsu Chemical Co., Ltd.
  • a vinyl resin having a hyperbranched structure can be prepared by reacting a trifunctional or higher-functional compound, a bifunctional compound, and a vinyl group-containing compound, and if necessary, further reacting the monofunctional compound.
  • the vinyl group-containing compound is a compound that introduces a vinyl group at the terminal.
  • examples of the vinyl group-containing compound include allyl bromide, 2-propenoyl bromide, metachloryl bromide, 4-bromostyrene, 4-vinylbenzyl bromide and the like.
  • the reaction temperature is preferably 10 ° C. or higher, more preferably 15 ° C. or higher, still more preferably 20 ° C. or higher, preferably 100 ° C. or lower, more preferably 50 ° C. or lower, still more preferably 30 ° C. or lower. Particularly preferably, it is room temperature (25 ° C.).
  • the reaction time is preferably 0.1 hours or more, more preferably 0.3 hours or more, still more preferably 0.5 hours or more, preferably 3 hours or less, more preferably 2 hours or less, still more preferably 1. .5 hours or less.
  • a commercially available product may be used as the vinyl resin having a hyperbranched structure.
  • Examples of commercially available products include "PDV-PM” manufactured by Nittetsu Chemical & Materials Co., Ltd.
  • (A) Specific examples of the vinyl resin having a hyperbranched structure include, but the present invention is not limited thereto.
  • the broken line means that the structure derived from the trifunctional or higher-functional compound and the probably branched structure in which the structure derived from the bifunctional compound is alternately bonded are further bonded.
  • R represents any group of the formulas (a) to (f).
  • the molecular weight of the vinyl resin having a hyperbranched structure is preferably 1000 or more, more preferably 1200 or more, still more preferably 1400 or more, and preferably 10,000 or less, from the viewpoint of remarkably obtaining the effect of the present invention. It is more preferably 9000 or less, still more preferably 8000 or less, 7500 or less, and 6000 or less.
  • the molecular weight can be measured with a mass spectrometer.
  • the weight average molecular weight of the vinyl resin having a hyperbranched structure is preferably 1000 or more, more preferably 1200 or more, still more preferably 1400 or more, and preferably 15000 from the viewpoint of remarkably obtaining the effect of the present invention. Below, it is more preferably 12000 or less, still more preferably 10000 or less, 7500 or less, and 6000 or less.
  • the weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.
  • the vinyl group equivalent of the vinyl resin having a hyperbranched structure is preferably 250 g / eq. From the viewpoint of remarkably obtaining the effect of the present invention. As mentioned above, more preferably 300 g / eq. Above, more preferably 350 g / eq. The above is preferable, and 3000 g / eq. Below, more preferably 2000 g / eq. Hereinafter, more preferably 1500 g / eq. Hereinafter, 700 g / eq. Hereinafter, 600 g / eq. Hereinafter, 500 g / eq. It is as follows.
  • the vinyl group equivalent is the mass of the vinyl resin containing one equivalent of vinyl groups.
  • the vinyl group equivalent is the mass of a vinyl resin having a hyperbranched structure containing one equivalent of vinyl groups.
  • the content of the vinyl resin having a hyperbranched structure is preferably 5% by mass or more when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of remarkably obtaining the effect of the present invention. It is preferably 10% by mass or more, more preferably 15% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less.
  • the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass, unless otherwise specified.
  • the content of the vinyl resin having a hyperbranched structure is preferably 50% by mass or more when the resin component in the resin composition is 100% by mass, from the viewpoint of remarkably obtaining the effect of the present invention. It is preferably 60% by mass or more, more preferably 70% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 88% by mass or less.
  • the resin component refers to a non-volatile component in the resin composition excluding (C) the inorganic filler.
  • the resin composition contains (B) a liquid curing agent as a component (B).
  • a liquid curing agent as a component (B).
  • the component (B) may be used alone or in combination of two or more.
  • the determination of liquid is performed in accordance with the "Liquid confirmation method" in Attachment 2 of the Ministerial Ordinance on Dangerous Goods Testing and Properties (Ministerial Ordinance No. 1 of 1989).
  • the specific determination method is as follows.
  • Equipment constant temperature water tank Use a stirrer, heater, thermometer, and automatic temperature controller (those that can control the temperature at ⁇ 0.1 ° C) with a depth of 150 mm or more.
  • tap water of about 22 was used in combination with a low-temperature constant temperature water tank (model BU300) manufactured by Yamato Kagaku Co., Ltd. and a charging type constant temperature device Thermomate (model BF500).
  • thermomate model BF500
  • Thermomate model BF500
  • Test tube As shown in FIG. 1, the test tube is made of flat-bottomed cylindrical transparent glass having an inner diameter of 30 mm and a height of 120 mm, and marked lines 11A and 12B are attached at heights of 55 mm and 85 mm from the tube bottom, respectively.
  • a test tube for liquid determination 10a in which the mouth of the test tube is sealed with a rubber stopper 13a, and a rubber stopper 13b having the same size but similarly marked and having a hole in the center for inserting and supporting a thermometer.
  • a test tube 10b for temperature measurement is used in which the mouth of the test tube is sealed and the thermometer 14 is inserted in the rubber stopper 13b.
  • the marked line having a height of 55 mm from the bottom of the pipe is referred to as "line A”
  • the marked line having a height of 85 mm from the bottom of the pipe is referred to as "line B”.
  • the thermometer 14 the one for measuring the freezing point (SOP-58 scale range 0 to 100 ° C.) specified in JIS B7410 (1982) "Glass thermometer for petroleum test” is used, but the temperature is 0 to 100 ° C. Anything that can measure the range will do.
  • Test implementation procedure Samples left for 24 hours or more under atmospheric pressure at a temperature of 60 ⁇ 5 ° C. are subjected to the liquid determination test tube 10a shown in FIG. 1 (a) and the temperature measurement test shown in FIG. 1 (b). Put up to 11A line in each tube 10b.
  • the two test tubes 10a and 10b are placed upright in a low-temperature constant temperature water tank so that the 12B line is below the water surface.
  • the thermometer should have its lower end 30 mm below the 11A line. After the sample temperature reaches the set temperature ⁇ 0.1 ° C, keep it as it is for 10 minutes.
  • the liquid judgment test tube 10a was taken out from the low temperature constant temperature water tank, immediately laid horizontally on a horizontal test table, and the time when the tip of the liquid level in the test tube moved from the 11A line to the 12B line was stopped with a stopwatch. Measure and record.
  • the test is carried out in the same manner as when the sample is left for 24 hours or more under an atmospheric pressure of 60 ⁇ 5 ° C., and the liquid in the test tube is used. The time when the tip of the surface moves from the 11A line to the 12B line is measured and recorded with a stopwatch.
  • the time measured at 20 ° C. is 90 seconds or less, or the time measured at 20 ° C. exceeds 90 seconds and the time measured at 60 ° C. is 90 seconds or less, it is determined to be liquid. If the measured time exceeds 90 seconds at 60 ° C., it is determined to be solid.
  • a component that is liquid and has a function of curing the component (A) can be used.
  • a liquid curing agent a compound having an ethylenically unsaturated bond and not having a hyperbranched structure can be usually used.
  • the component (B) is preferably at least one selected from, for example, an allyl-based liquid curing agent, a maleimide-based liquid curing agent, a (meth) acrylic-based liquid curing agent, and a butadiene-based liquid curing agent, and is preferably an allyl-based liquid. It is more preferably a curing agent.
  • the allyl-based liquid curing agent is a compound having at least one allyl group in the molecule.
  • the allyl group has a function of reacting with the vinyl group in the component (A) and curing the component (A).
  • the allyl-based liquid curing agent preferably has one or more allyl groups per molecule, and more preferably has two or more allyl groups.
  • the lower limit is not particularly limited, but may be preferably 10 or less, and more preferably 5 or less.
  • the allyl-based liquid curing agent contains any one of a benzoxazine ring, a phenol ring, an epoxy group, and a carboxylic acid derivative having a cyclic structure in addition to the allyl group from the viewpoint of remarkably obtaining the desired effect of the present invention. It is preferable to have a benzoxazine ring, and it is more preferable to have a benzoxazine ring from the viewpoint of obtaining the desired effect of the present invention more remarkably.
  • the allyl group is bonded to either a nitrogen atom constituting the benzoxazine ring or a carbon atom constituting the benzoxazine ring from the viewpoint of significantly obtaining the desired effect of the present invention. It is preferable that it is bonded to a carbon atom, and it is more preferable that it is bonded to a carbon atom.
  • an allyl-based liquid curing agent having a benzoxazine ring for example, an allyl-based liquid curing agent having a benzoxazine ring represented by the following formula (B-1) is preferable.
  • R 20 and R 21 represent an allyl group
  • R 22 represents a q-valent group.
  • q represents an integer of 1 to 4
  • p1 represents an integer of 0 to 4
  • p2 represents an integer of 0 to 2.
  • either p1 or p2 is 1 or more.
  • the q-valent group represented by R 22 is preferably an allyl group, a q-valent aromatic hydrocarbon group, a q-valent aliphatic hydrocarbon group, an oxygen atom, or a q-valent group consisting of a combination thereof.
  • the allyl group may be a substituent of either a q-valent aromatic hydrocarbon group or a q-valent aliphatic hydrocarbon group.
  • R 22 is preferably a group consisting of an arylene group, an alkylene group, an oxygen atom, or a combination of two or more divalent groups thereof, and an arylene group or two or more divalent groups. It is more preferable that the group is composed of a combination of two or more divalent groups, and further preferably, it is a group composed of a combination of two or more kinds of divalent groups.
  • an arylene group having 6 to 20 carbon atoms is preferable, an arylene group having 6 to 15 carbon atoms is more preferable, and an arylene group having 6 to 12 carbon atoms is further preferable.
  • Specific examples of the arylene group include a phenylene group, a naphthylene group, an anthrasenylene group, a biphenylene group and the like, and a phenylene group is preferable.
  • an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is further preferable.
  • Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group and the like, and a methylene group is preferable.
  • Examples of the group consisting of a combination of two or more divalent groups in R 22 include a group in which one or more arylene groups and one or more oxygen atoms are bonded; for example, a group having an arylene-alkylene-arylene structure. 1 or more arylene groups and 1 or more alkylene groups bonded; 1 or more alkylene groups and 1 or more oxygen atoms bonded; 1 or more arylene groups, 1 or more alkylene groups and 1 or more Examples thereof include a group in which an oxygen atom is bonded, and a group in which one or more arylene groups and one or more oxygen atoms are bonded is preferable, and a group in which one or more arylene groups and one or more alkylene groups are bonded is preferable.
  • Q represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2.
  • P1 represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 1.
  • p2 represents an integer of 0 to 2, represents 0 or 1, and 0 is preferred.
  • the allyl-based liquid curing agent having an allyl ring examples include a cresol resin containing an allyl group, a novolak-type phenol resin containing an allyl group, and a cresol novolak resin containing an allyl group.
  • the allyl-based liquid curing agent having a phenol ring is preferably an allyl-based liquid curing agent having a phenol ring represented by the following formula (B-2).
  • R 23 , R 24 , and R 25 each independently represent an allyl group
  • s1 independently represents an integer of 0 to 4
  • s2 independently represents an integer of 0 to 3.
  • s1 is 1 or more
  • r at least one of s1 and s2 is 1 or more.
  • R 23 to R 25 each independently represent an allyl group.
  • the number of allyl groups is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, preferably 25 or less, more preferably 10 or less, still more preferably. 5 or less.
  • S1 independently represents an integer of 0 to 4, preferably an integer of 1 to 3, and more preferably an integer of 1 to 2.
  • S2 independently represents an integer of 0 to 3, preferably an integer of 1 to 3, and more preferably an integer of 1 to 2.
  • R represents an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably an integer of 1 to 2.
  • the allyl liquid curing agent having an epoxy group preferably contains two or more epoxy groups in one molecule. Further, the allyl-based liquid curing agent having an epoxy group preferably has an aromatic structure, and when two or more kinds of allyl-based liquid curing agents having an epoxy group are used, at least one kind has an aromatic structure. preferable.
  • the allyl-based liquid curing agent having an epoxy group preferably has a bisphenol structure, and examples of the bisphenol structure include bisphenol A type, bisphenol F type, bisphenol AF type, and the like, among which the effects of the present invention can be achieved.
  • the bisphenol A type is preferable from the viewpoint of obtaining remarkably.
  • allyl carboxylate having a cyclic structure is preferable.
  • the cyclic structure may be either a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. Further, the cyclic group may have a ring skeleton formed of a hetero atom other than the carbon atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom and the like, and a nitrogen atom is preferable.
  • the heteroatom may have one in the ring or two or more.
  • the carboxylic acid derivative having a cyclic structure has a network structure with a cyclic structure, which improves the compatibility and dispersibility of the resin varnish, and as a result, it is possible to improve the laminateability, and a cured product having further excellent adhesion can be obtained. It will be possible to obtain.
  • Examples of the carboxylic acid having a cyclic structure include isocyanuric acid, diphenic acid, phthalic acid, cyclohexanedicarboxylic acid and the like.
  • Examples of the allyl-based liquid curing agent having a carboxylic acid derivative having a cyclic structure include allyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate, diallyl diphenate, allyl diphenylate, orthodialyl phthalate, metadialyl phthalate, and paradialyl phthalate. , Cyclohexanedicarboxylic acid allyl, cyclohexanedicarboxylic acid diallyl and the like.
  • a commercially available product can be used as the allyl-based liquid curing agent.
  • Examples of commercially available products include “MEH-8000H” and “MEH-8005" manufactured by Meiwa Kasei Co., Ltd. (allyl-based liquid curing agent having a phenol ring); “RE-810NM” manufactured by Nippon Kayaku Co., Ltd. (allyl having an epoxy group).
  • TAIC allyl-based liquid curing agent having an isocyanul ring
  • MDAC allyl-based liquid curing agent having a cyclohexanedicarboxylic acid derivative
  • DAD diallyl diphenate
  • Daisodap Monomer orthodiallyl phthalate
  • the allyl group equivalent of the allyl-based liquid curing agent is preferably 20 g / eq. From the viewpoint of remarkably obtaining the desired effect of the present invention. ⁇ 1000 g / eq. , More preferably 50 g / eq. ⁇ 500 g / eq. , More preferably 100 g / eq. ⁇ 300 g / eq. Is.
  • the allyl group equivalent is the mass of the allyl liquid curing agent containing 1 equivalent of allyl groups.
  • the maleimide-based liquid curing agent is a compound having at least one maleimide group in the molecule.
  • the maleimide-based liquid curing agent preferably contains an aliphatic group having 5 or more carbon atoms.
  • the aliphatic group preferably contains at least one of an alkyl group having 5 or more carbon atoms, an alkylene group having 5 or more carbon atoms, and an alkynylene group having 5 or more carbon atoms.
  • the number of carbon atoms of an alkyl group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less.
  • the alkyl group may be linear, branched or cyclic, and the linear group is preferable. Examples of such an alkyl group include a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and the like.
  • the alkyl group having 5 or more carbon atoms may have as a substituent of the alkylene group having 5 or more carbon atoms.
  • the number of carbon atoms of the alkylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less.
  • the alkylene group may be linear, branched or cyclic, and the linear group is preferable.
  • the cyclic alkylene group is a concept including a case where it is composed of only a cyclic alkylene group and a case where it contains both a linear alkylene group and a cyclic alkylene group.
  • Examples of such an alkylene group include a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecylene group, a hexatriacontylene group and an octylene-cyclohexylene.
  • Examples thereof include a group having a structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, and the like.
  • the number of carbon atoms of the alkynylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less.
  • the alkynylene group may be linear, branched or cyclic, and the linear group is preferable.
  • the cyclic alkynylene group is a concept including a case where it is composed of only a cyclic alkynylene group and a case where it contains both a linear alkynylene group and a cyclic alkynylene group.
  • alkynylene group examples include a pentynylene group, a hexynylene group, a heptinylene group, an octinilen group, a nonynylene group, a decinilen group, an undecinylene group, a dodecinylene group, a tridecinylene group, a heptadecynylene group, a hexatriacontinylene group, and an octynelen-cyclohexylene group.
  • Examples thereof include a group having a len structure, a group having an octinilen-cyclohexinylene-octinilen structure, a group having a propynylene-cyclohexynylene-octinilen structure, and the like.
  • the maleimide-based liquid curing agent preferably contains both an alkynylene group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms from the viewpoint of remarkably obtaining the effect of the present invention.
  • Aliphatic groups having 5 or more carbon atoms may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring.
  • the ring formed by bonding with each other include a cyclohexane ring and the like.
  • the aliphatic group having 5 or more carbon atoms preferably does not have a substituent, but may have a substituent.
  • Examples of the substituent include a halogen atom, -OH, -OC 1-10 alkyl group, -N (C 1-10 alkyl group) 2 , C 1-10 alkyl group, C 6-10 aryl group, and-.
  • Examples thereof include NH 2 , -CN, -C (O) OC 1-10 alkyl group, -COOH, -C (O) H, -NO 2 and the like.
  • C x-y (x and y are positive integers and satisfy x ⁇ y) is described immediately after this term in that the number of carbon atoms of the organic group is xy to xy. Represents that there is.
  • C 1-10 alkyl group indicates an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring.
  • the aliphatic group having 5 or more carbon atoms is directly bonded to the nitrogen atom of the maleimide group.
  • the number of maleimide groups per molecule of the maleimide-based liquid curing agent may be 1, but is preferably 2 or more, preferably 10 or less, more preferably 6 or less, and particularly preferably 3 or less. ..
  • the maleimide-based liquid curing agent is preferably a maleimide-based liquid curing agent represented by the following general formula (B-3).
  • M represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent
  • L represents a single bond or a divalent linking group.
  • M represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent.
  • the divalent aliphatic group of M include an alkylene group having 5 or more carbon atoms, an alkynylene group having 5 or more carbon atoms, an alkylene group having 5 or more carbon atoms, and an alkylene group having 5 or more carbon atoms.
  • the alkynylene groups of 5 or more are as described above.
  • the substituent of M include a halogen atom, -OH, -OC 1-10 alkyl group, -N (C 1-10 alkyl group) 2 , C 1-10 alkyl group, and C 6-10 aryl group.
  • C x-y (x and y are positive integers and satisfy x ⁇ y) is described immediately after this term in that the number of carbon atoms of the organic group is xy to xy. Represents that there is.
  • C 1-10 alkyl group indicates an alkyl group having 1 to 10 carbon atoms.
  • L represents a single bond or a divalent linking group.
  • a group consisting of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent group derived from phthalimide, a divalent group derived from diimide pyromellitic acid, and a combination of two or more divalent groups has a carbon atom number. May have 5 or more alkyl groups as substituents.
  • the phthalimide-derived divalent group represents a divalent group derived from phthalimide, and specifically, is a group represented by the general formula (A).
  • the divalent group derived from diimide pyromellitic acid represents a divalent group derived from diimide pyromellitic acid, and specifically, is a group represented by the general formula (B). In the formula, "*" represents a bond.
  • the alkylene group as the divalent linking group in L is preferably an alkylene group having 1 to 50 carbon atoms, more preferably an alkylene group having 1 to 45 carbon atoms, and particularly preferably an alkylene group having 1 to 40 carbon atoms. ..
  • the alkylene group may be linear, branched or cyclic.
  • Examples of such an alkylene group include a methylethylene group, a cyclohexylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecylene group and a hexatria.
  • Examples thereof include a contylene group, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure and the like.
  • the alkenylene group as the divalent linking group in L is preferably an alkenylene group having 2 to 50 carbon atoms, more preferably an alkenylene group having 2 to 45 carbon atoms, and particularly preferably an alkenylene group having 2 to 40 carbon atoms. ..
  • the alkenylene group may be linear, branched or cyclic. Examples of such an alkenylene group include a methylethyleneylene group, a cyclohexenylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group and the like.
  • the alkynylene group as the divalent linking group in L is preferably an alkynylene group having 2 to 50 carbon atoms, more preferably an alkynylene group having 2 to 45 carbon atoms, and particularly preferably an alkynylene group having 2 to 40 carbon atoms. ..
  • the alkynylene group may be linear, branched or cyclic. Examples of such an alkynylene group include a methylethynylene group, a cyclohexynylene group, a pentynylene group, a hexynylene group, a heptinylene group, an octynylene group and the like.
  • the arylene group as the divalent linking group in L is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, and even more preferably an arylene group having 6 to 14 carbon atoms.
  • An arylene group having 6 to 10 carbon atoms is even more preferable.
  • Examples of the arylene group include a phenylene group, a naphthylene group, an anthrasenylene group and the like.
  • the alkylene group, alkenylene group, alkynylene group, and arylene group, which are divalent linking groups in L, may have a substituent.
  • the substituent is the same as the substituent of M in the general formula (B-3), and is preferably an alkyl group having 5 or more carbon atoms.
  • Examples of the group consisting of a combination of two or more divalent groups in L include an alkylene group, a divalent group derived from phthalimide, and a divalent group consisting of a combination with an oxygen atom; a divalent group derived from phthalimide.
  • a group consisting of a combination of two or more divalent groups may form a ring such as a fused ring by the combination of the respective groups.
  • the group composed of a combination of two or more kinds of divalent groups may be a repeating unit having 1 to 10 repeating units.
  • L in the general formula (B-3) includes an oxygen atom, an arylene group having 6 to 24 carbon atoms which may have a substituent, and a carbon atom which may have a substituent.
  • a divalent group consisting of 1 to 50 alkylene groups, an alkyl group having 5 or more carbon atoms, a divalent group derived from phthalimide, a divalent group derived from diimide pyromellitic acid, or a combination of 2 or more of these groups. It is preferably a group.
  • L is an alkylene group; an alkylene group-a divalent group derived from phthalimide-an oxygen atom-a divalent group having a structure of a divalent group derived from phthalimide; an alkylene group-a divalent group derived from phthalimide- Oxygen atom-allylen group-alkylene group-allylen group-oxygen atom-divalent group having a divalent group structure derived from phthalimide; divalent group having a divalent group structure derived from alkylene-pyramellitic acid diimide Group; alkynylene group-divalent group derived from phthalimide-oxygen atom-divalent group having a divalent group structure derived from phthalimide; alkynylene group-divalent group derived from phthalimide-oxygen atom-allylen group-alkynylene A divalent group having a divalent group structure derived from a group-allylen group-oxygen atom-phthalimide
  • the maleimide-based liquid curing agent represented by the general formula (B-3) is preferably a maleimide-based liquid curing agent represented by the general formula (B-4).
  • M 1 represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent independently, and A has a substituent independently. It represents a divalent aliphatic group having 5 or more carbon atoms which may be present, or a divalent group having an aromatic ring which may have a substituent.
  • t represents an integer from 1 to 10.
  • M 1 represents a divalent aliphatic group having 5 or more carbon atoms, each of which may have a substituent independently. M 1 is the same as M in the general formula (B-3).
  • A represents a divalent aliphatic group having 5 or more carbon atoms which may independently have a substituent or a divalent group having an aromatic ring which may have a substituent.
  • Examples of the divalent aliphatic group of A include an alkylene group and an alkenylene group.
  • the aliphatic group in A may be chain-shaped, branched-chain-shaped, or cyclic, and among them, a cyclic, that is, a cyclic aliphatic group having 5 or more carbon atoms which may have a substituent is used.
  • the number of carbon atoms of the alkylene group is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less.
  • Examples of such an alkylene group include a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, and the like.
  • the number of carbon atoms of the alkenylene group in A is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less.
  • alkenylene group include a pentynylene group, a hexynylene group, a heptyrenylene group, an octinilen group, a noniniylene group, a decinilen group, an undecinylene group, a dodecinylene group, a tridecinylene group, a heptadecynylene group, a hexatriacontinylene group, and an octynelen-cyclohexylene.
  • Examples thereof include a group having a len structure, a group having an octinilen-cyclohexinylene-octinilen structure, a group having a propynylene-cyclohexynylene-octinilen structure, and the like.
  • Examples of the aromatic ring in the divalent group having the aromatic ring represented by A include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a diimide ring of pyromellitic acid, an aromatic heterocycle, and the like, and a benzene ring and a phthalimide. Rings and diimide rings of pyromellitic acids are preferable. That is, as the divalent group having an aromatic ring, a divalent group having a benzene ring which may have a substituent, a divalent group having a phthalimide ring which may have a substituent, and a substitution group.
  • a divalent group having a diimide ring of pyromellitic acid, which may have a group, is preferable.
  • the divalent group having an aromatic ring is, for example, a group composed of a combination of a divalent group derived from phthalimide and an oxygen atom; a divalent group derived from phthalimide, an oxygen atom, an arylene group and an alkylene group.
  • the arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (B-3).
  • the divalent aliphatic group represented by A and the divalent group having an aromatic ring may have a substituent.
  • the substituent is the same as the substituent represented by M in the above formula (B-3).
  • the maleimide-based liquid curing agent represented by the general formula (B-3) is a maleimide-based liquid curing agent represented by the general formula (B-5) and a maleimide-based liquid represented by the general formula (B-6). It is preferably one of the curing agents.
  • M 2 and M 3 each represent a divalent aliphatic group having 5 or more carbon atoms which may have a substituent independently, and R 30 is an independent group. Represents a divalent group consisting of an oxygen atom, an arylene group, an alkylene group, or a combination of two or more of these groups.
  • t1 represents an integer from 1 to 10.
  • M 4 , M 6 and M 7 each represent an alkylene group having 5 or more carbon atoms which may independently have a substituent, and M 5 is an independent substituent.
  • t2 represents an integer of 0 to 10
  • u1 and u2 independently represent an integer of 0 to 4.
  • M 2 and M 3 each represent a divalent aliphatic group having 5 or more carbon atoms which may have a substituent independently.
  • M 2 and M 3 are the same as the divalent aliphatic group having 5 or more carbon atoms represented by M in the general formula (B-3), and a hexatriacontinylene group is preferable.
  • Each of R 30 independently represents an oxygen atom, an arylene group, an alkylene group, or a group consisting of a combination of two or more divalent groups thereof.
  • the arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (B-3).
  • the R 30 is preferably a group consisting of a combination of two or more divalent groups or an oxygen atom.
  • Examples of the group consisting of a combination of two or more divalent groups in R 30 include a combination of an oxygen atom, an arylene group, and an alkylene group. Specific examples of a group consisting of a combination of two or more divalent groups include the following groups. In the formula, "*" represents a bond.
  • M 4 , M 6 and M 7 each represent an alkylene group having 5 or more carbon atoms which may independently have a substituent.
  • M 4 , M 6 and M 7 are the same as the alkylene group having 5 or more carbon atoms which may have a substituent represented by M in the general formula (B-3), and are a hexylene group and a heptylene group. , Octylene group, nonylene group, decylene group are preferable, and octylene group is more preferable.
  • M 5 represents a divalent group having an aromatic ring, each of which may independently have a substituent.
  • M 5 is the same as a divalent group having an aromatic ring which may have a substituent represented by A in the general formula (B-4), and is a divalent group derived from an alkylene group and diimide pyromellitic acid.
  • Group consisting of a combination of groups a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group is preferable, and a group consisting of a combination of an alkylene group and a divalent group derived from diimide pyromellitic acid is more preferable.
  • the arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (B-3).
  • R 31 and R 32 each independently represent an alkyl group having 5 or more carbon atoms.
  • R 31 and R 32 are the same as the above-mentioned alkyl group having 5 or more carbon atoms, preferably a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group, and more preferably a hexyl group and an octyl group.
  • U1 and u2 each independently represent an integer of 1 to 15, and an integer of 1 to 10 is preferable.
  • maleimide-based liquid curing agent examples include the following compounds (1B) to (3B). However, the maleimide-based liquid curing agent is not limited to these specific examples.
  • v represents an integer from 1 to 10.
  • maleimide-based liquid curing agent examples include "BMI1500” (compound of formula (1)), “BMI1700” (compound of formula (2)), and “BMI689” (formula (3)) manufactured by Designer Moleculars. Compounds), etc.
  • the maleimide group equivalent of the maleimide-based liquid curing agent is preferably 50 g / eq. From the viewpoint of remarkably obtaining the desired effect of the present invention. ⁇ 2000g / eq. , More preferably 100 g / eq. ⁇ 1000 g / eq. , More preferably 150 g / eq. ⁇ 500 g / eq. Is.
  • the maleimide group equivalent is the mass of the maleimide-based liquid curing agent containing 1 equivalent of the maleimide group.
  • the (meth) acrylic liquid curing agent is a curing agent containing acryloyl group, methacryloyl group, and a combination thereof.
  • the (meth) acrylic liquid curing agent preferably has two or more (meth) acryloyl groups per molecule from the viewpoint of remarkably obtaining the desired effect of the present invention.
  • the term "(meth) acryloyl group” includes acryloyl groups, methacryloyl groups and combinations thereof.
  • the (meth) acrylic liquid curing agent preferably has a cyclic structure from the viewpoint of remarkably obtaining the desired effect of the present invention.
  • a divalent cyclic group is preferable.
  • the divalent cyclic group may be either a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. Above all, from the viewpoint of remarkably obtaining the desired effect of the present invention, a cyclic group containing an alicyclic structure is preferable.
  • the divalent cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, still more preferably a 5-membered ring or more, and preferably a 20-membered ring, from the viewpoint of remarkably obtaining the desired effect of the present invention.
  • it is more preferably 15-membered ring or less, still more preferably 10-membered ring or less.
  • the divalent cyclic group may have a monocyclic structure or a polycyclic structure.
  • the ring in the divalent cyclic group may be composed of a heteroatom other than a carbon atom to form a ring skeleton.
  • the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom and the like, and an oxygen atom is preferable.
  • the heteroatom may have one in the ring or two or more.
  • divalent cyclic group examples include the following divalent groups (i) to (xi). Among them, (x) or (xi) is preferable as the divalent cyclic group.
  • the divalent cyclic group may have a substituent.
  • substituents include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group and a hydroxy group. Examples thereof include a mercapto group and an oxo group, and an alkyl group is preferable.
  • the (meth) acryloyl group may be directly bonded to a divalent cyclic group or may be bonded via a divalent linking group.
  • an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 4 carbon atoms. Is even more preferable.
  • the alkylene group may be linear, branched or cyclic. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a 1,1-dimethylethylene group and the like, and a methylene group, an ethylene group and 1,1 -A dimethylethylene group is preferred.
  • an alkenylene group having 2 to 10 carbon atoms is preferable, an alkenylene group having 2 to 6 carbon atoms is more preferable, and an alkenylene group having 2 to 5 carbon atoms is further preferable.
  • an arylene group and the heteroarylene group an arylene group or a heteroarylene group having 6 to 20 carbon atoms is preferable, and an arylene group or a heteroarylene group having 6 to 10 carbon atoms is more preferable.
  • the divalent linking group an alkylene group is preferable, and a methylene group and a 1,1-dimethylethylene group are particularly preferable.
  • the (meth) acrylic liquid curing agent is preferably represented by the following formula (B-7).
  • R 33 and R 36 each independently represent an acryloyl group or a methacryloyl group
  • R 34 and R 35 each independently represent a divalent linking group.
  • Ring B is a divalent group. Represents a cyclic group.
  • R 33 and R 36 independently represent an acryloyl group or a methacryloyl group, and an acryloyl group is preferable.
  • R 34 and R 35 each independently represent a divalent linking group.
  • the divalent linking group is the same as the divalent linking group to which the (meth) acryloyl group may be bonded.
  • Ring B represents a divalent cyclic group.
  • the ring B is the same as the above-mentioned divalent cyclic group.
  • Ring B may have a substituent.
  • the substituent is the same as the substituent that the above divalent cyclic group may have.
  • (meth) acrylic liquid curing agent examples include, but the present invention is not limited thereto.
  • (meth) acrylic liquid curing agent a commercially available product may be used, for example, “A-DOG” manufactured by Shin Nakamura Chemical Industry Co., Ltd., “DCP-A” manufactured by Kyoeisha Chemical Co., Ltd., and “DCP-A” manufactured by Nippon Kayaku Co., Ltd. Examples thereof include “NPDGA”, “FM-400”, “R-687”, “THE-330", “PET-30”, “DPHA”, and "NK Ester DCP” manufactured by Shin Nakamura Chemical Industry Co., Ltd.
  • the (meth) acryloyl group equivalent of the (meth) acrylic liquid curing agent is preferably 30 g / eq. From the viewpoint of remarkably obtaining the desired effect of the present invention. ⁇ 400 g / eq. , More preferably 50 g / eq. ⁇ 300 g / eq. , More preferably 75 g / eq. ⁇ 200 g / eq. Is.
  • the (meth) acryloyl group equivalent is the mass of the (meth) acrylic liquid curing agent containing 1 equivalent of the (meth) acryloyl group.
  • the butadiene liquid curing agent is a compound having at least one butadiene skeleton in the molecule.
  • the polybutadiene structure may be contained in the main chain or the side chain.
  • the polybutadiene structure may be partially hydrogenated, but preferably contains one or more ethylenically unsaturated bonds in the molecule.
  • Examples of the butadiene-based liquid curing agent include hydrided polybutadiene skeleton-containing resin, hydroxy group-containing butadiene resin, phenolic hydroxyl group-containing butadiene resin, carboxy group-containing butadiene resin, acid anhydride group-containing butadiene resin, epoxy group-containing butadiene resin, and isocyanate group.
  • One or more resins selected from the group consisting of the contained butadiene resin and the urethane group-containing butadiene resin are more preferable.
  • butadiene-based liquid curing agent examples include "JP-100” manufactured by Nippon Soda, "Ricon100”, “Ricon150”, “Ricon130MA8”, “Ricon130MA13”, “Ricon130MA20”, and “Ricon131MA5" manufactured by CRAY VALLY. , “Ricon131MA10”, “Ricon131MA17”, “Ricon131MA20”, “Ricon 184MA6” and the like.
  • the molecular weight of the component (B) is usually smaller than the weight average molecular weight of the component (A).
  • the specific range of the molecular weight of the component (B) is preferably 100 or more, more preferably 150 or more, particularly preferably 200 or more, preferably less than 1000, more preferably 700 or less, and particularly preferably 500 or less. ..
  • the non-volatile component in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 2% by mass. % Or more, more preferably 3% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less.
  • the resin component in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 5% by mass. % Or more, more preferably 10% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less.
  • the resin composition contains an inorganic filler as the component (C).
  • (C) By containing the inorganic filler in the resin composition, it is possible to obtain a cured product having excellent dielectric properties.
  • Inorganic compounds are used as the material for the inorganic filler.
  • materials for inorganic fillers include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, Magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconate titanate , Barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconate titanate, zirconate titanate phosphate and the like.
  • silica is particularly suitable.
  • examples of silica 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.
  • inorganic fillers include, for example, "UFP-30” manufactured by Denka Kagaku Kogyo Co., Ltd .; “SP60-05” and “SP507-05” manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C”; “UFP-30” manufactured by Denka Corporation; “Silfil NSS-3N”, “Silfil NSS-4N”, “Silfil NSS-” manufactured by Tokuyama Corporation. 5N ”;“ SC2500SQ ”,“ SO-C4 ”,“ SO-C2 ”,“ SO-C1 ”,“ SC2050-SXF ”, etc. manufactured by Admatex.
  • the average particle size of the inorganic filler is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, and particularly preferably 0.1 ⁇ m or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. It is preferably 5 ⁇ m or less, more preferably 2 ⁇ m or less, still more preferably 1 ⁇ m or less.
  • the average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it 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, 10 g of methyl ethyl ketone, and 0.1 g of a dispersant (“SN9228” manufactured by San Nopco Ltd.) are 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, and the obtained particle size distribution was used. Calculate the average particle size as the median diameter.
  • the laser diffraction type particle size distribution measuring device include "LA-960” manufactured by HORIBA, Ltd. and "SALD-2200” manufactured by Shimadzu Corporation.
  • the specific surface area of the inorganic filler is preferably 1 m 2 / g or more, more preferably 2 m 2 / g or more, and particularly preferably 3 m 2 / g or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. be.
  • the upper limit is not particularly limited, but is preferably 60 m 2 / g or less, 50 m 2 / g or less, or 40 m 2 / g or less.
  • the specific surface area is filled by inorganic filling by adsorbing nitrogen gas on the sample surface using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) and calculating the specific surface area using the BET multipoint method. It is obtained by measuring the specific surface area of the material.
  • the inorganic filler is preferably treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility.
  • a surface treatment agent include fluorine-containing silane coupling agents such as 3,3,3-trifluoropropyltrimethoxysilane; 3-aminopropyltriethoxysilane, N-phenyl-8-aminooctyl-trimethoxysilane, and the like.
  • Aminosilane-based coupling agents such as N-phenyl-3-aminopropyltrimethoxysilane; epoxysilane-based coupling agents such as 3-glycidoxypropyltrimethoxysilane; mercaptosilane-based cups such as 3-mercaptopropyltrimethoxysilane Ring agents; silane-based coupling agents; alkoxysilanes such as phenyltrimethoxysilane; organosilazane compounds such as hexamethyldisilazane, titanate-based coupling agents and the like can be mentioned.
  • one type of surface treatment agent may be used alone, or two or more types may be used in any combination.
  • Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd.
  • KBE903 (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.
  • KBM573 N-phenyl-3-aminopropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.
  • SZ-31 manufactured by Shin-Etsu Chemical Co., Ltd.
  • 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 parts by mass of the inorganic filler is preferably surface-treated with 0.2 parts by mass to 5 parts by mass of a surface treatment agent, and is surface-treated with 0.2 parts by mass to 3 parts by mass. It is preferable that the surface is treated with 0.3 parts by mass to 2 parts 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.
  • Carbon content per unit surface area of the inorganic filler from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / m 2 or more, 0.1 mg / m 2 or more preferably, 0.2 mg / m 2 The above is more preferable.
  • 1 mg / m 2 or less is preferable, 0.8 mg / m 2 or less is more preferable, and 0.5 mg / m 2 or less is further preferable. preferable.
  • 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 non-volatile component in the resin composition is 100% by mass, it is preferably 30% by mass or more, more preferably 40% by mass. % Or more, more preferably 50% by mass or more or 60% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less.
  • the resin composition may contain (D) a polymerization initiator as an arbitrary component in addition to the above-mentioned components.
  • the component (D) usually has a function of promoting the cross-linking of radically polymerizable unsaturated groups in the component (A).
  • the component (D) may be used alone or in combination of two or more.
  • Examples of the (D) polymerization initiator include dit-hexyl peroxide, t-butyl cumyl peroxide, t-butyl peroxyacetate, ⁇ , ⁇ '-di (t-butyl peroxy) diisopropylbenzene, and t-.
  • Examples thereof include peroxides such as butylperoxylaurate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, and t-butylperoxybenzoate.
  • polymerization initiators examples include “Perhexyl D”, “Perbutyl C”, “Perbutyl A”, “Perbutyl P”, “Perbutyl L”, “Perbutyl O”, and “Perbutyl O” manufactured by NOF CORPORATION. Examples thereof include “Perbutyl ND”, “Perbutyl Z”, “Park Mill P”, and “Park Mill D”.
  • the content of the (D) polymerization initiator is preferably 0.01% by mass or more, more preferably, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of remarkably obtaining the desired effect of the present invention. Is 0.02% by mass or more, more preferably 0.03% by mass or more, preferably 0.3% by mass or less, more preferably 0.2% by mass or less, still more preferably 0.1% by mass or less. ..
  • the content of the component (D) is preferably 0.1% by mass or more, more preferably 0.1% by mass or more, when the resin component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. It is 0.15% by mass or more, more preferably 0.3% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less.
  • the resin composition may contain (E) epoxy resin as an arbitrary component in addition to the above-mentioned components.
  • the component (A) may be used alone or in combination of two or more.
  • component (E) examples include bixilenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol type epoxy.
  • Resin naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, Cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedi Examples thereof include a methanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, and a tetraphenylethane type epoxy resin.
  • the resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the component (E).
  • the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 20% by mass with respect to 100% by mass of the non-volatile component of the component (E). As mentioned above, it is more preferably 30% by mass or more, and particularly preferably 40% by mass or more.
  • the epoxy resin may be a liquid epoxy resin at a temperature of 20 ° C. (hereinafter sometimes referred to as “liquid epoxy resin”) or a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “solid epoxy resin”). ).
  • the resin composition may contain only the liquid epoxy resin as the component (E), may contain only the solid epoxy resin, or may contain a combination of the liquid epoxy resin and the solid epoxy resin. However, from the viewpoint of remarkably obtaining the desired effect of the present invention, it is preferable to include the liquid epoxy resin and the solid epoxy resin in combination.
  • liquid epoxy resin a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.
  • liquid epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton.
  • An alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a naphthalene type epoxy resin is more preferable.
  • liquid epoxy resin examples include “HP4032”, “HP4032D” and “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC; “828US”, “jER828EL”, “825" and “Epicoat” manufactured by Mitsubishi Chemical Co., Ltd.
  • the viscosity of the liquid epoxy resin at 25 ° C. is preferably 300 mPa ⁇ s or more, more preferably 500 mPa ⁇ s or more, still more preferably 1000 mPa ⁇ s or more, from the viewpoint of allowing bubbles to stably exist in the resin composition. It is preferably 5000 mPa ⁇ s or less, more preferably 4000 mPa ⁇ s or less, and further preferably 3000 mPa ⁇ s or less.
  • the viscosity of the liquid epoxy resin can be measured using, for example, an E-type viscometer.
  • solid epoxy resin a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.
  • solid epoxy resin examples include bixilenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and biphenyl.
  • Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, and naphthol type epoxy resin is more preferable.
  • solid epoxy resin examples include "HP4032H” (naphthalene type epoxy resin) manufactured by DIC; "HP-4700” and “HP-4710” (naphthalen type tetrafunctional epoxy resin) manufactured by DIC; DIC. "N-690” (cresol novolac type epoxy resin); DIC “N-695" (cresol novolac type epoxy resin); DIC "HP-7200”, “HP-7200HH”, “HP” -7200H “(dicyclopentadiene type epoxy resin);” EXA-7311 “,” EXA-7311-G3 ",” EXA-7311-G4 ",” EXA-7311-G4S ",” HP6000 "manufactured by DIC.
  • Naphthylene ether type epoxy resin Naphthylene ether type epoxy resin
  • EPPN-502H trisphenol type epoxy resin
  • NC7000L naphthol novolac type epoxy resin
  • NC3000H naphthol novolac type epoxy resin
  • NC3100 biphenyl type epoxy resin
  • ESN475V naphthol type epoxy resin
  • ESN485" manufactured by Nittetsu Chemical & Materials Co., Ltd.
  • the amount ratio (liquid epoxy resin: solid epoxy resin) thereof is a mass ratio, preferably 1: 1 to 1:20. It is more preferably 1: 1.5 to 1:15, and particularly preferably 1: 2 to 1:10.
  • the desired effect of the present invention can be remarkably obtained.
  • moderate adhesiveness is provided.
  • sufficient flexibility is usually obtained and handleability is improved.
  • a cured product having sufficient breaking strength can be obtained.
  • the epoxy equivalent of the component (E) is preferably 50 g / eq. ⁇ 5000g / eq. , More preferably 50 g / eq. ⁇ 3000 g / eq. , More preferably 80 g / eq. ⁇ 2000g / eq. , Even more preferably 110 g / eq. ⁇ 1000 g / eq. Is. Within this range, the crosslink density of the cured product of the resin composition layer becomes sufficient, and an insulating layer having a small surface roughness can be obtained.
  • Epoxy equivalent is the mass of an epoxy resin containing 1 equivalent of an epoxy group. This epoxy equivalent can be measured according to JIS K7236.
  • the weight average molecular weight (Mw) of the component (E) is preferably 100 to 5000, more preferably 200 to 3000, still more preferably 250 to 1500, from the viewpoint of remarkably obtaining the desired effect of the present invention.
  • the content of the component (E) is preferably 1% by mass or more when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. It is preferably 5% by mass or more, more preferably 10% by mass or more.
  • the upper limit of the content of the epoxy resin is preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.
  • the content of the component (E) is preferably 1% by mass or more when the resin component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. It is more preferably 5% by mass or more, further preferably 10% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less.
  • the resin composition may contain (F) an epoxy curing agent as an optional component in addition to the above-mentioned components.
  • the component (F) does not correspond to the component (B).
  • the (F) epoxy curing agent usually has a function of reacting with the component (E) to cure the resin composition.
  • the epoxy curing agent may be used alone or in combination of two or more.
  • a compound capable of reacting with the component (E) to cure the resin composition can be used, and for example, an active ester-based curing agent, a phenol-based curing agent, and a benzoxazine-based curing agent can be used.
  • an active ester-based curing agent a compound capable of reacting with the component (E) to cure the resin composition
  • a phenol-based curing agent e.g., phenol-based curing agent
  • a benzoxazine-based curing agent e.g., a benzoxazine-based curing agent
  • examples thereof include agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, and cyanate ester-based curing agents.
  • any of an active ester-based curing agent, a phenol-based curing agent, a benzoxazine-based curing agent, and a carbodiimide-based curing agent is preferable from the viewpoint of remarkably obtaining the effect of the present invention, and the active ester-based curing agent and the phenol-based curing agent are preferable.
  • Any of the agents is more preferable, and it is further preferable to use an active ester-based curing agent and a phenol-based curing agent in combination.
  • the active ester-based curing agent examples include curing agents having one or more active ester groups in one molecule.
  • the active ester-based curing agent two or more ester groups having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds are contained in one molecule.
  • the compound to have is preferable.
  • the active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound.
  • an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. ..
  • carboxylic acid compound examples include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like.
  • phenol compound or naphthol compound examples include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-.
  • the "dicyclopentadiene-type diphenol compound” refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.
  • the active ester-based curing agent examples include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoyl compound of phenol novolac.
  • active ester compounds containing examples include active ester compounds containing. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable.
  • the "dicyclopentadiene-type diphenol structure” represents a divalent structure composed of phenylene-dicyclopentylene-phenylene.
  • HPC-8000-65T "," HPC-8000H-65TM ",” EXB-8000L “,” EXB-8000L-65TM “(manufactured by DIC);” HPC-8150-60T “as an active ester compound containing a naphthalene structure, "HPC-8150-62T”, “EXB-8150-65T”, “EXB-8100L-65T”, “EXB-8150L-65T”, “EXB9416-70BK” (manufactured by DIC); "DC808” as an active ester compound (manufactured by Mitsubishi Chemical Co., Ltd.); “YLH1026” (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing a benzoylated product of phenol novolac; "DC808” as an active ester-based curing agent which is an acetylated product of phenol novolac.
  • the phenolic curing agent examples include a curing agent having one or more, preferably two or more hydroxyl groups bonded to an aromatic ring (benzene ring, naphthalene ring, etc.) in one molecule. Of these, a compound having a hydroxyl group bonded to a benzene ring is preferable. Further, from the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolak structure is preferable. Further, from the viewpoint of adhesion, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. In particular, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion.
  • phenol-based curing agent and the naphthol-based curing agent include “MEH-7700”, “MEH-7810", “MEH-7851”, and “MEH-8000H” manufactured by Meiwa Kasei Co., Ltd .; manufactured by Nippon Kayaku Co., Ltd. "NHN”, “CBN”, “GPH”; “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485" manufactured by Nittetsu Chemical & Materials Co., Ltd. "SN-495”, “SN-495V”, “SN-375", “SN-395"; "TD-2090”, “TD-2090-60M”, "LA-7052”, “LA” manufactured by DIC Corporation.
  • benzoxazine-based curing agent examples include “HFB2006M” manufactured by Showa High Polymer Co., Ltd., “Pd” and “FA” manufactured by Shikoku Chemicals Corporation.
  • carbodiimide-based curing agent examples include "V-03”, “V-05”, “V-07” manufactured by Nisshinbo Chemical Co., Ltd .; Stavaxol (registered trademark) P manufactured by Rheinchemy Co., Ltd. and the like.
  • the acid anhydride-based curing agent examples include a curing agent having one or more acid anhydride groups in one molecule.
  • Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylnagic.
  • amine-based curing agent examples include curing agents having one or more amino groups in one molecule, and examples thereof include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. Among them, aromatic amines are preferable from the viewpoint of achieving the desired effect of the present invention.
  • the amine-based curing agent is preferably a primary amine or a secondary amine, more preferably a primary amine.
  • amine-based curing agent examples include 4,4'-methylenebis (2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'.
  • amine-based curing agent for example, "KAYABOND C-200S”, “KAYABOND C-100", “Kayahard A-A”, “Kayahard AB”, “Kayahard AB” manufactured by Nippon Kayaku Corporation.
  • Examples include “Kayahard AS” and “Epicure W” manufactured by Mitsubishi Chemical Corporation.
  • cyanate ester-based curing agent examples include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylencyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4.
  • cyanate ester-based curing agent examples include "PT30" and “PT60” manufactured by Lonza Japan Co., Ltd. (both are phenol novolac type polyfunctional cyanate ester resins); “ULL-950S” (polyfunctional cyanate ester resin); BA230 ”,“ BA230S75 ”(prepolymer in which part or all of bisphenol A dicyanate is triazined to form a trimer); and the like.
  • the content of the epoxy curing agent is preferably 1% by mass or more, more preferably 2% by mass or more when the non-volatile component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the effect of the present invention. It is more preferably 3% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less.
  • the resin component in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 5% by mass. % Or more, more preferably 10% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less.
  • the number of active groups of the (F) epoxy curing agent is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and is preferable. Is 2 or less, more preferably 1.8 or less, still more preferably 1.6 or less, and particularly preferably 1.4 or less.
  • the "number of epoxy groups of the component (E)" is a total value obtained by dividing the mass of the non-volatile component of the component (E) present in the resin composition by the epoxy equivalent.
  • the "(F) number of active groups of the epoxy curing agent” is a total value obtained by dividing the mass of the non-volatile component of the (F) epoxy curing agent present in the resin composition by the active group equivalent.
  • the resin composition may further contain (G) component curing accelerator as an arbitrary component.
  • the component (G) may be used alone or in combination of two or more.
  • component (G) examples include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, a metal-based curing accelerator, and the like.
  • Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium thiocyanate.
  • Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.
  • amine-based curing accelerator examples include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo. Examples thereof include (5,4,0) -undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.
  • imidazole-based curing accelerator examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and the like.
  • imidazole-based curing accelerator a commercially available product may be used, and examples thereof include "P200-H50” manufactured by Mitsubishi Chemical Corporation.
  • guanidine-based curing accelerator examples include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, and trimethylguanidine.
  • the metal-based curing accelerator examples include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin.
  • organometallic complex examples include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate.
  • Examples thereof include an organic zinc complex such as iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, and an organic manganese complex such as manganese (II) acetylacetonate.
  • organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.
  • the content of the component (G) is preferably 0.01% by mass or more, more preferably 0, when the non-volatile component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. It is 0.03% by mass or more, more preferably 0.05% by mass or more, preferably 1% by mass or less, more preferably 0.8% by mass or less, still more preferably 0.5% by mass or less.
  • the resin component in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 5% by mass. % Or more, more preferably 10% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less.
  • the resin composition may further contain other additives as arbitrary components.
  • additives include resin additives such as thermoplastic resins, flame retardants, thickeners, defoamers, leveling agents, and adhesion-imparting agents. These additives may be used alone or in combination of two or more. Each content can be appropriately set by those skilled in the art.
  • the method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which a compounding component is mixed and dispersed using a rotary mixer or the like by adding a solvent or the like as necessary.
  • the resin composition contains (A) a vinyl resin having a hyperbranched structure, (B) a liquid curing agent, and (C) an inorganic filler in combination, the occurrence of warpage is suppressed, and the copper foil adhesion and dielectric properties are improved. An excellent cured product can be obtained.
  • the cured product obtained by heat-curing the resin composition at 200 ° C. for 90 minutes exhibits a characteristic of excellent adhesion to the copper foil (copper foil adhesion before the reliability test). Therefore, the cured product provides an insulating layer having excellent adhesion to the copper foil.
  • the copper foil adhesion is preferably 0.40 kgf / cm or more, more preferably 0.43 kgf / cm or more, still more preferably 0.45 kgf / cm or more.
  • the upper limit of the copper foil adhesion may be 10 kgf / cm or less.
  • the copper foil adhesion can be measured according to the method described in Examples described later.
  • the cured product obtained by heat-curing the resin composition at 200 ° C. for 90 minutes usually has adhesion (after the reliability test) to the copper foil after the reliability test (130 ° C., humidity 85% RH, 200 hours). It exhibits the property of being excellent in copper foil adhesion). Therefore, the cured product usually provides an insulating layer having excellent adhesion to the copper foil after the reliability test.
  • the adhesion of the copper foil after the reliability test is preferably 0.30 kgf / cm or more, more preferably 0.33 kgf / cm or more, and further preferably 0.35 kgf / cm or more.
  • the upper limit of the copper foil adhesion after the reliability test may be 10 kgf / cm or less.
  • the copper foil adhesion after the reliability test can be measured according to the method described in Examples described later.
  • the cured product obtained by thermally curing the resin composition at 200 ° C. for 90 minutes exhibits a characteristic of low dielectric constant. Therefore, the cured product provides an insulating layer having a low dielectric constant.
  • the dielectric constant is preferably 3.0 or less, more preferably 2.95 or less, still more preferably 2.9 or less. On the other hand, the lower limit of the dielectric constant may be 0.01 or more. The dielectric constant can be measured according to the method described in Examples described later.
  • the cured product obtained by thermally curing the resin composition at 200 ° C. for 90 minutes exhibits a characteristic of low dielectric loss tangent. Therefore, the cured product provides an insulating layer having a low dielectric loss tangent.
  • the dielectric loss tangent is preferably 0.004 or less, more preferably 0.003 or less, still more preferably 0.0025 or less.
  • the lower limit of the dielectric loss tangent may be 0.0001 or more.
  • the dielectric loss tangent can be measured according to the method described in Examples described later.
  • the cured product obtained by thermally curing the resin composition at 190 ° C. for 90 minutes exhibits the characteristic that the amount of warpage is suppressed. Therefore, the cured product usually provides an insulating layer in which the amount of warpage is suppressed.
  • the resin composition is laminated on the copper foil to obtain a resin composition layer.
  • a sample substrate is obtained by sticking it on a SUS plate with a polyimide tape so that the resin composition layer is on the upper surface, and heat-curing it at 190 ° C. for 90 minutes.
  • the amount of warpage is determined by peeling off the polyimide tape and determining the height of the highest point from the SUS plate.
  • the amount of warpage is preferably less than 1 cm, more preferably 0.8 cm or less, still more preferably 0.7 cm or less.
  • the lower limit of the amount of warpage may be 0 cm or more. The details of the measurement of the amount of warpage can be measured according to the method described in Examples described later.
  • the resin composition of the present invention can be suitably used as a resin composition for insulating applications.
  • a resin composition for forming an insulating layer of the multilayer printed wiring board (resin composition for forming an insulating layer of the multilayer printed wiring board) and an interlayer insulating layer of the printed wiring board are formed. It can be suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for forming an interlayer insulating layer of a printed wiring board).
  • 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 sheet of the present invention includes a support and a resin composition layer provided on the support and formed of 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, more preferably 30 ⁇ 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.
  • 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 other layers, if necessary.
  • other layers include a protective film similar to the support provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). Be done.
  • the thickness of the protective film is not particularly limited, but is, for example, 1 ⁇ m to 40 ⁇ m. By laminating the protective film, it is possible to suppress the adhesion and scratches of dust and the like on the surface of the resin composition layer.
  • a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and this resin varnish is applied onto a support using a die coater or the like and further dried to form a resin composition layer. It can be manufactured by.
  • organic solvent examples include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol and the like.
  • Carbitols aromatic hydrocarbons such as toluene and xylene
  • amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone.
  • 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. Although it depends on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the resin composition is obtained by drying at 50 ° C. to 150 ° C. for 3 to 10 minutes. A layer can be formed.
  • 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 printed wiring board of the present invention includes an insulating layer formed of a cured product of 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).
  • 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 with built-in components can 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 is preferably carried out under reduced pressure conditions 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 after step (II).
  • step (II) the resin composition layer is thermally cured to form an insulating layer.
  • the thermosetting 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 the curing temperature is preferably 120 ° C. to 240 ° C., more preferably 150 ° C. to 220 ° C., still more preferably 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. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 115 ° C. or lower, more preferably 70 ° C. or higher and 110 ° C. or lower). Preheating may be performed for 5 minutes or longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes).
  • steps (III) to (V) may be carried out according to various methods known to those skilled in the art 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.
  • 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 SBU” and “Swelling Dip Security P” manufactured by Atotech Japan. Be done.
  • 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.
  • 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 Gant 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 1 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 arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 300 nm or less, more preferably 250 nm or less, still more preferably 200 nm or less.
  • the lower limit is not particularly limited, but is preferably 30 nm or more, more preferably 40 nm or more, and further preferably 50 nm or more.
  • the arithmetic mean roughness (Ra) 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).
  • a nickel alloy, a copper-titanium alloy alloy layer is preferable, a chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal layer, or a nickel-chromium alloy alloy layer is more preferable, and a copper single metal layer is preferable.
  • a metal layer is more preferred.
  • the conductor layer may be 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 a 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.
  • a conductor layer having a desired wiring pattern can be formed by plating the surface of an insulating layer by a conventionally known technique such as a semi-additive method or a full additive method, 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
  • 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 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.).
  • the semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board.
  • the "conduction point” is a "place for transmitting an electric signal in the printed wiring board", and the place may be a surface or an embedded place.
  • the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.
  • the mounting method of the semiconductor chip in manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and a bumpless build-up layer.
  • Examples thereof include a mounting method using (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like.
  • the "mounting method using the bumpless build-up layer (BBUL)” means "a mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board". Is.
  • a vinyl resin A having a hyperbranched structure having the following structure was obtained (in the formula, the broken line means that the branched structure is further bonded. The same applies hereinafter).
  • the weight average molecular weight of the vinyl resin A having a hyperbranched structure was measured and found to be 2600.
  • the vinyl equivalent of the vinyl resin A having a hyperbranched structure is 430 g / eq. Met.
  • Synthesis of vinyl resin B having a hyperbranched structure> 1 mmol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was changed to 1 mmol of 2,2-bis (4-hydroxyphenyl) hexafluoropropane.
  • a vinyl resin B having a hyperbranched structure having the following structure was obtained in the same manner as in Synthesis Example 1 except for the above items.
  • the weight average molecular weight of the vinyl resin B having a hyperbranched structure was 2780 as measured.
  • the vinyl equivalent of the vinyl resin B having a hyperbranched structure is 460 g / eq. Met.
  • the filtrate was washed with water and then dehydrated with anhydrous magnesium sulfate to concentrate and distill off the solvent.
  • the residue was crystallized from methanol to obtain a vinyl resin C having a hyperbranched structure having the following structure.
  • the weight average molecular weight of the vinyl resin C having a hyperbranched structure was measured and found to be 2670.
  • the vinyl equivalent of the vinyl resin C having a hyperbranched structure is 445 g / eq. Met.
  • Synthesis of vinyl resin D having a hyperbranched structure> In Synthesis Example 3, 0.5 mmol of 2-propenoyl bromide was changed to 0.5 mmol of methacrylyloyl bromide.
  • a vinyl resin D having a hyperbranched structure having the following structure was obtained in the same manner as in Synthesis Example 3 except for the above items.
  • the weight average molecular weight of the vinyl resin D having a hyperbranched structure was 2740 as measured.
  • the vinyl equivalent of the vinyl resin D having a hyperbranched structure is 425 g / eq. Met.
  • Example 1 Preparation of resin composition 1> 60 parts of the vinyl resin A having a hyperbranched structure synthesized in Synthesis Example 1 was heated and dissolved in 60 parts of MEK and 40 parts of toluene while stirring.
  • Example 2 Preparation of resin composition 2> In Example 1, 1) Using 6 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation “828US”, epoxy equivalent about 180) 2) Using 6 parts of bixylenol type epoxy resin (“YX4000H”, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 190 g / eq.) 3) Using 20 parts of an active ester-based curing agent ("HPC-8000-65T” manufactured by DIC Corporation, an active group equivalent of about 223 g / eq., A toluene solution having a solid content of 65% by mass) was used.
  • bisphenol A type epoxy resin Mitsubishi Chemical Corporation
  • a curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass), 5) 10 parts of (meth) acrylic liquid curing agent ("NK ester A-DOG” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight 326) and benzoxazine ring-containing allyl-based liquid curing agent ("ALP-” manufactured by Shikoku Chemicals Corporation).
  • Example 3 Preparation of resin composition 3>
  • 60 parts of vinyl resin A having a hyperbranched structure is changed to 60 parts of vinyl resin B having a hyperbranched structure.
  • 10 parts of (meth) acrylic liquid curing agent ("NK ester A-DOG” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight 326) and an allyl-based liquid curing agent having an epoxy group (“RE-” manufactured by Nippon Kayaku Co., Ltd.) 810NM ”, epoxy equivalent 220 g / eq.) 10 parts.
  • a resin composition 3 was produced in the same manner as in Example 1 except for the above items.
  • Example 4 Preparation of resin composition 4>
  • 60 parts of vinyl resin A having a hyperbranched structure is changed to 60 parts of vinyl resin C having a hyperbranched structure.
  • 10 parts of (meth) acrylic liquid curing agent ("NK Ester A-DOG” manufactured by Shin Nakamura Chemical Industry Co., Ltd., molecular weight 326), maleimide-based liquid curing agent (“BMI689” manufactured by Designer Molecule's Co., Ltd., maleimide group) Equivalent 345 g / eq.) was changed to 10 parts.
  • a resin composition 4 was produced in the same manner as in Example 1 except for the above items.
  • Example 5 Preparation of resin composition 5>
  • 60 parts of vinyl resin A having a hyperbranched structure is changed to 60 parts of vinyl resin D having a hyperbranched structure.
  • 10 parts of (meth) acrylic liquid curing agent ("NK ester A-DOG” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight 326), butadiene-based liquid curing agent ("Ricon100” manufactured by CRAY VALLEY, styrene content 25). %, Mn about 4500) 10 parts.
  • a resin composition 5 was produced in the same manner as in Example 1 except for the above items.
  • Example 6 Preparation of resin composition 6>
  • 60 parts of vinyl resin A having a hyperbranched structure is changed to 60 parts of vinyl resin E having a hyperbranched structure.
  • 10 parts of (meth) acrylic liquid curing agent ("NK ester A-DOG” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight 326), and an allyl-based liquid curing agent having an isocyanul ring (“TAIC” manufactured by Nihon Kasei Co., Ltd.).
  • TAIC isocyanul ring
  • a resin composition 6 was prepared in the same manner as in Example 1 except for the above items.
  • Example 7 Preparation of resin composition 7>
  • PDV-PM Vinyl resin A having a hyperbranched structure to 60 parts of vinyl resin having a hyperbranched structure
  • DAD allyl-based liquid curing agent
  • a resin composition 7 was produced in the same manner as in Example 1 except for the above items.
  • Example 8 Preparation of resin composition 8>
  • 60 parts of the vinyl resin A having a hyperbranched structure was changed to 60 parts of a vinyl resin having a hyperbranched structure (“PDV-PM” manufactured by Nittetsu Chemical & Materials Co., Ltd., molecular weight 5000 to 10000).
  • a resin composition 8 was produced in the same manner as in Example 2 except for the above items.
  • Example 9 Preparation of resin composition 9>
  • spherical silica surface-treated with N-phenyl-8-aminooctyl-trimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 325.2
  • SC2050-SXF manufactured by Admatex Co., Ltd., specific surface area 5
  • the amount of 9.9 m 2 / g, average particle size 0.77 ⁇ m) was changed from 165 parts to 270 parts.
  • a resin composition 9 was produced in the same manner as in Example 1 except for the above items.
  • Example 10 Preparation of resin composition 10>
  • spherical silica surface-treated with N-phenyl-8-aminooctyl-trimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 325.2
  • SC2050-SXF manufactured by Admatex Co., Ltd., specific surface area 5
  • the amount of 9.9 m 2 / g, average particle size 0.77 ⁇ m) was changed from 165 parts to 47 parts.
  • a resin composition 10 was produced in the same manner as in Example 1 except for the above items.
  • Example 11 Preparation of resin composition 11>
  • 60 parts of vinyl resin A having a hyperbranched structure is changed to 60 parts of vinyl resin F having a hyperbranched structure.
  • ALP-d benzoxazine ring-containing allyl liquid curing agent manufactured by Shikoku Chemicals Corporation, MEK solution having a solid content of 65%
  • Example 12 Preparation of resin composition 12>
  • 60 parts of the vinyl resin F having a hyperbranched structure was changed to 60 parts of the vinyl resin G having a hyperbranched structure.
  • a resin composition 12 was produced in the same manner as in Example 11 except for the above items.
  • Example 13 Preparation of resin composition 13>
  • 60 parts of the vinyl resin F having a hyperbranched structure was changed to 60 parts of the vinyl resin H having a hyperbranched structure.
  • a resin composition 13 was produced in the same manner as in Example 11 except for the above items.
  • Example 14 Preparation of resin composition 14>
  • 60 parts of vinyl resin F having a hyperbranched structure was changed to 60 parts of vinyl resin I having a hyperbranched structure.
  • a resin composition 14 was prepared in the same manner as in Example 11 except for the above items.
  • Example 1 Preparation of Resin Composition 15>
  • 60 parts of vinyl resin A having a hyperbranched structure was changed to 92 parts of oligophenylene ether / styrene resin (“OPE-2St” manufactured by Mitsubishi Gas Chemical Company, Inc., a toluene solution having a non-volatile content of 65%).
  • a resin composition 15 was prepared in the same manner as in Example 1 except for the above items.
  • Example 2 Preparation of Resin Composition 16>
  • 60 parts of the vinyl resin A having a hyperbranched structure was changed to 92 parts of an oligophenylene ether / styrene resin (“OPE-2St” manufactured by Mitsubishi Gas Chemical Company, Inc., a toluene solution having a non-volatile content of 65%).
  • a resin composition 16 was produced in the same manner as in Example 2 except for the above items.
  • Example 3 Preparation of Resin Composition 17>
  • (Meta) Acrylic liquid curing agent ("NK Ester A-DOG” manufactured by Shin Nakamura Chemical Industry Co., Ltd., molecular weight 326) without using 10 parts
  • 2) Spherical silica surface-treated with N-phenyl-8-aminooctyl-trimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 325.2
  • SC2050-SXF manufactured by Admatex Co., Ltd., specific surface area 5.9 m 2
  • the amount of / g, average particle size 0.77 ⁇ m) was changed from 165 parts to 140 parts.
  • a resin composition 17 was produced in the same manner as in Example 1 except for the above items.
  • a PET film (“Lumilar R80” manufactured by Toray Industries, Inc., thickness 38 ⁇ m, softening point 130 ° C., hereinafter "Release PET") treated with an alkyd resin-based mold release agent ("AL-5" manufactured by Lintec Corporation). There are times when.) Was prepared.
  • the resin compositions 1 to 17 are uniformly applied on the support with a die coater so that the thickness of the dried resin composition layer is 40 ⁇ m, and dried at 70 ° C. to 95 ° C. for 3 minutes. A resin composition layer was formed on the support. Next, a rough surface of a polypropylene film (“Alfan MA-411” manufactured by Oji F-Tex Co., Ltd., thickness 15 ⁇ m) was bonded to the surface of the resin composition layer that was not bonded to the support. As a result, a resin sheet having a support, a resin composition layer, and a protective film in this order was obtained.
  • the protective film was peeled off from the produced resin sheet to expose the resin composition layer.
  • a batch type vacuum pressure laminator (2-stage build-up laminator "CVP700” manufactured by Nikko Materials Co., Ltd.)
  • the resin composition layer was laminated on both sides of the inner layer substrate so as to be in contact with the inner layer substrate.
  • Laminating was carried out by reducing the pressure for 30 seconds, adjusting the atmospheric pressure to 13 hPa or less, and then crimping at 120 ° C. and a pressure of 0.74 MPa for 30 seconds. Then, heat pressing was performed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds.
  • the treated surface of the CZ copper foil was laminated on the resin composition layer under the same conditions as described above. Then, the resin composition layer was cured under the curing conditions of 200 ° C. for 90 minutes to form an insulating layer, thereby producing an evaluation substrate.
  • the prepared evaluation substrate was cut into small pieces of 150 ⁇ 30 mm. Make a notch in the copper foil part of a small piece with a width of 10 mm and a length of 100 mm using a cutter, peel off one end of the copper foil and grab it with a gripper, and at room temperature, in the vertical direction at a speed of 50 mm / min. The load (kgf / cm) when the 35 mm was peeled off was measured, and the peeling strength was determined. A tensile tester (“AC-50C-SL” manufactured by TSE) was used for the measurement.
  • the content (% by mass) of each component is the content when the non-volatile component in the resin composition is 100% by mass.

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Abstract

Composition de résine, selon la présente invention, comprenant : (A) une résine vinylique présentant une structure hyper-ramifiée ; (B) un agent de durcissement liquide ; et (C) une charge inorganique.
PCT/JP2021/024644 2020-06-30 2021-06-29 Composition de résine WO2022004756A1 (fr)

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JP2022534065A JP7414143B2 (ja) 2020-06-30 2021-06-29 樹脂組成物
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JPS63273643A (ja) * 1987-05-02 1988-11-10 Sumitomo Chem Co Ltd トリアジン環含有樹脂
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