WO2016104748A1 - 末端変性可溶性多官能ビニル芳香族共重合体、硬化性樹脂組成物及びこれを用いた光導波路 - Google Patents

末端変性可溶性多官能ビニル芳香族共重合体、硬化性樹脂組成物及びこれを用いた光導波路 Download PDF

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WO2016104748A1
WO2016104748A1 PCT/JP2015/086343 JP2015086343W WO2016104748A1 WO 2016104748 A1 WO2016104748 A1 WO 2016104748A1 JP 2015086343 W JP2015086343 W JP 2015086343W WO 2016104748 A1 WO2016104748 A1 WO 2016104748A1
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meth
compound
copolymer
acrylate
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PCT/JP2015/086343
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English (en)
French (fr)
Japanese (ja)
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川辺　正直
スレスタ・ニランジャン・クマール
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新日鉄住金化学株式会社
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Priority to JP2016566542A priority Critical patent/JP6634029B2/ja
Priority to KR1020177019810A priority patent/KR102498471B1/ko
Priority to CN201580070594.6A priority patent/CN107108782B/zh
Publication of WO2016104748A1 publication Critical patent/WO2016104748A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C08F212/36—Divinylbenzene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
    • C08F4/14—Boron halides or aluminium halides; Complexes thereof with organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type

Definitions

  • the present invention relates to a novel terminal-modified soluble polyfunctional vinyl aromatic copolymer having improved heat resistance, compatibility and toughness, and a curable resin composition.
  • a curable resin composition containing a novel terminal-modified soluble polyfunctional vinyl aromatic copolymer and useful as a substrate material in the field of advanced electronic equipment in a field requiring high reliability, its curable composite material, and
  • the present invention relates to a laminate, a resin composition for forming an optical waveguide excellent in transparency, light propagation loss, heat discoloration, environmental reliability, and light transmission loss, a resin film for forming an optical waveguide, and an optical waveguide using these.
  • Patent Document 1 a divinyl aromatic compound and a monovinyl aromatic compound are polymerized in an organic solvent at a temperature of 20 to 100 ° C. in the presence of a Lewis acid catalyst and an initiator having a specific structure.
  • the soluble polyfunctional vinyl aromatic copolymer obtained by making it to have been disclosed is disclosed.
  • Patent Document 2 discloses a monomer component containing 20 to 100 mol% of a divinyl aromatic compound in the presence of a quaternary ammonium salt and a Lewis acid catalyst and an initiator having a specific structure at 20 to 120 ° C.
  • a method for producing a soluble polyfunctional vinyl aromatic copolymer having a controlled molecular weight distribution by cationic polymerization at a temperature of 5 ° C is disclosed.
  • the soluble polyfunctional vinyl aromatic copolymer obtained by the techniques disclosed in these two patent documents is excellent in solvent solubility and processability, and by using this, a cured product excellent in heat resistance having a high glass transition temperature. Can be obtained.
  • the soluble polyfunctional vinyl aromatic copolymer obtained by these techniques itself has a polymerizable double bond, it is cured to give a cured product having a high glass transition temperature. Therefore, it can be said that this hardened
  • the polarity is high.
  • the compatibility or solubility between the epoxy compound and the phenol resin is not sufficient, and the thermal decomposition resistance to a high process temperature is not sufficient. Therefore, in many cases, an opaque composition is provided depending on the type of epoxy compound or phenol resin, and it becomes difficult to produce a uniform cured product of the epoxy compound or phenol resin and a soluble polyfunctional vinyl aromatic copolymer.
  • the degree of freedom in compounding formulation design is small and the toughness of the cured product is low, there are cases where defects such as blistering and peeling occur due to a high thermal history near 280 to 300 ° C.
  • Patent Document 3 discloses a copolymer obtained by copolymerizing a divinyl aromatic compound (a) and a monovinyl aromatic compound (b), and an ether bond or a thioether bond is formed on a part of the terminal group.
  • a soluble polyfunctional vinyl aromatic copolymer having a chain hydrocarbon group or an aromatic hydrocarbon group interposed therebetween is disclosed.
  • this soluble polyfunctional vinyl aromatic copolymer has insufficient toughness, sufficient mechanical properties cannot be obtained in the cured product of the curable composition.
  • problems such as insufficient delamination strength and reduced reliability.
  • an ester compound can be used as a cocatalyst
  • examples of specifically usable ester compounds include soluble polyfunctional vinyl aromatic copolymers such as ethyl acetate and methyl propionate. It was an ester compound that does not have a function of introducing a functional group at the end of the. Therefore, the terminal group of the soluble polyfunctional vinyl aromatic copolymer disclosed in Patent Document 3 is a chain hydrocarbon compound having an alcoholic hydroxyl group, an aromatic hydrocarbon compound and a chain having a thioalcohol mercapto group. Chain hydrocarbon groups or aromatic hydrocarbon groups via either ether bonds or thioether bonds derived from chain hydrocarbon compounds and aromatic hydrocarbon compounds as terminal groups.
  • Patent Document 4 and Patent Document 5 disclose a polyfunctional vinyl aromatic copolymer having a terminal group derived from an aromatic ether compound, and a soluble polyfunctional compound having a terminal group derived from a thio (meth) acrylate compound.
  • Functional vinyl aromatic copolymers are disclosed.
  • the soluble polyfunctional vinyl aromatic copolymer disclosed in these patent documents has improved toughness, it has a low dielectric property in a high frequency band accompanying an increase in information communication volume in recent years.
  • there is a problem that it cannot be applied to advanced technology fields that require high-performance, high-level electrical characteristics and thermal / mechanical characteristics such as the advanced electrical / electronic fields.
  • these soluble polyfunctional vinyl aromatic copolymers have the disadvantage that they cannot be used as substrate materials in fields that require a high degree of reliability because the adhesiveness at the interface with the glass cloth decreases after the history of wet heat. It was.
  • Patent Document 6 includes a polyphenylene ether oligomer having vinyl groups at both ends, and a polyfunctional vinyl aromatic copolymer having a structural unit derived from a monomer composed of a divinyl aromatic compound and an ethyl vinyl aromatic compound.
  • a curable resin composition is disclosed.
  • the curable resin composition using this soluble polyfunctional vinyl aromatic copolymer has insufficient delamination strength, plating peel strength and dielectric properties after wet heat history, it is used as a substrate material in the field of advanced electronic equipment. Had the disadvantage that it could not be used.
  • Patent Document 7 discloses a polyfunctional vinyl aromatic copolymer having a structural unit derived from a monomer composed of a divinyl aromatic compound and an ethyl vinyl aromatic compound, an epoxy group, a cyanate group, a vinyl group, an ethynyl group, an isocyanate group, and A curable resin composition comprising a thermosetting resin containing one or more functional groups selected from the group consisting of hydroxyl groups is disclosed.
  • the curable resin composition using the soluble polyfunctional vinyl aromatic copolymer has a problem that it cannot be applied to a high-functional advanced technology field that requires a high degree of miniaturization because the plating property is insufficient. was there.
  • the polymer optical waveguide As a form of the polymer optical waveguide, a rigid optical waveguide manufactured on a hard support substrate such as a glass epoxy resin that is supposed to be applied to an opto-electric hybrid substrate, or a flexible optical device that does not have a hard support substrate that assumes connection between boards Waveguides are considered suitable. Furthermore, by using an opto-electric composite flexible wiring board in which a flexible wiring board and an optical waveguide are integrally combined, the degree of mounting freedom can be further improved.
  • Polymer optical waveguides are required to have heat resistance and environmental reliability as well as transparency (low light propagation loss) from the viewpoint of the usage environment of equipment and component mounting.
  • the demand for toughness is increasing from the viewpoint of the strength and handleability of the optical waveguide.
  • an optical waveguide manufacturing process a method capable of easily forming a core pattern is required, and one of the methods is a pattern forming method by exposure and development widely used in a printed wiring board manufacturing process. be able to.
  • an optical waveguide material containing a (meth) acrylic polymer for example, see Patent Documents 8 to 11 is known.
  • the optical waveguide materials described in Patent Documents 8 and 9 can form a core pattern by exposure and development, have transparency at a wavelength of 850 nm, and have good light propagation loss after a high-temperature and high-humidity test, There is no specific description regarding evaluation, for example, test results such as light propagation loss after a solder reflow test.
  • the optical waveguide material described in Patent Document 10 exhibits excellent optical transmission loss and has good heat resistance, but is brittle and does not satisfy toughness.
  • the optical waveguide material described in Patent Document 11 has transparency at a wavelength of 850 nm and is excellent in toughness, it relates to test results such as heat resistance evaluation, for example, light propagation loss after a solder reflow test.
  • test results such as heat resistance evaluation, for example, light propagation loss after a solder reflow test.
  • environmental reliability for example, test results such as light propagation loss after a high temperature and high humidity storage test or a temperature cycle test.
  • JP 2004-123873 A Japanese Patent Laying-Open No. 2005-213443 JP 2007-332273 A JP 2010-229263 A JP 2010-209279 A WO2005 / 73264 JP 2006-274169 A JP 2006-146162 A JP 2008-33239 A JP 2006-71880 A JP 2007-1222023 A
  • the present invention provides a novel terminal-modified soluble polyfunctional vinyl aromatic copolymer with improved heat resistance, compatibility and toughness, and at the same time, a high-level electronic device field that requires high reliability.
  • An object of the present invention is to provide a curable resin composition for an optical waveguide capable of forming a waveguide with good productivity and workability, a resin film for forming an optical waveguide, and an optical waveguide using these.
  • a specific terminal-modified soluble polyfunctional vinyl aromatic copolymer has one or more unsaturated groups in the molecule and has one or more specific terminal groups.
  • the present inventors have found that a curable resin composition containing a vinyl compound and a radical polymerization initiator can solve the above-mentioned problems, and have reached the present invention.
  • the present invention is a copolymer having a divinyl aromatic compound (a) unit and a monovinyl aromatic compound (b) unit, and a terminal group represented by the following formula (2) and the following formula (3).
  • a terminal-modified soluble polyfunctional vinyl aromatic copolymer which is soluble in a solvent and has polymerizability.
  • R 1 represents a hydrocarbon group having 1 to 18 carbon atoms or hydrogen
  • R 2 to R 3 represents a hydrocarbon group having 1 to 18 carbon atoms
  • R 4 represents hydrogen or a methyl group.
  • the divinyl aromatic compound (a) unit preferably includes a structural unit having no vinyl group and a structural unit having one vinyl group.
  • the copolymer preferably has a number average molecular weight Mn of 300 to 100,000 and a molecular weight distribution (Mw / Mn) of 100.0 or less.
  • the copolymer preferably has a terminal group introduction amount (c1) represented by the above formula (3) of the following formula (4).
  • the molar fraction (a) of the structural unit derived from the divinyl aromatic compound in the copolymer and the molar fraction (b) of the structural unit derived from the monovinyl aromatic compound are represented by the following formula (5): 0.05 ⁇ (a) / ⁇ (a) + (b) ⁇ ⁇ 0.95 (5)
  • the molar fraction (c) of the end groups represented by the above formulas (1) and (2) is the following formula (6) 0.005 ⁇ (c) / ⁇ (a) + (b) ⁇ ⁇ 2.0 (6)
  • the present invention provides a divinyl aromatic compound (a), a monovinyl aromatic compound (b), a (meth) acrylic acid ester compound (c) represented by the following formula (1), a Lewis acid catalyst, an inorganic compound
  • a divinyl aromatic compound (a) a monovinyl aromatic compound (b), a (meth) acrylic acid ester compound (c) represented by the following formula (1), a Lewis acid catalyst, an inorganic compound
  • the terminal-modified soluble polyfunctional vinyl aromatic copolymer is produced by polymerizing in the presence of one or more catalysts (d) selected from the group consisting of strong acids and organic sulfonic acids. (Here, R 1 to R 4 are the same as the formulas (2) and (3))
  • the total amount of divinyl aromatic compound (a) and monovinyl aromatic compound (b) is 100 mol%, and divinyl aromatic compound (a) is 5 to 95 mol%, monovinyl aromatic.
  • Group compound (b) is used in an amount of 95 to 5 mol%, and (meth) acrylic acid ester compound (c) represented by the above formula (1) is further added in an amount of 0.5 to 500 mol, based on 100 mol of all monomers,
  • the catalyst (d) is used in an amount of 0.001 to 10 moles per mole of the (meth) acrylic ester compound (c), and the polymerization raw material containing these is used in a homogeneous solvent having a dielectric constant of 2.0 to 15.0. To polymerize.
  • the present invention is a curable composition
  • a curable composition comprising the above-mentioned terminal-modified soluble polyfunctional vinyl aromatic copolymer and a radical polymerization initiator.
  • the curable composition can contain a modified polyphenylene ether (XC).
  • XC modified polyphenylene ether
  • the curable composition includes an epoxy resin having two or more epoxy groups and an aromatic structure in one molecule, an epoxy resin having two or more epoxy groups and a cyanurate structure in one molecule, and / or two or more in one molecule.
  • One or more epoxy resins (XD) selected from the group consisting of epoxy resins having an epoxy group and an alicyclic structure (XD) and a curing agent (XE) can be contained.
  • the present invention is a cured product obtained by curing the above curable composition, or a film obtained by molding the above curable composition into a film.
  • the present invention is a curable composite material comprising the above curable composition and a base material, wherein the base material is contained in a proportion of 5 to 90% by weight, and A cured composite material obtained by curing the curable composite material, and a laminate comprising the cured composite material layer and a metal foil layer.
  • the present invention provides a resin-coated metal foil having a film formed from the above curable composition on one side of the metal foil, or a circuit board obtained by dissolving the above curable composition in an organic solvent It is a varnish for materials.
  • the divinyl aromatic compound (a), the monovinyl aromatic compound (b) and the (meth) acrylic acid ester compound (c) are selected from the group consisting of a Lewis acid catalyst, a strong inorganic acid and an organic sulfonic acid.
  • the molar fraction (A) of the structural unit derived from the divinyl aromatic compound and the molar fraction (B) of the structural unit derived from the monovinyl aromatic compound in the copolymer are represented by the following formula (4): 0.05 ⁇ (A) / ⁇ (A) + (B) ⁇ ⁇ 0.95 (4)
  • the molar fraction (C) of the terminal group is represented by the following formula (5): 0.005 ⁇ (C) / ⁇ (A) + (B) ⁇ ⁇ 2.0 (5)
  • the present invention also relates to a method for producing a copolymer by reacting a divinyl aromatic compound (a), a monovinyl aromatic compound (b) and a (meth) acrylic acid ester compound (c).
  • One or more catalysts (d) selected from the following are used, and a polymerization raw material containing them is polymerized at a temperature of 20 to 120 ° C.
  • Polymer end It has 1.0 (pieces / molecule) or more end groups derived from the (meth) acrylic acid ester compound (c) represented by the following formulas (2) to (3), and is toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. It is also a method for producing a terminal-modified soluble polyfunctional vinyl aromatic copolymer characterized by obtaining a copolymer that is soluble in water.
  • the present invention relates to a component (A): a divinyl aromatic compound (a) unit and a monovinyl aromatic compound (b) unit, and a terminal group represented by the following formula (2) and the following formula (3).
  • the blending amount of the component (A) is 5 to 94.9 wt%
  • the blending amount of the component (B) is 5.0 to 85 wt%
  • the blending amount of the component (C) is 0.1 to 10 wt%.
  • a curable resin composition is 5 to 94.9 wt%
  • the blending amount of the component (B) is 5.0 to 85 wt%
  • the blending amount of the component (C) is 0.1 to 10 wt%.
  • the component (A) is preferably a copolymer having divinyl aromatic compound (a) units and monovinyl aromatic compound (b) units, and terminal groups represented by the above formulas (2) and (3).
  • the divinyl aromatic compound (a) unit is represented by the structural unit represented by the following formula (a1), the structural unit represented by the following formula (a2), and the following formula (a3).
  • the monovinyl aromatic compound (b) unit having a structural unit has a structural unit represented by the following formula (b), is solvent-soluble, and has a terminal-modified soluble polyfunctional vinyl aromatic copolymer having a polymerizable property. It is good that it is united.
  • R 15 , R 16 and R 17 represent an aromatic hydrocarbon group having 6 to 30 carbon atoms.
  • R 18 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms.
  • Z represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydrogen atom.
  • the present invention is a curable resin composition for forming an optical waveguide, wherein the curable resin composition is for forming an optical waveguide.
  • the component (C) preferably contains a radical photopolymerization initiator.
  • (B) component contains the vinyl compound which has a structural unit represented by the following general formula (16) or (17), or the curable vinyl type polymer produced from this vinyl compound.
  • R 5 and R 8 represent a hydrogen atom or a methyl group
  • X 1 and X 2 are each selected from the group consisting of a single bond, or an ester bond, an ether bond, a thioester bond, a thioether bond, and an amide bond.
  • a divalent organic group having 1 to 20 carbon atoms which may contain the above bond is shown, and R 6 and R 9 are a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • the present invention is also a resin film for forming an optical waveguide formed by using the above curable resin composition for forming an optical waveguide. Furthermore, this invention is an optical waveguide which has a core part and / or a clad layer formed using said curable resin composition for optical waveguide formation, or said resin film for optical waveguide formation.
  • the optical waveguide preferably has a light propagation loss of 0.3 dB / cm or less in a light source having a wavelength of 850 nm.
  • the cured product obtained from the terminal-modified soluble polyfunctional vinyl aromatic copolymer of the present invention or a material containing the same has improved heat resistance, compatibility and toughness. Moreover, according to the production method of the present invention, the copolymer can be produced with high efficiency.
  • the terminal-modified soluble polyfunctional vinyl aromatic copolymer of the present invention as a curable compound, the molecule has a large free volume with a large molecular size and few polar groups. A cured product having low dielectric properties can be obtained, and good adhesion, plating properties, and dielectric loss tangent properties after wet heat history can be realized simultaneously.
  • the curable resin composition of the present invention is excellent in transparency, heat resistance, and toughness, and can form a highly accurate thick film, not only as a curable resin composition in a transparent material, but particularly in an optical waveguide. It is useful for forming applications and can be a resin composition or resin film for forming an optical waveguide with high productivity. Moreover, it can be set as the optical waveguide excellent in transparency, heat resistance, environmental reliability, and toughness by using such a resin composition and resin film for optical waveguide formation.
  • the soluble polyfunctional vinyl aromatic copolymer of the present invention comprises a structural unit having no vinyl group, a divinyl aromatic compound (a) unit and a monovinyl aromatic compound (b) unit comprising a structural unit having one vinyl group. And a copolymer having terminal groups represented by the above formulas (2) and (3), which is a solvent-soluble and terminal-modified soluble polyfunctional vinyl aromatic copolymer having polymerizability.
  • This terminal-modified soluble polyfunctional vinyl aromatic copolymer includes a divinyl aromatic compound (a) and a monovinyl aromatic compound (b), and a (meth) acrylic acid ester compound (c) represented by the above formula (1).
  • R 1 represents a hydrocarbon group having 1 to 18 carbon atoms or hydrogen
  • R 2 to R 3 represent hydrocarbon groups having 1 to 18 carbon atoms
  • R 4 represents hydrogen or a methyl group.
  • Preferred R 1 to R 3 are alkyl groups having 1 to 6 carbon atoms such as a methyl group and an ethyl group.
  • the soluble polyfunctional vinyl aromatic copolymer of the present invention comprises a divinyl aromatic compound (a), a monovinyl aromatic compound (b), and a (meth) acrylic ester compound (c) in the presence of a catalyst (d).
  • the copolymer is preferably a copolymer obtained by polymerization, and at least a part of the terminal is modified with a terminal group derived from the (meth) acrylic acid ester compound (c).
  • This copolymer has a structural unit derived from the divinyl aromatic compound (a) and a structural unit derived from the monovinyl aromatic compound (b).
  • the molecular weight of the copolymer tends to be large, and the crosslink density becomes excessively high, so that the etching characteristics may be deteriorated, the shape is excellent, and the optical waveguide has small optical loss. May be difficult to form.
  • the structural unit derived from the divinyl aromatic compound (a) includes a structural unit having no vinyl group and a structural unit having one vinyl group. Preferably, it is considered to have structural units represented by the above formulas (a1), (a2) and (a3). Hereinafter, these structural units are referred to as units (a1) to (a3).
  • a structural unit having one vinyl group for example, units (a1) and (a3) gives the copolymer polymerizability, and the copolymer is polyfunctional to form a curable resin.
  • the unit (a2) which is a structural unit having no vinyl group, gives a crosslinked structure and increases the degree of branching. However, if the crosslinking proceeds too much, the unit is cured and becomes insoluble in the solvent. And the unit (a3) must be present.
  • the units (a1) and (a3) is preferably 10 to 60 mol%, preferably 15 to 50 mol%, more preferably 20 to 40 mol%.
  • the content of the unit (a2) is preferably 5 to 50 mol%, and preferably 10 to 40 mol%.
  • the molar ratio between units (a1) and (a3) is preferably in the range of 99.999: 0.001 to 1:99.
  • the unit (a1) in the copolymer is preferably in the range of 99.99: 0.01 to 30:70 because the polymerizability upon curing is better than that of the unit (a3). More preferably, it is in the range of 99.99: 0.01 to 50:50.
  • the content of the structural unit having one vinyl group in the structural unit derived from the divinyl aromatic compound may be 10 to 90 mol%, preferably 20 to 80 mol%, more preferably Is 30 to 70 mol%.
  • the content of the structural unit or the degree of polymerization is controlled so as to exhibit solvent solubility.
  • R 15 , R 16 and R 17 represent an aromatic hydrocarbon group having 6 to 30 carbon atoms, which are derived from a divinyl aromatic compound. So it is understood from the explanation.
  • R 18 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms
  • Z represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydrogen atom.
  • the content in the structural unit derived from the divinyl aromatic compound (a) in the copolymer is preferably 5 to 95 mol%, preferably 10 to 90 mol%, more preferably 20 to 70 mol%. It is. If the content is small, the heat resistance decreases with a decrease in the crosslink density, so that it is difficult to maintain a good shape when subjected to a thermal history in the optical waveguide formation process, etc. Etching characteristics are deteriorated, and it becomes difficult to form an optical waveguide having a fine microstructure.
  • the structural unit (a) is contained in an amount of 30 to 90 mol% with respect to a total of 100 mol% of all the structural units.
  • the structural unit (a) contains a vinyl group as a cross-linking component for developing heat resistance, while the structural unit (b) derived from a monovinyl aromatic compound does not have it, thus giving moldability and the like. .
  • the copolymer of the present invention includes the structural unit derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b), the above formula (2) derived from the (meth) acrylic acid ester compound (c), and It has a terminal group represented by (3) as a structural unit.
  • the molar ratio of each structural unit is (a), (b), (c)
  • the molar fraction of end groups (c) / ⁇ (a) + (b) ⁇ is 0.005 or more, 2 Is less than 0.0, preferably 0.01 to 1.5, more preferably 0.05 to 1.0.
  • the introduction amount (c1) of the end group represented by the above formula (3) per molecule of the soluble polyfunctional vinyl aromatic copolymer is 1.0 or more on average, preferably 2 to 5 .
  • the Mn of the soluble polyfunctional vinyl aromatic copolymer (where Mn is the number average molecular weight in terms of standard polystyrene measured using gel permeation chromatography) is preferably 300 to 100,000, preferably Is 400 to 50,000, more preferably 500 to 10,000. If Mn is too low, the amount of the monofunctional copolymer contained in the copolymer increases, so the heat resistance of the cured product tends to decrease. If it is too high, a gel is likely to be formed and the viscosity increases. As a result, the moldability tends to decrease.
  • the value of the molecular weight distribution (Mw / Mn) is preferably 100.0 or less, preferably 50.0 or less, more preferably 1.5 to 10.0. Most preferably, it is 1.5 to 5.0. When this is too high, the processing characteristics of the copolymer are lowered, and gel tends to be generated.
  • the soluble polyfunctional vinyl aromatic copolymer is soluble in a solvent selected from toluene, xylene, tetrahydrofuran, dichloroethane or chloroform, but is preferably soluble in any of the above solvents.
  • “soluble in a solvent” means that 5 g or more, preferably 10 g or more is dissolved in 100 g of a solvent at 25 ° C.
  • the soluble polyfunctional vinyl aromatic copolymer has high compatibility with the (meth) acrylate compound because the terminal is modified with the above terminal group. Therefore, when the curable resin composition containing the (meth) acrylate compound is cured, it is excellent in uniform curability and transparency.
  • This copolymer comprises divinyl aromatic compound (a) and monovinyl aromatic compound (b) and (meth) acrylic acid ester compound (c) represented by formula (1), a catalyst such as a Lewis acid catalyst ( produced by polymerization using d).
  • a catalyst such as a Lewis acid catalyst ( produced by polymerization using d).
  • a (meth) acrylic acid ester compound does not have cationic polymerizability, it does not copolymerize with a vinyl aromatic compound.
  • the (meth) acrylic ester compound is an ester with a secondary or tertiary alcohol, it is cleaved at the secondary or tertiary carbon in the presence of an acid catalyst such as a Lewis acid catalyst, and the secondary Or a tertiary carbon cation and a (meth) acrylic acid anion are produced.
  • Polymerization starts from the secondary or tertiary carbon cation.
  • this initiation reaction is not necessarily high in initiator efficiency, and it is presumed that a part of the reaction is alkane such as butane and is discharged out of the system.
  • the (meth) acrylic acid anion generated by the initiation reaction reacts with the terminal carbon cation which is the active species and recombines to introduce a (meth) acrylic acid unit at the terminal end.
  • the terminal group derived from the (meth) acrylic acid ester compound (c) includes the terminal group represented by the above formulas (2) and (3), and the terminal group represented by the formula (2). Is composed of a secondary or tertiary alkyl group, but a part of this becomes an alkane and is discharged out of the system. Therefore, the amount of the end group of the formula (2) is the end group of the formula (3). It is considered that the amount is somewhat smaller than the amount of (c1). Therefore, it can be said that the amount of the terminal group is preferably specified by the amount of the terminal group (c1).
  • the amount of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) used is 5 to 95 mol% of the divinyl aromatic compound (a) and 95% of the monovinyl aromatic compound (b) with respect to 100 mol% in total.
  • the amount is preferably 5 to 5 mol%, preferably 15 to 70 mol% of the divinyl aromatic compound (a) and 85 to 30 mol% of the monovinyl aromatic compound (b).
  • the divinyl aromatic compound (a) plays an important role as a crosslinking component for branching the copolymer to make it polyfunctional and for developing heat resistance when the copolymer is thermally cured.
  • divinylbenzene including each isomer
  • divinylnaphthalene including each isomer
  • divinylbiphenyl including each isomer
  • these can be used individually or in combination of 2 or more types. From the viewpoint of molding processability and heat discoloration resistance, divinylbenzene (m-isomer, p-isomer or a mixture of isomers thereof) is more preferable.
  • Monovinyl aromatic compound (b) improves the solvent solubility and processability of the copolymer.
  • monovinyl aromatic compounds (b) include, but are not limited to, styrene, nuclear alkyl-substituted monovinyl aromatic compounds, ⁇ -alkyl substituted monovinyl aromatic compounds, ⁇ -alkyl substituted styrenes, alkoxy substituted styrenes, and the like. It is not a thing.
  • a trivinyl aromatic compound a trivinyl aliphatic compound and divinyl can be used as long as the effects of the present invention are not impaired.
  • Other monomers (e) such as aliphatic compounds and monovinyl aliphatic compounds can be used to introduce this unit into the copolymer.
  • the other monomer (e) examples include 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-trivinylcyclohexane, ethylene glycol diacrylate. , Butadiene and the like, but are not limited thereto. These can be used alone or in combination of two or more.
  • the other monomer (e) may be used within a range of less than 30 mol% of the total monomers.
  • the structural unit derived from the other monomer component (e) is within a range of less than 30 mol% with respect to the total amount of the structural unit in the copolymer.
  • monomers having a polymerizable double bond such as divinyl aromatic compound (a) and monovinyl aromatic compound (b), (meth) acrylic acid ester compounds ( c).
  • the (meth) acrylic acid ester compound (c) is represented by the above formula (1), which undergoes a cleavage reaction with the catalyst (d) during the initiation reaction and consists of a secondary or tertiary carbon cation.
  • the polymerization active species are generated and the (meth) acrylate anion generated by the above initiation reaction is recombined with the terminal carbon cation as the polymerization active species as a chain transfer agent, the end of the copolymer has toughness, Enables functions such as low light propagation loss and processability.
  • the terminal groups generated from the (meth) acrylic acid ester compound (c) are represented by the formulas (2) and (3), and are considered to be bonded to the start terminal and the terminal terminal of the copolymer, respectively.
  • the (meth) acrylic ester compound (c) is a kind of monomer as described above, but is also a polymerization additive. This is also a chain transfer agent because the end group (which is one of the structural units) is given to the copolymer by a chain transfer reaction.
  • t-butyl methacrylate, sec-butyl methacrylate, t-butyl acrylate, or Sec-Butyl acrylate is preferably used.
  • t-butyl methacrylate or t-butyl acrylate is more preferably used.
  • the amount of the (meth) acrylic acid ester compound (c) used is preferably 0.5 to 300 mol with respect to a total of 100 mol of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b). , Preferably 1 to 200 mol, more preferably 10 to 150 mol. If the amount used is too small, the amount of introduced end groups is reduced, and not only functions such as toughness are lowered, but also the molecular weight and molecular weight distribution are increased, and the molding processability is deteriorated. On the other hand, when the amount is too large, the polymerization rate is remarkably lowered, the productivity is lowered, and the refractive index is lowered.
  • the (meth) acrylic acid ester compound (c) reacts with the catalyst (d) during the polymerization reaction to start the polymerization reaction and to form a terminal group to stop the growth.
  • the amount used and reaction conditions are selected so that the amount of terminal groups derived from the (meth) acrylic acid ester compound (c) is within the range described for the copolymer.
  • the polymerization reaction uses a divinyl aromatic compound (a), a monovinyl aromatic compound (b), a (meth) acrylic acid ester compound (c), and a catalyst (d).
  • a terminal-modified copolymer may be obtained by cationic copolymerization at a temperature of 20 to 120 ° C. in a homogeneous solvent dissolved in a solvent having a ratio of 2.0 to 15.0.
  • the catalyst (d) one or more selected from the group consisting of Lewis acid catalysts, strong inorganic acids and organic sulfonic acids are used.
  • the Lewis acid catalyst can be used without particular limitation as long as it is a compound composed of a metal ion (acid) and a ligand (base) and can receive an electron pair.
  • a metal ion (acid) a metal ion (acid) and a ligand (base) and can receive an electron pair.
  • B Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Ti, W, Zn, Fe, V, etc.
  • Divalent to hexavalent metal fluorides are preferred.
  • strong inorganic acids include sulfuric acid, hydrochloric acid, and phosphoric acid.
  • the organic sulfonic acid include benzenesulfonic acid and paratoluenesulfonic acid.
  • catalysts can be used alone or in combination of two or more. From the viewpoint of controlling the molecular weight and molecular weight distribution of the obtained copolymer and polymerization activity, boron trifluoride ether (diethyl ether, dimethyl ether, etc.) complexes are most preferably used.
  • the catalyst (d) is preferably used in the range of 0.001 to 10 mol, more preferably 0.001 to 1 mol, relative to 1 mol of the (meth) acrylic ester compound (c). If it exceeds 10 moles, the polymerization rate becomes too high, so that not only the control of the molecular weight distribution becomes difficult, but also the amount of terminal groups derived from the compound (c) is reduced.
  • a terminal-modified soluble polyfunctional vinyl aromatic copolymer it is obtained from a primary alcohol such as ethyl acetate, n-propyl acetate, and n-butyl acetate and a carboxylic acid (excluding (meth) acrylic acid) as desired.
  • a primary alcohol such as ethyl acetate, n-propyl acetate, and n-butyl acetate and a carboxylic acid (excluding (meth) acrylic acid) as desired.
  • dialkyl ketones having 1 to 30 carbon atoms such as methyl ethyl ketone and methyl isobutyl ketone can be used as the cocatalyst (f).
  • the amount of the cocatalyst (f) used is less than 300 mol, preferably less than 200 mol, more preferably less than 150 mol with respect to 100 mol in total of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b). is there.
  • the co-catalyst interacts with the active species and the catalyst (d) during the polymerization reaction, and is effective for increasing the selectivity of the reaction and controlling the molecular weight. However, when used excessively, the polymerization rate is remarkably reduced. The yield of the copolymer is reduced.
  • This polymerization reaction is preferably performed in one or more organic solvents having a dielectric constant of 2 to 15 as a solvent for dissolving the terminal-modified soluble polyfunctional vinyl aromatic copolymer to be formed.
  • Organic solvent is a compound that does not essentially inhibit cationic polymerization, and dissolves catalyst, polymerization additive, co-catalyst, monomer and polyfunctional vinyl aromatic copolymer to form a uniform solution.
  • the dielectric constant is not particularly limited as long as it is in the range of 2 to 15, and can be used alone or in combination of two or more. When the dielectric constant of the solvent is low, the molecular weight distribution becomes wide, and when it is large, the polymerization rate decreases.
  • the organic solvent toluene, xylene, n-hexane, cyclohexane, methylcyclohexane and ethylcyclohexane are preferable from the viewpoint of the balance between polymerization activity and solubility.
  • the amount of the solvent used is such that the concentration of the copolymer in the polymerization solution at the end of the polymerization is 1 to 90 wt%, preferably 10 to 80 wt% in consideration of the viscosity of the resulting polymerization solution and the ease of heat removal. Particularly preferably, it is determined to be 20 to 70 wt%. If this concentration is less than 1 wt%, the polymerization efficiency is low, resulting in an increase in cost. If it exceeds 90 wt%, the molecular weight and molecular weight distribution increase, resulting in a decrease in molding processability.
  • the polymerization reaction temperature is preferably 20 to 120 ° C., and preferably 40 to 100 ° C. If the polymerization temperature is too high, the selectivity of the reaction will be reduced, causing problems such as an increase in molecular weight distribution and gel generation. If it is too low, the catalytic activity will be significantly reduced and a large amount of catalyst will need to be added .
  • the method for recovering the copolymer after the polymerization reaction is stopped is not particularly limited.
  • a commonly used method such as a steam stripping method or precipitation with a poor solvent may be used.
  • the terminal-modified soluble polyfunctional vinyl aromatic copolymer of the present invention can be advantageously obtained.
  • the curable composition according to the first aspect is useful as a substrate material in the field of advanced electronic equipment, for example, an electrical insulating material or a material for a laminate.
  • the curable composition according to the first embodiment contains a terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) and a radical polymerization initiator (also referred to as a radical polymerization catalyst) (XB).
  • XA terminal-modified soluble polyfunctional vinyl aromatic copolymer
  • XB radical polymerization initiator
  • the resin composition of the present invention is cured by causing a crosslinking reaction by means of heating or the like as described later.
  • a radical polymerization initiator (XB) may be used.
  • the amount of the radical polymerization initiator used for this purpose is 0.01 to 10% by weight, preferably 0.1 to 8% by weight, based on the sum of the components (XA) and (XB). Since the radical polymerization initiator is a radical polymerization catalyst, it is represented below by a radical polymerization initiator.
  • a known substance is used for the radical polymerization initiator.
  • Representative examples include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy ) Hexin-3, di-t-butyl peroxide, t-butylcumyl peroxide, ⁇ , ⁇ '-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (T-butylperoxy) hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (T-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy)
  • 2,3-dimethyl-2,3-diphenylbutane can also be used as a radical polymerization initiator (or polymerization catalyst).
  • the catalyst and radical polymerization initiator used for curing the resin composition are not limited to these examples.
  • the reaction can be satisfactorily performed without inhibiting the curing reaction. proceed.
  • terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) -containing curable composition can be copolymerized with the terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention, if necessary.
  • Other polymerizable monomers may be blended and cured.
  • the copolymerizable monomer a known substance is used. Typical examples are styrene, styrene dimer, alphamethylstyrene, alphamethylstyrene dimer, divinylbenzene, vinyltoluene, t-butylstyrene, chlorostyrene, dibromostyrene, vinylnaphthalene, vinylbiphenyl, acenaphthylene, divinylbenzyl ether. And allyl phenyl ether.
  • the curable composition containing the terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention includes known thermosetting resins such as vinyl ester resins, polyvinyl benzyl resins, unsaturated polyester resins, Curable vinyl resin, modified polyphenylene ether resin, maleimide resin, epoxy resin, polycyanate resin, phenol resin, etc., and known thermoplastic resins such as polystyrene, polyphenylene ether, polyetherimide, polyethersulfone, PPS resin, poly Cyclopentadiene resin, polycycloolefin resin, etc., or known thermoplastic elastomers such as styrene-ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer Polymer, Hydrogenated styrene - butadiene copolymer
  • the curable composition of the present invention is a curable composition containing a terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) and a radical polymerization initiator (XB), which is represented by the following formula (7). It contains polyphenylene ether (XC), particularly a group having at least one polymerizable unsaturated double bond at the end, for example, a modified polyphenylene ether (XC) having a phenolic hydroxyl group, a vinyl group or a (meth) acryl group. Good.
  • XC polyphenylene ether
  • terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention and the modified polyphenylene ether (XC) have good compatibility, and there is a problem that reliability is lowered due to a decrease in compatibility. Overcome and show improved properties in any formulation with high low dielectric properties and toughness, as well as properties such as formability and delamination strength.
  • m represents 1 or 2
  • L represents a polyphenylene ether chain represented by the following formula (8).
  • M represents a hydrogen atom, a group represented by the group represented by the following formula (9). When m is 1, M is not a hydrogen atom, and when m is 2, at least one of two M One of them is not a hydrogen atom.
  • T represents a hydrogen atom when m is 1, and an alkylene group or a group represented by the following formula (10) or (11) when m is 2.
  • n represents a positive integer of 50 or less
  • R 5 , R 6 , R 7 , and R 8 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, formyl A group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group;
  • X is an organic group having 1 or more carbon atoms and may contain an oxygen atom.
  • Y is a vinyl group.
  • j represents an integer of 0 or 1.
  • R 10 , R 11 , R 12 , and R 13 are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, formyl group, alkylcarbonyl group, alkenylcarbonyl group, or alkynyl. A carbonyl group is shown.
  • R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , and R 21 are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, formyl A group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group; F is a linear, branched or cyclic hydrocarbon group having 20 or less carbon atoms, including the case of 0 carbon atoms.
  • the modified polyphenylene ether represented by the formula (7) is one in which m in the formula (7) is 1 or 2.
  • the modified polyphenylene ether represented by the formula (7) is specifically a modified polyphenylene ether represented by TLMM or ML-TLM.
  • L represents a polyphenylene ether chain represented by the formula (8).
  • n represents a positive integer of 50 or less.
  • R 5 , R 6 , R 7 , and R 8 are independent of each other. That is, R 5 , R 6 , R 7 , and R 8 may be the same group or different groups.
  • R 5 , R 6 , R 7 , and R 8 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. Among these, a hydrogen atom and an alkyl group are preferable.
  • M represents a hydrogen atom or a group represented by the formula (9).
  • M represents a group represented by the formula (9) instead of a hydrogen atom when m is 1, that is, when the modified polyphenylene ether is TLM.
  • M is 2, that is, when the modified polyphenylene ether is MLTLM, at least one of the two Ms is not a hydrogen atom, and the heat resistance of the cured product It is preferable that the two Ms are groups represented by the formula (9) for the reasons of property and toughness.
  • T represents a hydrogen atom when m is 1, that is, when the modified polyphenylene ether is TLM.
  • the modified polyphenylene ether represented by TLM is a modified polyphenylene ether represented by HLM.
  • T is m, that is, when the modified polyphenylene ether is MLTLM, an alkylene group, a group represented by the formula (10), or a formula (11) The group represented by these is shown.
  • m is preferably 2
  • T is an alkylene group
  • m is 2
  • T is a 2,2-propylene group because of the toughness of the cured product and the solubility of the modified polyphenylene ether. Is preferred.
  • R 10 , R 11 , R 12 , and R 13 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, Or an alkynylcarbonyl group is shown.
  • R 10 , R 11 , R 12 , and R 13 may be the same group or different groups.
  • R 5 to R 21 Specific examples of the functional groups listed in R 5 to R 21 include the following.
  • the alkyl group is not particularly limited.
  • an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable.
  • Specific examples include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.
  • the alkenyl group is not particularly limited, but for example, an alkenyl group having 2 to 18 carbon atoms is preferable, and an alkenyl group having 2 to 10 carbon atoms is more preferable. Specific examples include a vinyl group, an allyl group, and a 3-butenyl group.
  • alkynyl group is not particularly limited, but for example, an alkynyl group having 2 to 18 carbon atoms is preferable, and an alkynyl group having 2 to 10 carbon atoms is more preferable. Specific examples include an ethynyl group and a prop-2-yn-1-yl group (propargyl group).
  • the alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group.
  • an alkylcarbonyl group having 2 to 18 carbon atoms is preferable, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferable.
  • Specific examples include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, an octanoyl group, and a cyclohexylcarbonyl group.
  • the alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group.
  • an alkenylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferable.
  • an acryloyl group, a methacryloyl group, a crotonoyl group, etc. are mentioned, for example.
  • the alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group.
  • an alkynylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferable.
  • a propioyl group etc. are mentioned, for example.
  • the number average molecular weight of the modified polyphenylene ether is not particularly limited, but is preferably 800 to 7000, more preferably 1000 to 5000. Most preferably, it is 1000 to 3000. Further, as described above, n is a positive integer of 50 or less, and is preferably a numerical value such that the number average molecular weight of the modified polyphenylene ether falls within such a range. Specifically, it is preferably 1 to 50. In addition, the number average molecular weight should just be what was measured by the general molecular weight measuring method here, and the value etc. which were specifically measured using gel permeation chromatography (GPC) are mentioned.
  • GPC gel permeation chromatography
  • the toughness and moldability of the cured product of the obtained curable composition become higher. This is because when the number average molecular weight of the modified polyphenylene ether is within such a range, it has a relatively low molecular weight, so that the fluidity is improved while maintaining toughness. When a normal polyphenylene ether having such a low molecular weight is used, the heat resistance and toughness of the cured product tend to be lowered.
  • the modified polyphenylene ether used in the present embodiment has a polymerizable unsaturated double bond at the terminal
  • the modified polyphenylene ether and the thermally crosslinked curable resin are cured by curing together with a vinyl-based thermally crosslinked curable resin.
  • Crosslinking with the resin proceeds suitably, and a cured product having sufficiently high heat resistance and toughness can be obtained. Therefore, the cured product of the obtained curable composition will be excellent in both heat resistance and toughness.
  • the curable composition of the present invention comprises a terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) and a radical polymerization initiator (XB) for the purpose of improving the adhesion reliability between different materials.
  • XA terminal-modified soluble polyfunctional vinyl aromatic copolymer
  • XB radical polymerization initiator
  • a curable composition characterized by containing an epoxy resin (XD) and a curing agent (XE) is also a preferred embodiment.
  • the epoxy resin of component (XD) is not particularly limited, but the epoxy resin is an epoxy resin having two or more epoxy groups and an aromatic structure in one molecule, and two or more epoxy groups and a cyanurate structure in one molecule. It is preferable to use one or more epoxy resins selected from the group consisting of an epoxy resin having an epoxy resin and / or an epoxy resin having two or more epoxy groups and an alicyclic structure in one molecule.
  • (XD) component includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alkylphenol novolac type epoxy resin, xylylene modified phenol novolac type epoxy resin, xylylene modified alkylphenol novolak type epoxy resin, biphenyl type epoxy It is more preferably one or more epoxy resins selected from the group consisting of resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, triglycidyl isocyanurate, cyclohexane type epoxy resins and adamantane type epoxy resins.
  • Examples of the bisphenol F type epoxy resin used as the (XD) component include, for example, an epoxy resin mainly composed of 4,4′-methylenebis (2,6-dimethylphenol) diglycidyl ether, 4,4 ′ An epoxy resin mainly composed of diglycidyl ether of -methylenebis (2,3,6-trimethylphenol), and an epoxy resin mainly composed of diglycidyl ether of 4,4'-methylenebisphenol. Among them, an epoxy resin mainly composed of 4,4'-methylenebis (2,6-dimethylphenol) diglycidyl ether is preferable.
  • the bisphenol F-type epoxy resin is commercially available as a trade name YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • biphenyl type epoxy resin examples include epoxy resins such as 4,4'-diglycidyl biphenyl and 4,4'-diglycidyl-3,3 ', 5,5'-tetramethylbiphenyl.
  • the biphenyl type epoxy resins are commercially available as trade names YX-4000 and YL-6121H manufactured by Mitsubishi Chemical Corporation.
  • dicyclopentadiene type epoxy resin examples include dicyclopentadiene dioxide and phenol novolac epoxy monomers having a dicyclopentadiene skeleton.
  • naphthalene type epoxy resins 1,2-diglycidylnaphthalene, 1,5-diglycidylnaphthalene, 1,6-diglycidylnaphthalene, 1,7-diglycidylnaphthalene, 2,7-diglycidylnaphthalene, triglycidylnaphthalene , And 1,2,5,6-tetraglycidylnaphthalene, naphthol / aralkyl type epoxy resin, naphthalene skeleton modified cresol novolak type epoxy resin, methoxynaphthalene modified cresol novolak type epoxy resin, naphthylene ether type epoxy resin, methoxynaphthalene dimethylene Modified naphthalene type epoxy resins such as type epoxy resins.
  • Examples of the adamantane type epoxy resin include 1- (2,4-diglycidyloxyphenyl) adamantane, 1- (2,3,4-triglycidyloxyphenyl) adamantane, 1,3-bis (2,4-didiene).
  • Glycidyloxyphenyl) adamantane 1,3-bis (2,3,4-triglycidyloxyphenyl) adamantane, 2,2-bis (2,4-diglycidyloxyphenyl) adamantane, 1- (2,3,4 -Trihydroxyphenyl) adamantane, 1,3-bis (2,4-dihydroxyphenyl) adamantane, 1,3-bis (2,3,4-trihydroxyphenyl) adamantane, and 2,2-bis (2, 4-dihydroxyphenyl) adamantane and the like.
  • epoxy resins from the viewpoint of compatibility with the (XA) component, dielectric properties, and small warpage of the molded product, bisphenol F type epoxy resin, alkylphenol novolac type epoxy resin, xylylene modified phenol novolak type epoxy Resins, xylylene-modified alkylphenol novolac type epoxy resins, biphenyl type epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, triglycidyl isocyanurate, cyclohexane type epoxy resins and adamantene type epoxy resins are preferably used.
  • the weight average molecular weight (Mw) of the epoxy resin used as the (XD) component is preferably less than 10,000. More preferable Mw is 600 or less, and more preferably 200 or more and 550 or less. When Mw is less than 200, the volatility of this component increases, and the handleability of the cast film / sheet tends to deteriorate. On the other hand, if Mw exceeds 10,000, the cast film / sheet tends to be hard and brittle, and the adhesiveness of the cured product of the cast film / sheet tends to be lowered.
  • the content of the component (XD) is preferably 5 parts by weight with respect to 100 parts by weight of the component (XA) and 100 parts by weight with the upper limit. More preferably, the lower limit of the content of the component (XD) is 10 parts by weight with respect to 100 parts by weight of the component (XA). On the other hand, a more preferred upper limit is 80 parts by weight, and a still more preferred upper limit is 60 parts by weight.
  • fills the said preferable minimum the adhesiveness of the hardened
  • Component curing agent is a phenol resin, or an acid anhydride having an aromatic or alicyclic skeleton, a water additive of the acid anhydride, a modified product of the acid anhydride, a hydroxyl-terminated polyphenylene ether oligomer, And it is preferable that it is an active ester compound.
  • a curable composition that becomes a cured product having an excellent balance of heat resistance, moisture resistance and dielectric properties.
  • the phenol resin used as a curing agent for the component is not particularly limited.
  • Specific examples of the phenol resin include phenol novolak, o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, polyparavinylphenol, bisphenol A type novolak, phenol aralkyl resin, naphthol aralkyl resin, Biphenyl type phenol novolak resin, biphenyl type naphthol novolak resin, decalin modified novolak, poly (di-o-hydroxyphenyl) methane, poly (di-m-hydroxyphenyl) methane, poly (di-p-hydroxyphenyl) methane, etc.
  • the phenol resin which has a melamine skeleton, the phenol resin which has a triazine skeleton, or the phenol resin which has an allyl group is preferable.
  • phenol resins include MEH-8005, MEH-8010, and NEH-8015 (all of which are manufactured by Meiwa Kasei Co., Ltd.), YLH903 (manufactured by Japan Epoxy Resin Co., Ltd.), LA-7052, LA-7054, and LA-7751.
  • LA-1356 and LA-3018-50P all of which are manufactured by DIC Corporation
  • PS6313 and PS6492 manufactured by Gunei Chemical Co., Ltd.
  • the structure of the acid anhydride having an aromatic skeleton used as a curing agent for the (XE) component, a water additive of the acid anhydride, or a modified product of the acid anhydride is not particularly limited.
  • the acid anhydride having an aromatic skeleton, a water addition of the acid anhydride, or a modified product of the acid anhydride include, for example, a styrene / maleic anhydride copolymer, benzophenone tetracarboxylic acid anhydride, pyromellitic acid anhydride, Trimellitic anhydride, 4,4'-oxydiphthalic anhydride, phenylethynylphthalic anhydride, glycerol bis (anhydrotrimellitate) monoacetate, ethylene glycol bis (anhydrotrimellitate), methyltetrahydrophthalic anhydride Acid, methylhexahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride
  • Examples of commercially available acid anhydrides having an aromatic skeleton, water additives of the acid anhydrides, or modified products of the acid anhydrides include SMA Resin EF30, SMA Resin EF40, SMA Resin EF60, and SMA Resin EF80 (any of the above Is also manufactured by Sartomer Japan), ODPA-M and PEPA (all of which are manufactured by Manac), Rikagit MTA-10, Rikagit MTA-15, Rikagit TMTA, Rikagit TMEG-100, Rikagit TMEG-200, Rikagit TMEG-300, Rikagit TMEG-500, Rikagit TMEG-S, Rikagit TH, Rikagit HT-1A, Rikagit HH, Rikagit MH-700, Rikagit MT-500, Rikagit DSDA and Rikagit TDA-100 (all of which are manufactured by Shin Nippon Rika) EPICLON B4400, EPICLON B650, and EPICLON B570
  • the acid anhydride having an alicyclic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride is an acid anhydride having a polyalicyclic skeleton, a water additive of the acid anhydride, or the A modified product of an acid anhydride, or an acid anhydride having an alicyclic skeleton obtained by addition reaction of a terpene compound and maleic anhydride, a water additive of the acid anhydride, or a modified product of the acid anhydride It is preferable. In this case, the flexibility, moisture resistance or adhesion of the insulating sheet can be further enhanced.
  • Examples of the acid anhydride having the alicyclic skeleton, a water addition of the acid anhydride, or a modified product of the acid anhydride include methyl nadic acid anhydride, acid anhydride having a dicyclopentadiene skeleton, and the acid.
  • Examples of the modified product include anhydrides.
  • Examples of commercially available acid anhydrides having the alicyclic skeleton, water additions of the acid anhydrides, or modified products of the acid anhydrides include RICAJIT HNA and RICAJIT HNA-100 (all manufactured by Shin Nippon Rika Co., Ltd.) , And EpiCure YH306, EpiCure YH307, EpiCure YH308H, EpiCure YH309 (all of which are manufactured by Japan Epoxy Resin Co., Ltd.) and the like.
  • a hydroxyl-terminated polyphenylene ether oligomer can also be used.
  • a hydroxyl group-terminated polyphenylene ether oligomer represented by the following formula (12) can be exemplified.
  • E represents a polyphenylene ether chain represented by the following formula (13)
  • G represents a hydrogen atom
  • p represents an integer of 1 or 2.
  • V represents a hydrogen atom when p is 1, and when p is 2, it represents an alkylene group or a group represented by the following formula (14) or formula (15).
  • q represents a positive integer of 50 or less
  • R 22 , R 23 , R 24 , and R 25 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, formyl A group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group;
  • R 26 , R 27 , R 28 , and R 29 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or Represents an alkynylcarbonyl group.
  • R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , and R 37 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, formyl A group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group; F is a linear, branched or cyclic hydrocarbon group having 20 or less carbon atoms, including the case of 0 carbon atoms.
  • An active ester compound can also be used as a component. Any compound having an active ester group may be used, but in the present invention, a compound having at least two active ester groups in the molecule is preferable.
  • the active ester compound used as the component (XE) is an active ester obtained from a product obtained by reacting a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound from the viewpoint of heat resistance and the like.
  • a compound is preferable, and an active ester compound obtained by reacting a carboxylic acid compound with one or more selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound is more preferable.
  • An aromatic compound obtained from a reaction of a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group and having at least two active ester groups in the molecule is particularly preferred.
  • the active ester compound used as the component (XE) may be linear or multi-branched, and the active ester compound is derived from a compound having at least two carboxylic acids in the molecule.
  • the compatibility with the epoxy resin can be increased, and when it has an aromatic ring, Sexuality can be increased.
  • carboxylic acid compound for forming the active ester compound examples include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like.
  • succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid and terephthalic acid are preferred, phthalic acid, isophthalic acid and terephthalic acid are more preferred, and isophthalic acid and terephthalic acid are further preferred. preferable.
  • thiocarboxylic acid compound for forming the active ester compound examples include thioacetic acid and thiobenzoic acid.
  • phenolic compounds and naphtholic compounds for forming active ester compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S.
  • 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl Diphenol and phenol novolak are preferable, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol and phenol novolak are more preferable, and dicyclopentadienyl diphenol and phenol novolak are more preferable.
  • Specific examples of the thiol compound for forming the active ester compound include benzenedithiol and triazinedithiol.
  • active ester compound for example, active ester compounds disclosed in JP-A Nos. 2002-12650 and 2004-277460, or commercially available compounds can be used.
  • Commercially available active ester compounds include, for example, trade names “EXB9451, EXB9460, EXB9460S, HPC-8000-65T” (manufactured by DIC), trade names “DC808” (manufactured by Japan Epoxy Resins), trade names, and the like.
  • “YLH1026” manufactured by Japan Epoxy Resin Co., Ltd.
  • the production method of the active ester compound is not particularly limited and can be produced by a known method.
  • the curable composition of the present invention can be obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. it can.
  • the amount of the active ester compound (XE) in the curable composition of the present invention is preferably 20 to 120 parts by weight, more preferably 40 to 100 parts by weight, based on 100 parts by weight of the epoxy resin (XD). More preferably, it is in the range of 50 to 90 parts by weight.
  • Examples of the curing agent used as the component (XE) include o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dithiol from the viewpoint of compatibility with the component (XA) of the present invention, moisture resistance, and adhesion.
  • Cyclopentadiene cresol polyparavinylphenol, xylylene-modified novolak, poly (di-o-hydroxyphenyl) methane, poly (di-m-hydroxyphenyl) methane, poly (di-p-hydroxyphenyl) methane, methyl nadic anhydride It is preferable to select from a product, a trialkyltetrahydrophthalic anhydride, an acid anhydride having a dicyclopentadiene skeleton or a modified product of the acid anhydride, a hydroxyl-terminated polyphenylene ether oligomer, or an active ester compound.
  • the curable composition containing the terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention includes an inorganic filler such as fused silica, crystalline silica, alumina, silicon nitride, aluminum nitride, decabromodiphenylethane, Use in combination with flame retardant imparting agents such as brominated polystyrene, especially useful as electrical or electronic component materials that require dielectric properties, flame retardancy, or heat resistance, especially semiconductor encapsulating materials and circuit board varnishes it can.
  • the varnish for circuit board material can be produced by dissolving the curable composition of the present invention in an organic solvent such as toluene, xylene, tetrahydrofuran, dioxolane and the like.
  • organic solvent such as toluene, xylene, tetrahydrofuran, dioxolane and the like.
  • Specific examples of the circuit board material include a printed wiring board, a printed circuit board, a flexible printed wiring board, and a build-up wiring board.
  • Cured products obtained by curing the curable composition containing the terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention are molded products, laminates, cast products, adhesives, coating films, and films.
  • a cured product of a semiconductor sealing material is a cast or molded product.
  • the compound is cast or molded using a transfer molding machine, an injection molding machine, or the like. Further, a cured product can be obtained by heating at 80 to 230 ° C. for 0.5 to 10 hours.
  • cured material of the varnish for circuit boards is a laminated body, and as a method of obtaining this hardened
  • an inorganic high dielectric powder such as barium titanate or an inorganic magnetic substance such as ferrite.
  • the curable composition of the present invention can be used by being bonded to a metal foil (meaning including a metal plate, hereinafter the same), as with the cured composite material described later.
  • a substrate is added to the curable composite material of the curable composition of the present invention in order to increase mechanical strength and increase dimensional stability.
  • a substrate known materials can be used.
  • various glass cloths such as roving cloth, cloth, chopped mat, and surfacing mat, asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloth.
  • Woven fabrics or nonwoven fabrics obtained from liquid crystal fibers such as wholly aromatic polyamide fibers, wholly aromatic polyester fibers, polybenzozar fibers, woven fabrics or nonwoven fabrics obtained from synthetic fibers such as polyvinyl alcohol fibers, polyester fibers, acrylic fibers, Natural fiber cloth such as cotton cloth, linen cloth, felt, carbon fiber cloth, kraft paper, cotton paper, natural cellulosic cloth such as paper-glass mixed paper, paper, etc., each alone or in combination of two or more. Used.
  • the proportion of the substrate is 5 to 90 wt%, preferably 10 to 80 wt%, more preferably 20 to 70 wt% in the curable composite material. If the substrate is less than 5 wt%, the composite material is insufficient in dimensional stability and strength after curing, and if the substrate is more than 90 wt%, the dielectric properties of the composite material are inferior.
  • a coupling agent can be used for the purpose of improving the adhesiveness at the interface between the resin and the substrate, if necessary.
  • the coupling agent general ones such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zircoaluminate coupling agent can be used.
  • the curable composition of the present invention and other components as necessary are uniformly mixed in the above-mentioned aromatic or ketone-based solvents or mixed solvents thereof. And a method in which the substrate is impregnated and then dried. Impregnation is performed by dipping or coating. The impregnation can be repeated multiple times as necessary, and at this time, the impregnation can be repeated using a plurality of solutions having different compositions and concentrations, and finally adjusted to a desired resin composition and resin amount. Is possible.
  • a cured composite material is obtained by curing the curable composite material of the present invention by a method such as heating.
  • the manufacturing method is not particularly limited.
  • a plurality of curable composite materials are stacked, and each layer is bonded under heat and pressure, and at the same time, thermosetting is performed to obtain a cured composite material having a desired thickness. it can.
  • Lamination molding and curing are usually performed simultaneously using a hot press or the like, but both may be performed independently. That is, the uncured or semi-cured composite material obtained by lamination molding in advance can be cured by heat treatment or another method.
  • Molding and curing are performed at a temperature of 80 to 300 ° C., a pressure of 0.1 to 1000 kg / cm 2, a time of 1 minute to 10 hours, and more preferably a temperature of 150 to 250 ° C. and a pressure of 1 to 500 kg / cm 2 Time: Can be performed in the range of 1 minute to 5 hours.
  • the laminate of the present invention comprises a layer of the cured composite material of the present invention and a metal foil layer.
  • the metal foil used here include a copper foil and an aluminum foil.
  • the thickness is not particularly limited, but is in the range of 3 to 200 ⁇ m, more preferably 3 to 105 ⁇ m.
  • the above-described curable composition of the present invention and a curable composite material obtained from a substrate and a metal foil are laminated in a layer configuration according to the purpose, and heated.
  • An example is a method in which the respective layers are bonded together under pressure and thermally cured.
  • the cured composite material and the metal foil are laminated in an arbitrary layer configuration.
  • the metal foil can be used as a surface layer or an intermediate layer. In addition to the above, it is possible to make a multilayer by repeating lamination and curing a plurality of times.
  • An adhesive can also be used for bonding to the metal foil.
  • the adhesive include, but are not limited to, epoxy, acrylic, phenol, and cyanoacrylate.
  • the film of the present invention is obtained by forming the curable composition of the present invention into a film.
  • the thickness is not particularly limited, but is in the range of 3 to 200 ⁇ m, more preferably 5 to 100 ⁇ m.
  • the method for producing the film of the present invention is not particularly limited.
  • the curable composition and other components as required are uniformly dissolved in an aromatic solvent, a ketone solvent, or a mixed solvent thereof.
  • a method of dispersing, applying to a resin film such as a PET film, and drying may be used.
  • the application can be repeated multiple times as necessary. In this case, the application can be repeated using a plurality of solutions having different compositions and concentrations, and finally the desired resin composition and resin amount can be adjusted. It is.
  • the metal foil with resin of the present invention is composed of the curable composition of the present invention and the metal foil.
  • the metal foil used here include a copper foil and an aluminum foil.
  • the thickness is not particularly limited, but is in the range of 3 to 200 ⁇ m, more preferably 5 to 105 ⁇ m.
  • the method for producing the resin-coated metal foil of the present invention is not particularly limited.
  • the curable composition and other components as necessary in an aromatic solvent, a ketone solvent or a mixed solvent thereof.
  • a method of uniformly dissolving or dispersing, applying to a metal foil and then drying is exemplified.
  • the application can be repeated a plurality of times as necessary. At this time, the application can be repeated using a plurality of solutions having different compositions and concentrations, and finally adjusted to a desired resin composition and resin amount. Is possible.
  • the terminal-modified soluble polyfunctional vinyl aromatic copolymer of the present invention can be processed into a molding material, a sheet or a film, and has a low dielectric constant, a low water absorption rate and a high heat resistance in the fields of the electrical industry, the space / aircraft industry, etc.
  • it can be used as a single-sided, double-sided, multilayer printed board, flexible printed board, build-up board or the like.
  • semiconductor-related materials or optical materials paints, photosensitive materials, adhesives, sewage treatment agents, heavy metal scavengers, ion exchange resins, antistatic agents, antioxidants, antifogging agents, rustproofing agents It can be applied to anti-dyeing agents, bactericides, insect repellents, medical materials, flocculants, surfactants, lubricants, solid fuel binders, conductive treatment agents and the like.
  • the curable composition of the present invention has high dielectric properties (low dielectric constant and low dielectric loss tangent) even after severe thermal history, and has high adhesion reliability even in severe environments.
  • it has excellent resin fluidity, low linear expansion, and excellent wiring embedding flatness. Therefore, in the fields of electrical / electronics industry, space / aircraft industry, etc., molding defects such as warping etc. corresponding to the miniaturization and thinning that have been strongly demanded in recent years as dielectric materials, insulating materials, heat resistant materials, structural materials, etc.
  • a cured molded product having no phenomenon can be provided.
  • the curable resin composition according to the second embodiment is particularly useful as an optical waveguide material.
  • the curable resin composition which concerns on the 2nd aspect of this invention contains (A) component, (B) component, and (C) component as an essential component.
  • the component (A) is a terminal-modified soluble polyfunctional vinyl aromatic copolymer
  • the component (B) is one or more kinds having one or more unsaturated groups in one or more molecules in the molecule. It is a vinyl compound
  • the component (C) is a radical polymerization initiator.
  • the terminal-modified soluble polyfunctional vinyl aromatic copolymer used as the component (A) is as already described in detail.
  • Component (B) is one or more vinyl compounds having one or more unsaturated groups in the molecule.
  • the component (B) is not the same as the component (A). That is, the component (A) is not treated as the component (B).
  • the vinyl compound may be a polymerizable compound having an olefinic double bond (unsaturated group), the position of the unsaturated group is not limited, and the number of unsaturated groups is one. There may be a plurality.
  • the unsaturated group is also referred to as a vinyl group.
  • the vinyl group of component (B) can be copolymerized with the vinyl group of component (A).
  • Preferred component (B) includes one or more (meth) acrylates having one or more (meth) acryloyl groups in the molecule. Furthermore, there are one or more (meth) acrylates having a hydroxyl group and / or a carboxyl group.
  • the (meth) acrylate used as the component (B) is not particularly limited as long as it has one or more (meth) acryloyl groups in the molecule, and any one can be used.
  • Examples of the (meth) acrylate compound having one (meth) acryloyl group in the molecule include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) ) Acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, butoxyethyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth)
  • polyfunctional (meth) acrylates having two or more (meth) acryloyl groups in the molecule examples include 1,4-butanediol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate.
  • the component (B) has a structural unit represented by the general formula (16) or (17). It is preferable to include a vinyl compound or a curable vinyl polymer generated from the vinyl compound.
  • R 5 and R 8 represent a hydrogen atom or a methyl group
  • R 7 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms
  • R 6 , R 9 Represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • X 1 and X 2 are each a single bond or a divalent group having 1 to 20 carbon atoms that may contain one or more bonds selected from the group consisting of ester bonds, ether bonds, thioester bonds, thioether bonds, and amide bonds.
  • the vinyl compound having the structural unit represented by the general formula (16) or (17) or the curable vinyl polymer produced from the vinyl compound is preferably a (meth) acrylate or a (meth) acrylate polymer.
  • the curable vinyl polymer may be obtained by homopolymerizing or copolymerizing the vinyl compound and having at least one vinyl group.
  • the divalent organic group when X 1 and X 2 are divalent organic groups having 1 to 20 carbon atoms is not particularly limited, and examples thereof include an alkylene group
  • examples include divalent organic groups including a cycloalkylene group, a phenylene group, a biphenylene group, a polyether group, a polysiloxane group, a carbonyl group, an ester group, an amide group, and a urethane group, and further include a halogen atom, an alkyl group, It may be substituted with a cycloalkyl group, an aryl group, an aralkyl group, a carbonyl group, a formyl group, an ester group, an amide group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a silyl group, or a silyloxy group.
  • R 7 , R 6 , and R 9 are monovalent organic groups having 1 to 20 carbon atoms
  • the organic group is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, Monovalent organic groups such as acyl groups (—CO—R), ester groups (—CO—O—R or —O—CO—R), amide groups (—CO—NR 2 or —NR—CO—R)
  • acyl groups such as acyl groups (—CO—R), ester groups (—CO—O—R or —O—CO—R), amide groups (—CO—NR 2 or —NR—CO—R)
  • These are further hydroxyl group, halogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, carbonyl group, formyl group, ester group, amide group, alkoxy group, aryloxy group, alkylthio group,
  • the (meth) acrylate is not particularly limited.
  • 2-hydroxyethyl Aliphatic (meth) acrylates such as (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy-3 -Phenoxypropyl (meth) acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl (meth) acrylate, 2-hydroxy-3- (1-naphthoxy) propyl (meth) acrylate, 2-hydroxy-3- ( Aromatic (meth) such as 2-naphthoxy) propyl (meth) acrylate Acrylate, and the like.
  • aliphatic (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, or 2 Aromatic (meth) acrylates such as -hydroxy-3-phenoxypropyl (meth) acrylate and 2-hydroxy-3- (o-phenylphenoxy) propyl (meth) acrylate are preferred. These compounds can be used alone or in combination of two or more.
  • vinyl compounds are not particularly limited.
  • vinyl compounds having two or more carboxy groups such as maleic anhydride and citraconic anhydride, or vinyl compounds obtained by partial esterification of a part of the carboxylic groups of the acid anhydride with an appropriate alcohol such as methanol, ethanol or propanol. Used for.
  • an appropriate alcohol such as methanol, ethanol or propanol is used.
  • a partially esterified vinyl compound is also preferably used.
  • a curable (meth) acrylate (B1) having a urethane bond and one or more (meth) acryloyl groups is preferably used as the vinyl compound as the component (B).
  • the curable (meth) acrylate (B1) is not particularly limited, and examples thereof include the following urethane (meth) acrylates (1) to (4).
  • urethane (meth) acrylate having at least one selected from the group consisting of an alicyclic structure, an aromatic ring structure, and a heterocyclic structure in the molecule is preferable from the viewpoint of transparency and heat resistance.
  • the bifunctional alcohol compound that is, the diol compound is not particularly limited, and examples thereof include a polyether diol compound, a polyester diol compound, a polycarbonate diol compound, a polycaprolactone diol compound, and other diol compounds.
  • the polyether diol compound is not particularly limited, and examples thereof include ethylene oxide, propylene oxide, isobutene oxide, butyl glycidyl ether, butene-1-oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3
  • An alicyclic diol compound such as tricyclodecane dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F or the like is selected from the above cyclic ether compounds.
  • Both are selected from the above-mentioned cyclic ether compounds as polyether diol compounds obtained by ring-opening addition of one kind, bifunctional phenol compounds such as hydroquinone, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol AF, biphenol, fluorene bisphenol, etc. And polyether diol compounds obtained by ring-opening addition of at least one selected from the above.
  • the polyester diol compound is not particularly limited.
  • malonic acid succinic acid, glutaric acid, adipic acid, sebacic acid, tetrahydrophthalic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, Bifunctional carboxylic acid compounds such as fumaric acid and itaconic acid, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butanediol, dibutanediol, polybutanediol, pentanediol, neopentylglycol, 3-methyl-1,5-pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, cyclohexanedimethanol,
  • the polycarbonate diol compound is not particularly limited.
  • phosgene, triphosgene, dialkyl carbonate, diaryl carbonate and the like ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butanediol, dibutanediol, Polybutanediol, pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A, polycarbonate diol obtained by copolymerizing diol compounds such as hydrogenated bisphenol F Such compounds.
  • the polycaprolactone diol compound is not particularly limited.
  • ⁇ -caprolactone and ethylene glycol diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butanediol, dibutanediol, polybutanediol, pentane.
  • diol compounds such as diol, neopentyl glycol, 3-methyl-1,5-pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, cyclohexanedimethanol, tricyclodecanedimethanol
  • diol compounds such as diol, neopentyl glycol, 3-methyl-1,5-pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, cyclohexanedimethanol, tricyclodecanedimethanol
  • diol compounds such as diol, neopentyl glycol, 3-methyl-1,5-pentanediol, hexanediol,
  • diol compounds examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, dibutanediol, pentanediol, neopentylglycol, 3-methyl-1,5-pentanediol, hexanediol, and heptane.
  • Aliphatic diol compounds such as diol, octanediol, nonanediol, decanediol; cycloaliphatic diol compounds such as cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F; polybutadiene-modified diol compound, water Examples thereof include modified diol compounds such as an additive polybutadiene-modified diol compound and diricone-modified diol compound. These diol compounds can be used alone or in combination of two or more.
  • the bifunctional isocyanate compound is not particularly limited, and examples thereof include aliphatic bifunctional isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, decamethylene diisocyanate, and dodecamethylene diisocyanate.
  • the hydroxyl group-containing (meth) acrylate is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2- Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl (meth) acrylate, 2-hydroxy-3- (1-naphthoxy) propyl Monofunctional (meth) acrylates such as (meth) acrylate, 2-hydroxy-3- (2-naphthoxy) propyl (meth) acrylate, ethoxylated compounds thereof, propoxylated compounds thereof, ethoxylated propoxylated compounds thereof, And their caprolactone modifications Bifunctional (meth) acrylates such as bis (2- (meth) acryloyloxyethyl) (2-hydroxyethyl
  • the ethoxylated form, propoxylated form, and ethoxylated propoxylated form of (meth) acrylate are alcohol compounds or phenolic compounds (for example, monofunctional (meth) acrylate; CH 2 ⁇ CH (R 7 )) -COO-R 8 (R 7 is a hydrogen atom or a methyl group, R 8 is a monovalent organic group) in the case of, instead of one) represented by HO-R 8, the alcohol compound or a phenol compound, respectively
  • the modified caprolactone is a (meth) acrylate obtained by using, as a raw material, an alcohol compound obtained by modifying an alcohol compound as a raw material of (meth) acrylate with ⁇ -caprolactone (for example, monofunctional (meth) acrylate)
  • ⁇ -caprolactone for example, monofunctional (meth) acrylate
  • the modified caprolactone it is represented by CH 2 ⁇ CH (R 7 ) —COO — ((CH 2 ) 5 COO) q —R 8 (q, R 7 and R 8 are as defined above)).
  • the (meth) acrylate having an isocyanate group is not particularly limited.
  • N- (meth) acryloyl isocyanate, (meth) acryloyloxymethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) Examples include acryloyloxyethoxyethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate. These compounds can be used alone or in combination of two or more.
  • polyfunctional isocyanate compound there is no restriction
  • multimers such as the said bifunctional isocyanate compound;
  • the two or three bifunctional isocyanate compounds constituting the multimer may be the same or different. These compounds can be used alone or in combination of two or more.
  • the polyfunctional alcohol compound is not particularly limited, and may be, for example, the above-mentioned bifunctional alcohol compound; Alcohol compounds, adducts obtained by ring-opening addition of at least one selected from the above cyclic ether compounds to these, caprolactone-modified products thereof; tricyclic or higher functional phenol compounds such as phenol novolac and cresol novolak to the cyclic ether Examples include alcohol compounds obtained by ring-opening addition of at least one selected from the compounds, and modified caprolactones thereof. These compounds can be used alone or in combination of two or more.
  • the curable (meth) acrylate having a urethane bond may further contain a carboxyl group as necessary from the viewpoint of heat resistance and solubility in an alkali developer.
  • the (meth) acrylate having a carboxyl group and a urethane bond is not particularly limited.
  • a carboxyl group-containing diol compound is used in combination with the diol compound, or Examples thereof include urethane (meth) acrylate obtained by using instead of the diol compound.
  • the carboxyl group-containing diol compound is not particularly limited, and examples thereof include 2,2-dimethylolbutanoic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, and 2,2-dimethylolpentanoic acid. Can be mentioned. These compounds can be used alone or in combination of two or more.
  • the curable (meth) acrylate having a carboxyl group and a urethane bond can have an acid value so that it can be developed with an alkali developer described later.
  • the acid value is preferably 5 to 200 mgKOH / g, more preferably 10 to 170 mgKOH / g, and particularly preferably 15 to 150 mgKOH / g. When it is 5 mgKOH / g or more, the solubility in an alkali developer is good, and when it is 200 mgKOH / g or less, the developer resistance is good.
  • the component (F) A component reacts with the component which has a hydroxyl group and / or a carboxyl group, and produces a crosslinked structure.
  • the component (B) is preferably a vinyl compound having a hydroxyl group or a carboxyl group, and if not, it is desirable to incorporate a compound (E) having a hydroxyl group or a carboxyl group that causes this reaction.
  • the polyfunctional blocked isocyanate compound as the component (F) is a compound produced by a reaction between the polyfunctional isocyanate compound and a blocking agent. Further, it is a compound that is temporarily inactivated by a group derived from a blocking agent, and when heated to a predetermined temperature, the group derived from the blocking agent is dissociated to produce an isocyanate group.
  • a polyfunctional blocked isocyanate compound is used, a new cross-linked structure is formed by reacting an isocyanate group generated from the polyfunctional blocked isocyanate compound by heating with the hydroxyl group and / or carboxyl group of the component (A), and heat resistance
  • environmental reliability can be improved.
  • the polyfunctional isocyanate compound that can react with the blocking agent is not particularly limited, and examples thereof include 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate.
  • Aromatic polyfunctional isocyanate compounds such as diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate; 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 2,5- Bis (isocyanatomethyl) norbornene, bis (4-isocyanatocyclohexyl) methane, 1,2-bis (4-isocyanatocyclohexyl) ethane, 2,2-bis (4-isocyanatocyclohexyl) propane, 2,2- Cycloaliphatic polyfunctional isocyanate compounds such as bis (4-isocyanatocyclohexyl) hexafluoropropane and bicycloheptane triisocyanate; tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexam
  • the polyfunctional isocyanate compound from the viewpoints of transparency and heat resistance, a compound containing in the molecule thereof at least one selected from an alicyclic structure and an aliphatic structure is preferable, and among them, the alicyclic polyfunctional isocyanate compound; Aliphatic polyfunctional isocyanate compounds are preferred.
  • the polyfunctional isocyanate compound may be a multimer such as a uretdione type dimer, isocyanurate type trimer, or biuret type trimer, and two or three polyfunctional isocyanates constituting these.
  • the compounds may be the same or different.
  • the combination of a polyfunctional isocyanate compound of a different kind may be sufficient like the combination of an alicyclic polyfunctional isocyanate compound and an aliphatic polyfunctional isocyanate compound, for example.
  • the above polyfunctional isocyanate compounds can be used alone or in combination of two or more.
  • those having active hydrogen are preferable, for example, active methylene compounds such as malonic acid diester, acetoacetic acid ester, malonic acid dinitrile, acetylacetone, methylenedisulfone, dibenzoylmethane, dipivalylmethane, and acetonedicarboxylic acid diester.
  • active methylene compounds such as malonic acid diester, acetoacetic acid ester, malonic acid dinitrile, acetylacetone, methylenedisulfone, dibenzoylmethane, dipivalylmethane, and acetonedicarboxylic acid diester.
  • Oxime compounds such as acetone oxime, methyl ethyl ketone oxime, diethyl ketone oxime, methyl isobutyl ketone oxime, and cyclohexanone oxime; phenol compounds such as phenol, alkylphenol, and alkylnaphthol; lactam compounds such as ⁇ -butyrolactam, ⁇ -valerolactam, and ⁇ -caprolactam Etc.
  • the active methylene compound; the oxime compound; and the lactam compound are preferable.
  • the above blocking agents can be used alone or in combination of two or more.
  • the radical polymerization initiator used as the component (C) is a radical polymerization of the components (A) and (B) by heating or irradiation with actinic rays such as ultraviolet rays and visible rays.
  • the radical polymerization initiator is not particularly limited as long as it initiates radical polymerization by heating or irradiation with actinic rays such as ultraviolet rays and visible rays, and examples thereof include a thermal radical polymerization initiator and a photo radical polymerization initiator. It is done.
  • the thermal radical polymerization initiator is not particularly limited, and examples thereof include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis (t-butylperoxy) cyclohexane, 1,1 -Bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane Peroxyketals such as 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane; hydroperoxides such as p-menthane hydroperoxide; ⁇ , ⁇ ′-bis (t-butyl Peroxy) diisopropylbenzene, dicumyl peroxide, t- Dialky
  • the radical photopolymerization initiator is not particularly limited as long as it initiates radical polymerization by irradiation with actinic rays such as ultraviolet rays and visible rays.
  • actinic rays such as ultraviolet rays and visible rays.
  • actinic rays such as ultraviolet rays and visible rays.
  • 2,2-dimethoxy-1,2-diphenylethane-1- Benzoinketals such as ON; 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2- ⁇ -hydroxy ketones such as methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4 [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl ⁇ -2-methylpropan-1-one Methyl methyl phenylglyoxylate, ethyl phenylg
  • the aryl group substituents at the two triarylimidazole sites may give the same and symmetric compounds, but give differently asymmetric compounds. May be.
  • radical photopolymerization initiators ⁇ -hydroxy ketone, glyoxy ester, oxime ester or phosphine oxide as described above are preferable from the viewpoint of curability and transparency.
  • the above radical polymerization initiators (such as a thermal radical polymerization initiator and a photo radical polymerization initiator) can be used alone or in combination of two or more, and can also be used in combination with an appropriate sensitizer.
  • the blending amount of the component (A), the component (B), and the component (C) is 5-94.9 wt% for the component (A), and 5. for the component (B). 0 to 85 wt%, and the component (C) is 0.1 to 10 wt%.
  • the component (A) is 30 to 94.9 wt%
  • the component (B) is 5.0 to 60 wt%
  • the component (C) is 0.1 to 10 wt%, more preferably the component (A) Is 40 to 80 wt%
  • the component (B) is 10 to 50 wt%
  • the component (C) is 1 to 5 wt%.
  • the curable resin composition of the present invention may contain a solvent and other additives. And in calculation of the compounding quantity in a curable resin composition, volatile matters, such as a solvent which will be removed after hardening, are excluded from calculation.
  • the blending amount of the component (A), the component (B), and the component (C) is (A) with respect to the sum of the component (A), the component (B), and the component (C).
  • Component is 5 to 94.9 wt%
  • component (B) is 5.0 to 85 wt%
  • component (C) is 0.1 to 10 wt%.
  • the component (A) is 30 to 94.9 wt%
  • the component (B) is 5.0 to 60 wt%
  • the component (C) is 0.1 to 10 wt%, more preferably the component (A) Is 40 to 80 wt%, the component (B) is 10 to 50 wt%, and the component (C) is 1 to 5 wt%.
  • the blending amount of the component (A), the component (B), and the component (C) is such that the component (A) is 10 to 70 wt%, (B)
  • the component is preferably 15 to 70 wt%, and the component (C) is preferably 0.1 to 10 wt%.
  • the component (E) is 0 to 40 wt%.
  • the component (B) is preferably the above component (B1), and further preferably contains 10 to 70 wt% of vinyl (B2) having a hydroxyl group or a carboxyl group in the component (B).
  • a component is a vinyl compound which has a hydroxyl group or a carboxyl group, it calculates as a component applicable to both (B) component and (E) component.
  • the blending amount of the component (F) is preferably 1 to 40% by mass with respect to the total amount of the components (A) to (C) when the component (E) is not included.
  • the amount of the component (F) is preferably 1 to 40% by mass with respect to the total amount of the components (A) to (C) and the component (E).
  • the blending amount of the component (F) is in the above range, the hydroxyl group and / or carboxyl group of the component (E) reacts with the isocyanate group generated from the polyfunctional blocked isocyanate compound to form a sufficient crosslinked structure.
  • a cured product that has good heat resistance, good toughness, and does not become brittle can be obtained.
  • the amount of component (F) is more preferably 3 to 35% by mass, and particularly preferably 5 to 30% by mass.
  • the (meth) acrylate (B1) having the urethane bond is used as the component (B)
  • the (meth) acrylate (B1) having a urethane bond is used.
  • it is good also as all of (B) component you may use another vinyl compound as needed.
  • an antioxidant if necessary, an antioxidant, a yellowing inhibitor, an ultraviolet absorber, a visible light absorber, a colorant, a plasticizer, and a stabilizer
  • These resin compositions may be diluted with an appropriate organic solvent and used as a resin varnish.
  • the organic solvent used here is not particularly limited as long as it can dissolve the resin composition.
  • aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, p-cymene; diethyl ether, tert-butylmethyl Chain ethers such as ether, cyclopentyl methyl ether and dibutyl ether; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol and propylene glycol; acetone, methyl ethyl ketone and methyl isobutyl ketone Ketones such as cyclohexanone and 4-hydroxy-4-methyl-2-pentanone; esters such as methyl acetate, ethyl acetate, butyl
  • the rotation speed of the propeller during stirring is preferably 10 to 1,000 rpm.
  • the rotation speed of the propeller is 10 rpm or more, the respective components are sufficiently mixed.
  • the rotation speed of the propeller is more preferably 50 to 800 rpm, and particularly preferably 100 to 500 rpm.
  • the stirring time is not particularly limited, but is preferably 1 to 24 hours. When the stirring time is 1 hour or more, the respective components are sufficiently mixed, and when it is 24 hours or less, the preparation time can be shortened, and the productivity is improved.
  • the varnish is preferably filtered using a filter having a pore size of 50 ⁇ m or less.
  • a filter having a pore diameter of 50 ⁇ m or less large foreign matters are not removed, and repellency is not caused at the time of application, and light scattering is suppressed and transparency is not impaired. From the above viewpoint, it is more preferable to filter using a filter having a pore diameter of 30 ⁇ m or less, and it is particularly preferable to filter using a filter having a pore diameter of 10 ⁇ m or less.
  • the resin composition is a prepared resin varnish or a resin composition that is not a varnish and contains a volatile component
  • the defoaming method For example, the method of using a vacuum pump, a bell jar, and the defoaming apparatus with a vacuum apparatus is mentioned.
  • the pressure at the time of pressure reduction The pressure in which the low boiling point component contained in a resin composition does not boil is preferable.
  • the vacuum degassing time is preferably 3 to 60 minutes.
  • the vacuum degassing time is 3 minutes or more, bubbles dissolved in the resin composition can be removed, and if it is 60 minutes or less, the organic solvent contained in the resin composition does not volatilize and is removed. Bubble time can be shortened and productivity can be improved.
  • This resin film is formed using the resin composition for forming an optical waveguide. For example, it can be easily produced by applying an optical waveguide forming resin composition to an appropriate support film. Moreover, when this resin composition is the resin varnish diluted with the organic solvent, it can manufacture by apply
  • the support film is not particularly limited.
  • polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate
  • polyolefins such as polyethylene and polypropylene
  • polycarbonates polyamides, polyimides, polyamideimides, polyetherimides, polyether sulfides
  • examples include polyethersulfone, polyetherketone, polyphenylene ether, polyphenylene sulfide, polyarylate, polysulfone, and liquid crystal polymer.
  • polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene, polycarbonate, polyamide, polyimide, polyamideimide, polyphenylene ether, polyphenylene sulfide, polyarylate, and polysulfone are preferable from the viewpoints of flexibility and toughness.
  • a film that has been subjected to a release treatment with a silicone compound, a fluorine-containing compound, or the like may be used as necessary.
  • the thickness of the support film may be appropriately changed depending on the desired flexibility, but is preferably 3 to 250 ⁇ m, more preferably 5 to 200 ⁇ m, and more preferably 7 to 150 ⁇ m from the viewpoint of film strength and flexibility. It is particularly preferred.
  • a film in which a resin composition for forming an optical waveguide is coated on a support film may have a three-layer structure including a support film, a resin layer, and a protective film by attaching a protective film on the resin layer as necessary.
  • the protective film is not particularly limited, but from the viewpoint of flexibility and toughness, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefins such as polyethylene and polypropylene are preferable.
  • a film that has been subjected to a release treatment with a silicone compound, a fluorine-containing compound, or the like may be used as necessary.
  • the thickness of the protective film is preferably 10 to 250 ⁇ m, more preferably 15 to 200 ⁇ m, and particularly preferably 20 to 150 ⁇ m.
  • the thickness of the resin layer of the resin film for forming an optical waveguide of the present invention is not particularly limited, but is preferably 5 to 500 ⁇ m after drying. Within the above range, the strength of the resin film or the cured product of the resin film is sufficient, and at the same time, the cured product of the resin film is heated without increasing the amount of residual solvent in the resin film because drying can be performed sufficiently. Sometimes it does not foam.
  • the resin film for forming an optical waveguide thus obtained can be easily stored, for example, by winding it into a roll. Moreover, a roll-shaped film can be cut out to a desired size and stored in a sheet shape.
  • the support film in this case is not particularly limited as long as it can transmit the actinic ray for exposure used for forming the core pattern.
  • polyesters and polyolefins are preferable from the viewpoints of the transmittance of actinic rays for exposure, flexibility, and toughness.
  • Examples of such a highly transparent support film include commercially available “Cosmo Shine A1517”, “Cosmo Shine A4100” manufactured by Toyobo Co., Ltd., “Lumirror FB50” manufactured by Toray Industries, Inc., and the like.
  • the thickness of the support film is preferably 5 to 50 ⁇ m, more preferably 10 to 40 ⁇ m, and particularly preferably 15 to 30 ⁇ m from the viewpoint of strength and pattern resolution when forming the core pattern.
  • the resin film for forming an optical waveguide of the present invention is a resin film for forming a clad layer (an upper clad layer forming resin film, a lower clad layer forming resin film)
  • the support film in this case is not particularly limited as long as it can transmit the actinic ray for exposure used for forming the clad.
  • it is described as a specific example of the support film of the resin film for forming an optical waveguide described above.
  • polyesters and polyolefins are preferable from the viewpoints of the transmittance of actinic rays for exposure, flexibility, and toughness.
  • a highly transparent support film from the viewpoint of improving the transmittance of exposure actinic rays and reducing the roughness of the side wall of the cladding pattern.
  • a highly transparent support film examples include commercially available “Cosmo Shine A1517”, “Cosmo Shine A4100” manufactured by Toyobo Co., Ltd., “Lumirror FB50” manufactured by Toray Industries, Inc., and the like.
  • the thickness of the support film of the clad layer forming resin film is preferably 5 to 50 ⁇ m, more preferably 10 to 40 ⁇ m, and particularly preferably 15 to 30 ⁇ m.
  • FIG. 1A to 1D are sectional views of the optical waveguide.
  • an optical waveguide 1 is formed on a substrate 5 and is made of a core part 2 resin composition having a high refractive index and a clad layer forming resin composition having a low refractive index.
  • the lower clad layer 4 and the upper clad layer 3 are made of a material.
  • (B) to (d) of FIG. 1 show different embodiments.
  • (B) shows a mode in which the substrate 5 is disposed as a protective film outside the upper clad layer 3.
  • C shows a mode in which the substrate 5 is disposed as a protective film on the outside of both the lower clad layer 4 and the upper clad layer 3.
  • the aspect in which the base material as the protective film 5 is not arranged is shown.
  • the resin composition for forming an optical waveguide and the resin film for forming an optical waveguide of the present invention are preferably used for at least one of the lower cladding layer 4, the core portion 2, and the upper cladding layer 3 of the optical waveguide 1, Preferably, those with adjusted refractive index are used for all layers.
  • the flatness of each layer, the interlayer adhesion between the clad and the core, and the resolution (correspondence between thin lines or narrow lines) at the time of forming the optical waveguide core pattern can be further improved. It is excellent in flatness, and it is possible to form a fine pattern with a small line width and line spacing.
  • the material of the base material 5 is not particularly limited.
  • a glass epoxy resin substrate, a ceramic substrate, a glass substrate, a silicon substrate, a plastic substrate, a metal substrate, a substrate with a resin layer, a substrate with a metal layer examples thereof include a plastic film, a plastic film with a resin layer, and a plastic film with a metal layer.
  • the optical waveguide 1 may be a flexible optical waveguide by using a base material having flexibility and toughness as the base material 5, for example, a support film of the resin film for forming an optical waveguide as a base material. 5 may function as a protective film for the optical waveguide 1. By disposing the protective film, the flexibility and toughness of the protective film can be imparted to the optical waveguide 1. Furthermore, since the optical waveguide 1 is not damaged or scratched, the ease of handling is improved.
  • the modes (b) to (c) may be suitable instead of the mode (a) of FIG. If the optical waveguide has sufficient flexibility and toughness, the protective film can be omitted as shown in (d).
  • the thickness of the lower cladding layer 4 is not particularly limited, but is preferably 2 to 200 ⁇ m. If it is 2 ⁇ m or more, it becomes easy to confine the propagating light inside the core, and if it is 200 ⁇ m or less, the entire thickness of the optical waveguide 1 is not too large.
  • the thickness of the lower cladding layer 4 is a value from the boundary between the core portion 2 and the lower cladding layer 4 to the lower surface of the lower cladding layer 4. There is no restriction
  • the height of the core part 2 is not particularly limited, but is preferably 10 to 150 ⁇ m.
  • the height of the core is 10 ⁇ m or more, the alignment tolerance is not reduced in coupling with the light emitting / receiving element or the optical fiber after the optical waveguide is formed, and when the core portion is 150 ⁇ m or less, the light is received and emitted after the optical waveguide is formed. In coupling with an element or an optical fiber, coupling efficiency is not reduced.
  • the height of the core part is more preferably 15 to 130 ⁇ m, and particularly preferably 20 to 120 ⁇ m.
  • Thickness is adjusted so that the height of the core part after hardening may become said range.
  • the thickness of the upper clad layer 3 is not particularly limited as long as the core portion 2 can be embedded, but the thickness after drying is preferably 12 to 500 ⁇ m.
  • the thickness of the upper clad layer 3 may be the same as or different from the thickness of the lower clad layer 4 formed first, but is thicker than the thickness of the lower clad layer 4 from the viewpoint of embedding the core portion 2. It is preferable.
  • the thickness of the upper cladding layer 3 is a value from the boundary between the core portion 2 and the lower cladding layer 4 to the upper surface of the upper cladding layer 3.
  • the light propagation loss in a light source having a wavelength of 850 nm is preferably 0.3 dB / cm or less, more preferably 0.2 dB / cm or less, and particularly preferably 0.1 dB / cm or less.
  • the light propagation loss in a light source with a wavelength of 850 nm after 1000 hours of a high-temperature and high-humidity test at a temperature of 85 ° C. and a humidity of 85% is preferably 0.3 dB / cm or less, and 0.2 dB / cm or less. More preferably, it is particularly preferably 0.1 dB / cm or less.
  • the high-temperature and high-humidity standing test means a high-temperature and high-humidity standing test performed under conditions in accordance with the JPCA standard (JPCA-PE02-05-01S).
  • the light propagation loss in a light source with a wavelength of 850 nm after 1000 cycles of a temperature cycle test between ⁇ 55 ° C. and 125 ° C. is preferably 0.3 dB / cm or less, and is 0.2 dB / cm or less. More preferably, it is particularly preferably 0.1 dB / cm or less.
  • the above temperature cycle test means a temperature cycle test performed under conditions in accordance with the JPCA standard (JPCAPE02-05-01S).
  • the light propagation loss in the light source having a wavelength of 850 nm after the reflow test at the maximum temperature of 265 ° C. is performed three times is preferably 0.3 dB / cm or less, more preferably 0.2 dB / cm or less, It is particularly preferably 0.1 dB / cm or less.
  • the said reflow test means the lead-free solder reflow test implemented on the conditions according to JEDEC specification (JEDEC JESD22A113E).
  • the optical waveguide of the present invention is excellent in transparency, environmental reliability, and heat resistance, and may be used as an optical transmission line of an optical module.
  • the optical module include an optical waveguide with an optical fiber in which optical fibers are connected to both ends of the optical waveguide, an optical waveguide with a connector in which connectors are connected to both ends of the optical waveguide, and an opto-electrical device in which the optical waveguide and the printed wiring board are combined.
  • Examples include a composite substrate, an optical / electrical conversion module that combines an optical waveguide and an optical / electrical conversion element that mutually converts an optical signal and an electrical signal, and a wavelength multiplexer / demultiplexer that combines an optical waveguide and a wavelength division filter.
  • the printed wiring board to be combined is not particularly limited, and examples thereof include rigid substrates such as glass epoxy substrates and ceramic substrates; flexible substrates such as polyimide substrates and polyethylene terephthalate substrates.
  • the manufacturing method for forming an optical waveguide using the resin composition for forming an optical waveguide or the resin film for forming an optical waveguide of the present invention will be described.
  • limiting in particular as a method of manufacturing an optical waveguide For example, the method etc. which form and manufacture the resin layer for optical waveguide formation on a base material using the said resin composition or film are mentioned.
  • the method for forming the optical waveguide forming resin layer is not particularly limited.
  • the coating method include a curtain coating method, a gravure coating method, a screen coating method, and an inkjet coating method.
  • a step of drying after forming a resin layer may be added as necessary.
  • a drying method For example, heat drying, vacuum drying, etc. are mentioned. Moreover, you may use these together as needed.
  • optical waveguide forming resin layer examples include a method of forming the optical waveguide forming resin film by a lamination method.
  • a method of producing by a lamination method using a resin film for forming an optical waveguide is preferable.
  • a resin film for forming a lower clad layer is laminated on the substrate 5.
  • stacking method in a 1st process For example, the method of laminating
  • the flat plate laminator in the present invention refers to a laminator in which a laminated material is sandwiched between a pair of flat plates and pressed by pressing the flat plate.
  • a vacuum pressurizing laminator can be suitably used.
  • the laminating temperature is not particularly limited but is preferably 20 to 130 ° C.
  • the laminating pressure is not particularly limited, but is preferably 0.1 to 1.0 MPa.
  • a resin film for forming a lower clad layer may be temporarily pasted on the substrate 5 in advance using a roll laminator.
  • a laminator having a heat roll may be used while heating.
  • the laminating temperature is preferably 20 to 150 ° C, more preferably 40 to 130 ° C. If it is this range, the adhesiveness of a resin film and a base material will improve, a resin layer will not flow too much at the time of roll lamination, and the required film thickness will be obtained.
  • the laminating pressure is not particularly limited, but is preferably 0.2 to 0.9 MPa, and the laminating speed is not particularly limited, but is preferably 0.1 to 3 m / min.
  • the lower clad layer forming resin layer laminated on the substrate 5 is cured by light and / or heat to form the lower clad layer 4.
  • the removal of the support film of the lower clad layer forming resin film may be performed either before or after curing.
  • the irradiation amount of the actinic ray when the lower clad layer forming resin layer is cured by light is not particularly limited, but is preferably 0.1 to 5 J / cm 2.
  • a heat treatment at 50 to 200 ° C. may be performed as necessary.
  • the heating temperature for curing the lower clad layer forming resin layer with heat is not particularly limited, but is preferably 50 to 200 ° C.
  • the support film for the resin film for forming the lower clad layer functions as the protective film 5 for the optical waveguide 1, it is cured under the same conditions as described above by light and / or heat without laminating the resin film for forming the lower clad layer. Then, the lower cladding layer 4 may be formed.
  • the protective film for the resin film for forming the lower cladding layer may be removed before curing or after curing.
  • the resin layer for forming the core part is designed to have a higher refractive index than the resin layer for forming the lower clad layer, and is made of a photosensitive resin composition capable of forming the core part 2 (core pattern) by actinic rays. Is preferred.
  • the core portion 2 is exposed.
  • the method for exposing the core part 2 is not particularly limited.
  • Examples include a method of directly irradiating an image with an actinic ray.
  • the light source of the actinic ray for example, a light source that effectively emits ultraviolet rays such as an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a mercury vapor arc lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp; A light source that effectively emits visible light, such as a light bulb and a solar lamp.
  • the amount of active light irradiation when exposing the core part 2 is preferably 0.01 to 10 J / cm 2 , more preferably 0.03 to 5 J / cm 2 , and still more preferably 0.05 to 10 J / cm 2. 3 J / cm 2 .
  • the core part 2 may be exposed through the support film of the core part forming resin film or after the support film is removed. Moreover, you may perform post-exposure heating as needed from a viewpoint of the resolution of the core part 2 and adhesive improvement after exposure.
  • the time from ultraviolet irradiation to post-exposure heating is preferably within 10 minutes, but this condition is not particularly limited.
  • the post-exposure heating temperature is preferably 40 to 160 ° C. and the time is preferably 30 seconds to 10 minutes, but these conditions are not particularly limited.
  • the development method is not particularly limited, and examples thereof include a spray method, a dip method, a paddle method, a spin method, a brushing method, and a scraping method. Moreover, you may use these image development methods together as needed.
  • the developer is not particularly limited, and examples thereof include an organic solvent, a semi-aqueous developer composed of an organic solvent and water, a water-based alkaline developer composed of an aqueous alkali solution, and a semi-aqueous alkaline developer composed of an alkaline aqueous solution and an organic solvent. It is done.
  • the development temperature is adjusted according to the developability of the core layer forming resin layer.
  • an organic solvent For example, the thing similar to the organic solvent used for dilution of the said resin composition for optical waveguide formation can be mentioned suitably. These compounds can be used alone or in combination of two or more. Further, a surface active agent, an antifoaming agent or the like may be mixed in the organic solvent.
  • the semi-aqueous developer is not particularly limited as long as it is composed of one or more organic solvents and water. The concentration of the organic solvent is preferably 5 to 90% by mass. Further, a small amount of a surfactant, an antifoaming agent or the like may be mixed in the semi-aqueous developer.
  • Alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide
  • Alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate
  • Hydrogen carbonate Alkali metal bicarbonates such as lithium, sodium bicarbonate and potassium bicarbonate
  • alkali metal phosphates such as potassium phosphate and sodium phosphate
  • alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate
  • tetraboric acid Sodium salts such as sodium and sodium metasilicate
  • ammonium salts such as ammonium carbonate and ammonium hydrogen carbonate
  • tetramethylammonium hydroxide triethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3 Propanediol, organic bases such as 1,3-diamino-propanol-2-morpholine.
  • the pH of the aqueous alkaline developer is preferably 9-14. Further, a surfactant, an antifoaming agent or the like may be mixed in the aqueous alkaline developer.
  • the quasi-aqueous alkaline developer is not particularly limited as long as it comprises an aqueous alkali solution and one or more organic solvents. In addition, there is no restriction
  • the pH of the quasi-aqueous alkaline developer is preferably as low as possible within a range where development is sufficiently possible, preferably pH 8 to 13, and more preferably pH 9 to 12.
  • the concentration of the organic solvent is usually preferably 5 to 90% by mass.
  • a small amount of a surfactant, an antifoaming agent or the like may be mixed in the semi-aqueous alkaline developer.
  • the cleaning method is not particularly limited, and examples thereof include a spray method, a dipping method, a paddle method, a spin method, a brushing method, and a scraping method. Moreover, you may use these washing
  • An organic solvent can be used individually or in combination of 2 or more types.
  • the concentration of the organic solvent is usually preferably 5 to 90% by mass.
  • the washing temperature is adjusted in accordance with the developability of the core portion forming resin layer. As processing after development or washing, exposure and / or heating may be performed as necessary from the viewpoint of improving the curability and adhesion of the core portion 2.
  • the heating temperature is not particularly limited, but is preferably 40 to 200 ° C., and the irradiation amount of active light is not particularly limited, but is preferably 0.01 to 10 J / cm 2 .
  • an upper clad layer forming resin film is laminated on the lower clad layer 4 and the core portion 2 by the same method as the first and second steps.
  • the upper clad layer forming resin layer is designed to have a lower refractive index than the core portion forming resin layer.
  • the thickness of the upper clad forming resin layer is preferably larger than the height of the core portion 2.
  • the upper clad layer forming resin layer is cured by light and / or heat to form the upper clad layer 3 in the same manner as in the first step.
  • the irradiation amount of actinic rays when the upper clad layer-forming resin layer is cured with light is not particularly limited, but is preferably 0.1 to 30 J / cm 2 .
  • the double-sided exposure machine which can irradiate actinic light simultaneously from both surfaces can be used.
  • the heating temperature during and / or after irradiation with actinic rays is not particularly limited, but is preferably 50 to 200 ° C.
  • the heating temperature when the upper clad layer-forming resin layer is cured by heat is not particularly limited, but is preferably 50 to 200 ° C.
  • the removal of the support film of the resin film for upper clad layer formation it may remove before hardening or after hardening.
  • the optical waveguide 1 can be manufactured through the above steps.
  • Tg glass transition temperature
  • softening temperature of cured product Copolymer solution was uniformly applied to a glass substrate so that the thickness after drying was 20 ⁇ m, and 30 minutes in 90 minutes using a hot plate. Heated and dried.
  • the resin film obtained together with the glass substrate is set in TMA (thermomechanical analyzer), heated to 220 ° C. at a temperature rising rate of 10 ° C./min under a nitrogen stream, and further heat-treated at 220 ° C. for 20 minutes. At the same time as the remaining solvent was removed, the copolymer was cured. After allowing the glass substrate to cool to room temperature, an analytical probe is brought into contact with the sample in the TMA measuring apparatus, and scan measurement is performed from 30 ° C.
  • TMA thermomechanical analyzer
  • the softening temperature was determined.
  • the glass transition temperature is measured by setting the above test piece in a DMA (dynamic viscoelasticity device) measuring device and scanning from 30 ° C. to 320 ° C. at a temperature rising rate of 3 ° C./min under a nitrogen stream.
  • the Tg was determined from the peak top of the tan ⁇ curve.
  • the heat resistance of the copolymer is evaluated by setting the sample in a TGA (thermobalance) measuring device, and at a temperature increase rate of 10 ° C./min under a nitrogen stream at 30 ° C. to 400 ° C. The measurement was performed by scanning until the weight loss at 350 ° C. was determined as heat resistance.
  • 6.0 g of copolymer, 4.0 g of benzyl methacrylate and 0.02 g of t-butylperoxy-2-ethylhexanoate were mixed and measured at 200 ° C. under a nitrogen stream. Heated for hours to obtain a cured product. And the amount of discoloration of the obtained hardened
  • Synthesis example 1 1.28 mol (182.7 mL) of divinylbenzene (a mixture of 1,4-divinylbenzene and 1,3-divinylbenzene, and the following examples), ethylvinylbenzene (1-ethyl-4-vinylbenzene, and 1 A mixture of ethyl-3-vinylbenzene, the same in the following example) 0.97 mol (137.8 mL), t-butyl methacrylate 2.00 mol (323.2 mL), toluene 300 mL 2.0 L reactor Then, 50 mmol of boron trifluoride diethyl ether complex was added at 50 ° C. and reacted for 4 hours.
  • divinylbenzene a mixture of 1,4-divinylbenzene and 1,3-divinylbenzene, and the following examples
  • ethylvinylbenzene (1-ethyl-4-vinylbenzene, and
  • Mn of the obtained copolymer A was 842, Mw was 3640, and Mw / Mn was 4.32.
  • end group resonance lines derived from t-butyl methacrylate were observed.
  • the amount (c1) of structural units derived from t-butyl methacrylate in the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis results and the number average molecular weight in terms of standard polystyrene was 2.3 (pieces / molecule). It was.
  • Mn of the obtained copolymer A was 952, Mw was 4490, and Mw / Mn was 4.72.
  • end group resonance lines derived from t-butyl acrylate were observed in the copolymer B.
  • Copolymer B contained 59.3 mol% of structural units derived from divinylbenzene and 40.7 mol% in total of structural units derived from ethylvinylbenzene (excluding terminal structural units).
  • the vinyl group content contained in the copolymer B was 34.7 mol% (excluding the terminal structural unit).
  • clear Tg was not observed as a result of TMA measurement of hardened
  • the weight loss at 350 ° C. was 3.04 wt%, and the heat discoloration resistance was ⁇ .
  • the compatibility with the epoxy resin was ⁇ .
  • Copolymer B was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was formed.
  • Mn of the obtained copolymer C was 2030, Mw was 5180, and Mw / Mn was 2.55.
  • end group resonance lines derived from 2-phenoxyethyl methacrylate were observed.
  • the amount (c1) of structural units derived from 2-phenoxyethyl methacrylate in the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis results and the number average molecular weight in terms of standard polystyrene was 2.3 (pieces / molecule).
  • Synthesis example 4 (comparative example) 1.92 mol (273.5 mL) of divinylbenzene, 0.08 mol (11.4 mL) of ethylvinylbenzene, 2.0 mol (229.2 mL) of styrene, 2.00 mol (348.1 mL) of 2-phenoxyethyl acrylate Then, 250.0 mL of butyl acetate and 1000 mL of toluene were put into a 3.0 L reactor, and 80 mmol of boron trifluoride diethyl ether complex was added at 70 ° C. and reacted for 6 hours.
  • Mn of the obtained copolymer D was 2330, Mw was 4940, and Mw / Mn was 2.12.
  • end group resonance lines derived from 2-phenoxyethyl acrylate were observed.
  • it was C: 84.4 wt%, H: 7.3 wt%, and O: 7.9 wt%.
  • Copolymer D was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was observed.
  • Mn of the obtained copolymer E was 789, Mw was 3450, and Mw / Mn was 4.37.
  • end group resonance lines derived from t-butyl methacrylate were observed in the copolymer E.
  • copolymer E contained 47.1 mol% of structural units derived from divinylbenzene, 34.0 mol% of structural units derived from ethylvinylbenzene, and 18.9 mol% of structural units derived from styrene (terminal structural units). except for).
  • the vinyl group content contained in the copolymer E was 33.8 mol% (excluding the terminal structural unit).
  • clear Tg was not observed as a result of TMA measurement of hardened
  • the weight loss at 350 ° C. was 3.37 wt%, and the heat discoloration was ⁇ .
  • the compatibility with the epoxy resin was ⁇ .
  • Copolymer E was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was observed.
  • Mn of the obtained copolymer F was 913, Mw was 4210, and Mw / Mn was 4.61.
  • end group resonance lines derived from t-butyl methacrylate were observed in the copolymer F.
  • copolymer F contained 47.3 mol% of structural units derived from divinylbenzene, 34.5 mol% of structural units derived from ethylvinylbenzene, and 18.2 mol% of structural units derived from styrene (terminal structural units). except for).
  • the vinyl group content contained in the copolymer F was 32.9 mol% (excluding the terminal structural unit).
  • clear Tg was not observed as a result of TMA measurement of hardened
  • the weight loss at 350 ° C. was 2.92 wt%, and the heat discoloration resistance was ⁇ .
  • the compatibility with the epoxy resin was ⁇ .
  • Copolymer F was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was formed.
  • the test piece used for the bending test was prepared by placing the curable resin composition on a mold under a vacuum press molding machine and placing the solvent under a heating vacuum. Volatilized. Thereafter, an upper mold was placed, heated and pressed under vacuum, and held at 200 ° C. for 1 hour to form a flat plate having a thickness of 1.0 mm.
  • a test piece having a width of 5.0 mm, a thickness of 1.0 mm, a length of 120 mm was prepared from a flat plate obtained by molding, and a bending test was performed. The bending strength and bending elongation at break of the prepared bending test pieces were measured using a universal testing apparatus.
  • the bending strength and the bending elongation at break are ⁇ when the value is less than ⁇ 10% with respect to the measurement value of the reference blend, ⁇ when the value is 10% or more, and ⁇ 10 to ⁇ 20%.
  • the evaluation was made with ⁇ for the range value and x for the value of ⁇ 20% or less.
  • a test piece having a width of 3.0 mm, a thickness of 0.2 mm, a length of 40 mm is prepared from the flat plate obtained by molding, and is set only on the chuck above the TMA (thermomechanical analyzer). Under an air stream, the temperature was raised to 220 ° C. at a heating rate of 10 ° C./min, and the remaining solvent was removed by heat treatment at 220 ° C. for 20 minutes, and the molding distortion in the test piece was removed. After allowing the TMA to cool to room temperature, the lower part of the test piece in the TMA measuring device is also set on the probe for analysis, and scan measurement is performed from 30 ° C. to 360 ° C. at a heating rate of 10 ° C./min in a nitrogen stream.
  • TMA thermomechanical analyzer
  • the linear expansion coefficient was calculated from the dimensional change at 0 to 40 ° C.
  • the above test piece is set in a DMA (dynamic viscoelasticity device) measuring device and scanned from 30 ° C. to 320 ° C. at a temperature rising rate of 3 ° C./min under a nitrogen stream. Measurement was performed and Tg was obtained from the peak top of the tan ⁇ curve.
  • DMA dynamic viscoelasticity device
  • Dielectric constant and dielectric loss tangent In accordance with JIS C2565 standard, cured after storing for 24 hours in a room at 23 ° C and 50% humidity after dry-drying using a cavity resonator method dielectric constant measuring device manufactured by AET Co., Ltd. Using a flat plate test piece, the dielectric constant and dielectric loss tangent at 18 GHz were measured. Moreover, after leaving the hardened
  • a plurality of the above curable composite materials are stacked as necessary so that the thickness after molding becomes about 0.6 mm to 1.0 mm, and a copper foil having a thickness of 18 ⁇ m on both sides thereof (Product name: F2-WS copper foil, Rz: 2.0 ⁇ m, Ra: 0.3 ⁇ m) was placed and molded and cured by a vacuum press molding machine to obtain a laminate for evaluation.
  • Curing conditions were as follows: the temperature was increased at 3 ° C./min, the pressure was 3 MPa, and the temperature was maintained at 200 ° C. for 60 minutes to obtain a copper clad laminate for evaluation.
  • a test piece having a width of 20 mm and a length of 100 mm was cut out from the cured laminate thus obtained, and a parallel cut having a width of 10 mm was made on the copper foil surface.
  • the copper foil was continuously peeled off at a speed of minutes, the stress at that time was measured with a tensile tester, and the minimum value of the stress was recorded as the copper foil peel strength. (Conforms to JIS C 6481).
  • the copper foil peel strength test after the wet heat resistance test was measured in the same manner as described above after the test piece was left at 85 ° C. and a relative humidity of 85% for 2 weeks.
  • the laminate from which the sample was not removed was immersed in a circulated MLB conditioner 211 (trade name, manufactured by Rohm & Haas Japan Co., Ltd.) with a swelling aqueous solution at 80 ° C. for 5 minutes. Further, after 3 minutes of treatment at room temperature in running water, Circoposit MLB promoter 213 (trade name, manufactured by Rohm & Haas Japan Co., Ltd.) is used as a strongly alkaline aqueous solution of permanganate, and similarly at 80 ° C. for 10 minutes by the dip method. Immersion treatment. Next, immersion treatment was carried out at 40 ° C.
  • a base copper having a thickness of 0.5 ⁇ m is formed on both sides of the laminate by dipping at room temperature for 15 minutes, and further on the electrolytic copper. Then, the copper was plated up to a thickness of 20 ⁇ m.
  • the above cured test laminate with plating is etched into a line having a copper width of 10 mm and a length of 100 mm, and one end thereof is peeled off and is gripped with a gripper, and is vertically aligned in accordance with JIS-C-6421.
  • the minimum value of the load when peeled off at room temperature of about 50 mm was recorded as the copper plating peel strength.
  • the laminated substrate for evaluation was immersed in boiling water for 4 hours and then immersed in a solder bath at 280 ° C. At that time, the presence of voids could not be confirmed, and even if immersed in a solder bath, it was swollen, and no defects such as delamination and measling (white spots) were evaluated as “ ⁇ ”. In addition, the case where generation of any one of delamination and measling (white spots) was confirmed was evaluated as “x”.
  • Example 5 20 g of the copolymer-A obtained in Synthesis Example 1, 0.2 g of Parkmill P as a polymerization initiator, 0.2 g of AO-60 as an antioxidant as a curing accelerator, and 8.6 g of toluene were dissolved in 8.6 g. A resin composition (varnish A) was obtained.
  • the prepared varnish A was dropped on the lower mold, the solvent was devolatilized at 130 ° C. under reduced pressure, the mold was assembled, and vacuum pressing was performed at 200 ° C. and 3 MPa for 1 hour to perform thermosetting.
  • various characteristics including the dielectric constant of 18 GHz and a dielectric loss tangent were measured.
  • the dielectric constant and dielectric loss tangent were measured, and the dielectric constant and dielectric loss tangent after a heat-and-moisture resistance test were measured. The results obtained from these measurements are shown in Table 1.
  • Examples 6-8, Comparative Examples 3-4 A curable resin composition (varnish) was obtained in the same manner as in Example 5 except that the formulation shown in Table 1 was used. And the hardened
  • Examples 9 to 19 and Comparative Examples 5 to 8 A curable resin composition (varnish) was obtained in the same manner as in Example 5 except that the formulation shown in Tables 2 and 3 was used. And the hardened
  • Example 29 in order to facilitate the dissolution of the stabilizer and the initiator, 30 parts by weight of toluene as a solvent was added to 100 parts by weight of the resin component to form a resin varnish in which each component was dissolved, and molding The resin varnish was devolatilized under reduced pressure at 50 ° C. immediately before performing the process, and the resin composition after removing the solvent was used as a test piece.
  • test pieces were blended with only a thermal initiator (Examples 21 to 28, Comparative Examples 11 to 12), and the curable resin composition was placed on the lower mold and b-staged under heating vacuum. .
  • the upper mold is placed on the lower mold, the mold is placed on the heating plate of a vacuum press molding machine, and the hot press is performed under vacuum at 200 ° C. Was held for 1 hour to form a cured resin flat plate A1 having a thickness of 1.0 mm.
  • a silicon rubber spacer having a thickness of 1.0 mm is used between two glass plates having a width of 50 mm, a length of 50 mm, and a thickness of 1.0 mm. Then, the composition is poured into a glass mold having a gap of 1.0 mm in thickness and the outer periphery is wound and fixed with polyimide tape, and ultraviolet light is irradiated for several seconds from one side of the glass mold with a high-pressure mercury lamp. After the primary curing, the glass mold was placed in an inert gas oven under a nitrogen gas stream and heated at 200 ° C. for 1 hour to form a cured resin flat plate A2.
  • test piece A A test piece obtained by setting the cured resin flat plate A1 or A2 having a thickness of 1.0 mm to a predetermined size is referred to as a test piece A.
  • test piece B A test piece obtained by making the cured resin flat plate B1 or B2 having a thickness of 0.2 mm obtained in the same manner as described above into a predetermined size is referred to as a test piece B.
  • a test piece B having a width of 3.0 mm, a thickness of 0.2 mm, and a length of 40 mm was prepared.
  • the lower part of the test piece in the TMA measuring device is also set on the probe for analysis, and scan measurement is performed from 30 ° C. to 360 ° C. at a heating rate of 10 ° C./min in a nitrogen stream.
  • the linear expansion coefficient was calculated from the dimensional change at 0 to 40 ° C. Moreover, the glass transition temperature was calculated
  • Haze (turbidity) and total light transmittance are measured using an integrating sphere light transmittance measuring device (Nippon Denshoku Co., Ltd.). Manufactured by SZ- ⁇ 90).
  • the curable resin composition was placed on a mold having a spherical lens shape having a diameter of 3.0 mm, Place the glass upper mold on the lower mold, and irradiate ultraviolet rays from the upper surface of the glass upper mold with a high-pressure mercury lamp for several seconds to perform primary curing, and then the inert gas in a nitrogen gas stream is passed through the glass mold.
  • a spherical lens having a diameter of 3.0 mm was molded by placing in an oven and heating at 200 ° C. for 1 hour. The molding of the spherical lens was repeated 5 times, and the releasability was evaluated based on the degree of difficulty when the cured resin lens was released from the mold. ⁇ ⁇
  • the mold reproducibility was evaluated by observing the surface shape of the cured resin lens and the surface shape of the mold. ⁇ ⁇ ⁇ ⁇ ⁇ Reproducibility is good ⁇ ⁇ ⁇ ⁇ ⁇ Reproducibility is poor
  • burrs and moles were evaluated based on the size of the burrs generated outside the product part of the molded product and the degree of resin leakage into the mold clearance when the cured resin lens was released from the mold.
  • ⁇ ⁇ ⁇ ⁇ ⁇ Burr size is less than 0.05mm and resin leakage is less than 1.0mm.
  • ⁇ ⁇ ⁇ ⁇ ⁇ Burr size is less than 0.2mm and resin leakage is less than 3.0mm.
  • ... Burr size is 0.2mm or more, resin leakage is 3.0mm or more
  • FANCLIL FA-BZA manufactured by Hitachi Chemical Co., Ltd., benzyl acrylate FANCLIL FA-302A; manufactured by Hitachi Chemical Co., Ltd., o-phenylphenoxyethyl acrylate light acrylate PO-A: manufactured by Kyoeisha Chemical Co., Ltd., phenoxyethyl acrylate og Sole EA-0200: manufactured by Osaka Gas Chemical Co., Ltd., fluorene skeleton-containing acrylate light acrylate TMP-A: manufactured by Kyoeisha Chemical Co., Ltd., trimethylolpropane triacrylate
  • Adeka Stub AO-412S manufactured by Adeka Co., Ltd., pentaerythritol-tetrakis Thiopropionate)
  • ADK STAB AO-60 Pentaerythritol tetrakis [3- (3,5-di-tert-buty
  • Synthesis example 7 50 parts by weight of propylene glycol monomethyl ether acetate and 19 parts by weight of methyl lactate were added to a flask equipped with a stirrer, a cooling pipe, a gas introduction pipe, a dropping funnel and a thermometer, and stirred while introducing nitrogen gas.
  • the temperature was raised to 65 ° C., 45 parts by weight of methyl methacrylate, 35 parts by weight of butyl acrylate, 17 parts by weight of 2-hydroxyethyl methacrylate, 13 parts by weight of methacrylic acid, 2,2′-azobis (2,4-dimethylvaleronitrile)
  • a mixture of 3 parts by weight, 49 parts by weight of propylene glycol monomethyl ether acetate and 20 parts by weight of methyl lactate was added dropwise over 3 hours, followed by stirring at 65 ° C. for 3 hours and further stirring at 95 ° C. for 1 hour.
  • a solution of combined G (solid content: 45% by mass) was obtained.
  • Mn of the obtained copolymer G was 16700, Mw was 38100, Mw / Mn was 2.28, and the acid value was 79 mgKOH / g.
  • component (A) 10 parts by weight of the copolymer A, as the component (E) 62 parts by weight of the solution of the copolymer G (solid content 45% by mass) (solid content 28 parts by mass), and as the component (B), polyester 33 parts by mass of urethane (meth) acrylate having a skeleton ("U-200AX” manufactured by Shin-Nakamura Chemical Co., Ltd.) and urethane (meth) acrylate having a polypropylene glycol skeleton ("UA-" manufactured by Shin-Nakamura Chemical Co., Ltd.) 4200 ") 15 parts by mass, as component (F), polyfunctional block isocyanate solution (solid content 75% by mass) obtained by protecting isocyanurate type trimer of hexamethylene diisocyanate with methyl ethyl ketone oxime (manufactured by Sumika Bayer Urethane Co., Ltd.) "Sumidur BL3175”) 20 parts by mass (
  • the varnish WI was applied on the non-treated surface of a PET film (“Cosmo Shine A4100” manufactured by Toyobo Co., Ltd., thickness 50 ⁇ m) using the coating machine, dried at 100 ° C. for 20 minutes, A surface release-treated PET film (“Purex A31” manufactured by Teijin DuPont Films, Inc., thickness 25 ⁇ m) was applied as a cover film to obtain a resin film FI for forming a cladding layer. At this time, the thickness of the resin layer was adjusted such that the cured film thickness was 20 ⁇ m for the lower clad layer forming resin film and 60 ⁇ m for the upper clad layer forming resin film.
  • the core part-forming resin varnish W-II was applied to a non-treated surface of a PET film (“Cosmo Shine A1517” manufactured by Toyobo Co., Ltd., thickness 16 ⁇ m) using a coating machine, and the coating was performed at 80 ° C. for 10 minutes. After drying at 100 ° C. for 10 minutes, a surface release-treated PET film (manufactured by Teijin DuPont Films, Inc .; Purex A31, thickness 25 ⁇ m) was applied as a protective film to obtain a resin film F-II for forming a core part. At this time, the thickness of the resin layer was adjusted so that the film thickness after curing was 50 ⁇ m.
  • Example 31 The lower clad layer-forming resin film FI from which the protective film was removed using a roll laminator was laminated on a PET film (thickness 50 ⁇ m) under the conditions of a pressure of 0.5 MPa and a temperature of 80 ° C. Furthermore, pressure bonding was performed using a vacuum pressurizing laminator under conditions of a pressure of 0.4 MPa and a temperature of 80 ° C. Next, using a UV exposure machine, the support film was removed after irradiation with 2000 mJ / cm 2 of UV light (wavelength 365 nm). Then, the lower clad layer 4 was formed by heat-curing at 160 degreeC for 1 hour.
  • the core part-forming resin film F-II from which the protective film was removed, was laminated on the lower clad layer 4 under the conditions of a pressure of 0.5 MPa and a temperature of 80 ° C. using a roll laminator. Further, the vacuum pressurizing laminator was used for pressure bonding under conditions of a pressure of 0.4 MPa and a temperature of 80 ° C.
  • the core part 2 was exposed by irradiating ultraviolet rays (wavelength 365 nm) at 1000 mJ / cm 2 with an ultraviolet exposure machine through a negative photomask having a width of 50 ⁇ m. After exposure at 80 ° C.
  • the support film was removed and developed using propylene glycol monomethyl ether acetate / N, N-dimethylacetamide (70/30 mass ratio). Subsequently, after washing with propylene glycol monomethyl ether acetate, further washing with 2-propanol. After drying, it was cured by heating at 160 ° C. for 1 hour. Next, the resin film FI for forming the upper clad layer from which the protective film has been removed is laminated on the core 2 and the lower clad layer 4 under the conditions of a pressure of 0.4 MPa and a temperature of 100 ° C. did.
  • the upper clad layer 3 was formed by irradiating with ultraviolet rays (wavelength 365 nm) at 2000 mJ / cm 2 to remove the support film, followed by heat curing at 160 ° C. for 1 hour. Thereafter, the surface release treatment PET film was removed to obtain an optical waveguide 1 shown in FIG. Thereafter, a flexible optical waveguide having a length of 10 cm was cut out using a dicing saw.
  • ultraviolet rays wavelength 365 nm
  • the obtained flexible optical waveguide was subjected to a temperature of 85 ° C. and humidity under the conditions according to the JPCA standard (JPCA-PE02-05-01S) using a high temperature and high humidity tester (“PL-2KT” manufactured by ESPEC Corporation). An 85% high temperature and high humidity test was conducted for 1000 hours.
  • the light propagation loss of the optical waveguide after the high-temperature and high-humidity standing test was measured using the same light source, light receiving element, incident fiber, and outgoing fiber as those described above, and evaluated according to the criteria shown in Table 8.
  • optical propagation loss of the optical waveguide after the temperature cycle test was measured using the same light source, light receiving element, incident fiber, and outgoing fiber as those described above, and evaluated according to the criteria shown in Table 8.
  • the light propagation loss of the optical waveguide after the reflow test was measured using the same light source, light receiving element, incident fiber, and outgoing fiber as those described above, and evaluated according to the criteria shown in Table 8.
  • Table 9 shows the evaluation of the flexible optical waveguide obtained in Example 31.
  • the cured product obtained from the terminal-modified soluble polyfunctional vinyl aromatic copolymer of the present invention or a material containing the same has improved heat resistance, compatibility and toughness, and is excellent in low dielectric properties. It is useful as a material for laminates. Further, the curable resin composition of the present invention is excellent in transparency, heat resistance and toughness, and can form a highly accurate thick film, not only as a curable resin composition in a transparent material, but also in particular an optical waveguide. Useful for forming applications.
  • Optical waveguide 2 Core part 3: Upper clad layer 4: Lower clad layer 5: Base material

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