WO2016104748A1 - Terminal-modified soluble polyfunctional vinyl aromatic copolymer, and curable resin composition and optical waveguide produced using same - Google Patents
Terminal-modified soluble polyfunctional vinyl aromatic copolymer, and curable resin composition and optical waveguide produced using same Download PDFInfo
- Publication number
- 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
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- meth
- compound
- copolymer
- acrylate
- Prior art date
Links
- 0 CC(C)(C)c(c(*)c1*)c(*)c(*)c1OC(C)(C)C Chemical compound CC(C)(C)c(c(*)c1*)c(*)c(*)c1OC(C)(C)C 0.000 description 2
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
Description
しかしながら、この可溶性多官能ビニル芳香族共重合体は、靱性が不足しているために、その硬化性組成物の硬化物において、十分な力学的性質が得られない為、複合体硬化物に於いて、層間剥離強度の不足、信頼性の低下といった課題があった。また、助触媒としてエステル化合物が使用できることが記載されているものの、具体的に使用可能なエステル化合物として例示されているのは、酢酸エチル、プロピオン酸メチルといった、可溶性多官能ビニル芳香族共重合体の末端に官能基を導入する機能を持たないエステル化合物であった。このため、特許文献3に開示されている可溶性多官能ビニル芳香族共重合体の末端基は、アルコール性水酸基を有する鎖状炭化水素化合物及び芳香族炭化水素化合物及びチオアルコール性メルカプト基を有する鎖状炭化水素化合物及び芳香族炭化水素化合物に由来するエーテル結合又はチオエーテル結合のいずれかを介した鎖状炭化水素基又は芳香族炭化水素基を末端基として含有したものであった。
However, since this soluble polyfunctional vinyl aromatic copolymer has insufficient toughness, sufficient mechanical properties cannot be obtained in the cured product of the curable composition. However, there are problems such as insufficient delamination strength and reduced reliability. Moreover, although it is described that 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
ポリマー光導波路の形態としては、光電気混載基板への適用を想定したガラスエポキシ樹脂などの硬い支持基板上に作製するリジッド光導波路や、ボード同士の接続を想定した硬い支持基板を持たないフレキシブル光導波路が好適と考えられている。
さらにフレキシブル配線板と光導波路を一体複合化した光電気複合フレキシブル配線板とすることで、実装の自由度をより一層向上することが可能となる。 By the way, in high-speed and high-density signal transmission between electronic elements and between wiring boards, signal transmission interference and attenuation are barriers in conventional transmission using electric wiring, and the limits of high-speed and high-density are beginning to appear. In order to overcome this, development of a technology for connecting electronic elements and wiring boards with light, so-called optical interconnection technology, has been underway. As an optical transmission line, a polymer optical waveguide has attracted attention because of its ease of processing, low cost, high degree of freedom of wiring, and high density.
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.
(c1)≧1.0(個/分子) (4)
を満足し、共重合体中のジビニル芳香族化合物由来の構造単位のモル分率(a)及びモノビニル芳香族化合物由来の構造単位のモル分率(b)が下記式(5)
0.05≦(a)/{(a)+(b)}≦0.95 (5)
を満足し、上記式(1)及び式(2)で表される末端基のモル分率(c)が下記式(6)
0.005≦(c)/{(a)+(b)}<2.0 (6)
を満足し、かつ、トルエン、キシレン、テトラヒドロフラン、ジクロロエタン又はクロロホルムに可溶である。 The copolymer preferably has a terminal group introduction amount (c1) represented by the above formula (3) of the following formula (4).
(C1) ≧ 1.0 (pieces / molecule) (4)
And 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)
And 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)
And is soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.
(c1)≧1.0(個/分子) (3)
を満足し、共重合体中のジビニル芳香族化合物由来の構造単位のモル分率(A)及びモノビニル芳香族化合物由来の構造単位のモル分率(B)が下記式(4)
0.05≦(A)/{(A)+(B)}≦0.95 (4)
を満足し、上記末端基のモル分率(C)が下記式(5)
0.005≦(C)/{(A)+(B)}<2.0 (5)
を満足し、かつ、トルエン、キシレン、テトラヒドロフラン、ジクロロエタン又はクロロホルムに可溶であることを特徴とする末端変性可溶性多官能ビニル芳香族共重合体でもある。 In the present invention, 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. A copolymer obtained by reacting in the presence of at least one catalyst (d), which is represented by the above formula (2) and the above formula (3) at a part of the terminal of the copolymer. A molecular weight distribution having a terminal group derived from the (meth) acrylic acid ester compound (c), a number average molecular weight Mn of 300 to 100,000, and represented by a ratio of the weight average molecular weight Mw to the number average molecular weight Mn ( Mw / Mn) is 100.0 or less, and the introduction amount (c1) of the end group is the following formula (3)
(C1) ≧ 1.0 (pieces / molecule) (3)
And 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)
And the molar fraction (C) of the terminal group is represented by the following formula (5):
0.005 ≦ (C) / {(A) + (B)} <2.0 (5)
And a terminal-modified soluble polyfunctional vinyl aromatic copolymer characterized by being soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.
(B)成分:分子中に1個以上の不飽和基を有する1種以上のビニル化合物、及び
(C)成分:ラジカル重合開始剤を含有し、
(A)成分の配合量が5~94.9wt%、(B)成分の配合量が5.0~85wt%、及び(C)成分の配合量が0.1~10wt%であることを特徴とする硬化性樹脂組成物である。 Furthermore, 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). A polymer, a solvent-soluble, polymerizable terminal-modified soluble polyfunctional vinyl aromatic copolymer,
(B) component: one or more vinyl compounds having one or more unsaturated groups in the molecule, and (C) component: a radical polymerization initiator,
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%, and the blending amount of the component (C) is 0.1 to 10 wt%. And a curable resin composition.
これは、ジビニル芳香族化合物(a)及びモノビニル芳香族化合物(b)と、上記式(1)で表される(メタ)アクリル酸エステル化合物(c)を、ルイス酸触媒、無機強酸及び有機スルホン酸からなる群から選ばれる一種以上の触媒(d)の存在下で、重合して得られる共重合体であることが好ましいが、それ以外の原料や条件で重合して得られる共重合体であってもよい。 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.
This includes divinyl aromatic compound (a) and monovinyl aromatic compound (b), and (meth) acrylic acid ester compound (c) represented by the above formula (1), Lewis acid catalyst, strong inorganic acid and organic sulfone. It is preferably a copolymer obtained by polymerization in the presence of one or more catalysts (d) selected from the group consisting of acids, but is a copolymer obtained by polymerization under other raw materials and conditions. There may be.
(式中、R5、R8は水素原子又はメチル基を示し、X1、X2は単結合、又はエステル結合、エーテル結合、チオエステル結合、チオエーテル結合及びアミド結合からなる群から選ばれる1種以上の結合を含有していてもよい炭素数1~20の2価の有機基を示し、R6、R9は水素原子又は炭素数1~20の1価の有機基を示す。)
(In the formula, R 5 and R 8 represent a hydrogen atom or a methyl group, and 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.)
さらに、本発明の硬化型樹脂組成物は、透明性、耐熱性、強靭性に優れ、高精度な厚膜形成が可能であり、透明材料における硬化型樹脂組成物としてのみならず、特に光導波路形成用途に有用であり、生産性の高い光導波路形成用の樹脂組成物や樹脂フィルムとすることができる。また、こうした光導波路形成用の樹脂組成物や樹脂フィルムを使用することによって、透明性、耐熱性、環境信頼性、強靭性に優れた光導波路とすることができる。 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. In addition, by using 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.
Furthermore, 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.
この末端変性可溶性多官能ビニル芳香族共重合体は、ジビニル芳香族化合物(a)及びモノビニル芳香族化合物(b)と、上記式(1)で表される(メタ)アクリル酸エステル化合物(c)を、ルイス酸触媒、無機強酸及び有機スルホン酸からなる群から選ばれる一種以上の触媒(d)の存在下で、重合して得られる共重合体であることができる。
式中、R1は炭素数1~18の炭化水素基又は水素を示し、R2~R3は炭素数1~18の炭化水素基を示し、R4は水素又はメチル基を示す。好ましいR1~R3は、メチル基、エチル基等の炭素数1~6のアルキル基である。 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). Can be a copolymer obtained by polymerizing in the presence of one or more catalysts (d) selected from the group consisting of Lewis acid catalysts, strong inorganic acids and organic sulfonic acids.
In the formula, 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, and 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.
ビニル基を1つ有する構造単位、例えば単位(a1)、(a3)は共重合体に重合性を与え、共重合体を多官能とし、硬化性樹脂とする。ビニル基を有しない構造単位である単位(a2)は架橋構造を与え、分岐度を増やすが、架橋が進行しすぎると硬化して溶剤不溶性となるので、架橋に関与していない単位(a1)及び単位(a3)が存在することが必要である。 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.
別の観点からは、ジビニル芳香族化合物由来の構造単位中のビニル基を1つ有する構造単位の含有量は、10~90モル%であることがよく、好ましくは20~80モル%、より好ましくは30~70モル%である。しかし、溶剤可溶性を示すようにこの構造単位の含有量又は重合度は制御される。 And with respect to the sum total of 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, the units (a1) and ( The content of 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.
From another viewpoint, 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%. However, the content of the structural unit or the degree of polymerization is controlled so as to exhibit solvent solubility.
上記含有量が少ないと、架橋密度の低下に伴って、耐熱性が低下するため、光導波路形成プロセス等に於ける熱履歴を受けたとき、良好な形状の維持が困難となり、多すぎるといと、エッチング特性が悪化して、微細構造が優れた形状の光導波路等を形成することが困難となる。 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.
共重合体の末端に上記末端基を上記の関係を満足するように導入することによって、低光損失で、靱性が高く、優れた耐熱性を有し、(メタ)アクリレート化合物との相溶性に優れ、成形加工性にも優れた樹脂組成物又は製品とすることができる。末端基のモル分率が小さいと(メタ)アクリレート化合物との相溶性と成形加工性が低下し、大きいと、湿熱履歴を受けたあとの寸法変化が大きくなり、上記特性が低下する。 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. When 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.
By introducing the above end groups to the end of the copolymer so as to satisfy the above relationship, low light loss, high toughness, excellent heat resistance, and compatibility with (meth) acrylate compounds It can be set as the resin composition or product which was excellent also in the moldability. If the molar fraction of the terminal group is small, the compatibility with the (meth) acrylate compound and the molding processability are reduced. If it is large, the dimensional change after receiving the wet heat history becomes large, and the above characteristics are deteriorated.
(メタ)アクリル酸エステル系化合物(c)から生じる末端基は、式(2)、及び(3)で表わされ、それぞれ共重合体の開始末端及び停止末端に結合すると考えられる。
(メタ)アクリル酸エステル系化合物(c)は、上記のように単量体の一種であるが、を重合添加剤でもある。これは共重合体に、連鎖移動反応によって、上記の末端基(構造単位の一つである)を与えるので、連鎖移動剤でもある。 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. As 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.
第一の態様に係る硬化性組成物は、末端変性可溶性多官能ビニル芳香族共重合体(XA)とラジカル重合開始剤(ラジカル重合触媒ともいう。)(XB)とを含有する。ラジカル重合開始剤(XB)としては、例えば、本発明の樹脂組成物は後述するように加熱等の手段により架橋反応を起こして硬化するが、その際の反応温度を低くしたり、不飽和基の架橋反応を促進する目的でラジカル重合開始剤(XB)を含有させて使用してもよい。この目的で用いられるラジカル重合開始剤の量は(XA)成分と(XB)成分の和を基準として0.01~10重量%、好ましくは0.1~8重量%である。ラジカル重合開始剤はラジカル重合触媒であるので、以下ラジカル重合開始剤で代表する。 Next, a 1st aspect is demonstrated about the curable composition of this invention. 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). As the radical polymerization initiator (XB), for example, the resin composition of the present invention is cured by causing a crosslinking reaction by means of heating or the like as described later. For the purpose of accelerating the crosslinking reaction, 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.
式(7)中、mは1又は2を示し、Lは下記式(8)で表されるポリフェニレンエーテル鎖を示す。Mは水素原子、下記式(9)で表される基で表される基を示し、mが1の場合は、Mは水素原子でなく、mが2の場合は、2つのMの少なくともいずれか一方は水素原子ではない。Tは、mが1のとき水素原子を示し、mが2のときアルキレン基、下記式(10)、又は(11)で表される基を示す。
In formula (7), m represents 1 or 2, and 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.
式(8)中、nは、50以下の正の整数を示し、R5、R6、R7、及びR8は、それぞれ独立して、水素原子、アルキル基、アルケニル基、アルキニル基、ホルミル基、アルキルカルボニル基、アルケニルカルボニル基、又はアルキニルカルボニル基を示す。
In the formula (8), n represents a positive integer of 50 or less, and 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;
式(9)中、Xは、炭素数1以上の有機基であり、酸素原子を含むこともある。Yはビニル基である。jは0又は1の整数を示す。
In formula (9), 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.
式(10)中、R10、R11、R12、及びR13は、それぞれ独立して、水素原子、アルキル基、アルケニル基、アルキニル基、ホルミル基、アルキルカルボニル基、アルケニルカルボニル基、又はアルキニルカルボニル基を示す。
In formula (10), 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.
式(11)中、R14、R15、R16、R17、R18、R19、R20、及びR21は、それぞれ独立して、水素原子、アルキル基、アルケニル基、アルキニル基、ホルミル基、アルキルカルボニル基、アルケニルカルボニル基、又はアルキニルカルボニル基を示す。Fは、炭素数0の場合を含む、炭素数20以下の直鎖状、分岐状又は環状の炭化水素基である。
In formula (11), 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.
式(12)中、pは、1又は2を示し、Eは、下記式(13)で表されるポリフェニレンエーテル鎖を示し、Gは、水素原子を示し、pは1又は2の整数を示す。Vは、pが1の場合に水素原子を示し、pが2の場合に、アルキレン基、下記式(14)、又は式(15)で表される基を示す。
In formula (12), p represents 1 or 2, E represents a polyphenylene ether chain represented by the following formula (13), G represents a hydrogen atom, and 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).
式(13)中、qは、50以下の正の整数を示し、R22、R23、R24、及びR25は、それぞれ独立して、水素原子、アルキル基、アルケニル基、アルキニル基、ホルミル基、アルキルカルボニル基、アルケニルカルボニル基、又はアルキニルカルボニル基を示す。
In the formula (13), q represents a positive integer of 50 or less, and 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;
(式(14)中、R26、R27、R28、及びR29は、それぞれ独立して、水素原子、アルキル基、アルケニル基、アルキニル基、ホルミル基、アルキルカルボニル基、アルケニルカルボニル基、又はアルキニルカルボニル基を示す。)
(In formula (14), 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.)
式(15)中、R30、R31、R32、R33、R34、R35、R36、及びR37は、それぞれ独立して、水素原子、アルキル基、アルケニル基、アルキニル基、ホルミル基、アルキルカルボニル基、アルケニルカルボニル基、又はアルキニルカルボニル基を示す。Fは、炭素数0の場合を含む、炭素数20以下の直鎖状、分岐状又は環状の炭化水素基である。
In formula (15), 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.
活性エステル化合物を形成するためのフェノール化合物及びナフトール化合物の具体例としては、ハイドロキノン、レゾルシン、ビスフェノールA、ビスフェノールF、ビスフェノールS、フェノールフタリン、メチル化ビスフェノールA、メチル化ビスフェノールF、メチル化ビスフェノールS、フェノール、o-クレゾール、m-クレゾール、p-クレゾール、カテコール、α-ナフトール、β-ナフトール、1,5-ジヒドロキシナフタレン、1,6-ジヒドロキシナフタレン、2,6-ジヒドロキシナフタレン、ジヒドロキシベンゾフェノン、トリヒドロキシベンゾフェノン、テトラヒドロキシベンゾフェノン、フロログルシン、ベンゼントリオール、ジシクロペンタジエニルジフェノール、フェノールノボラック等が挙げられる。これらのなかでも耐熱性、溶解性の観点から、1,5-ジヒドロキシナフタレン、1,6-ジヒドロキシナフタレン、2,6-ジヒドロキシナフタレン、ジヒドロキシベンゾフェノン、トリヒドロキシベンゾフェノン、テトラヒドロキシベンゾフェノン、ジシクロペンタジエニルジフェノール、フェノールノボラックが好ましく、ジヒドロキシベンゾフェノン、トリヒドロキシベンゾフェノン、テトラヒドロキシベンゾフェノン、ジシクロペンタジエニルジフェノール、フェノールノボラックがより好ましく、ジシクロペンタジエニルジフェノール、フェノールノボラックがさらに好まし好ましい。
活性エステル化合物を形成するためのチオール化合物の具体例としては、ベンゼンジチオール、トリアジンジチオール等が挙げられる。 Specific examples of the thiocarboxylic acid compound for forming the active ester compound include thioacetic acid and thiobenzoic acid.
Specific examples of 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. , Phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, tri Examples thereof include hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, and phenol novolac. Among these, from the viewpoint of heat resistance and solubility, 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.
活性エステル化合物の製造方法は特に限定されず、公知の方法により製造することができるが、たとえば、カルボン酸化合物及び/又はチオカルボン酸化合物とヒドロキシ化合物及び/又はチオール化合物との縮合反応によって得ることができる。
本発明の硬化性組成物中における、活性エステル化合物(XE)の配合量は、エポキシ樹脂(XD)100重量部に対して、好ましくは、20~120重量部、より好ましくは40~100重量部、さらに好ましくは50~90重量部の範囲である。活性エステル化合物(XE)の配合量を上記範囲とすることにより、硬化物としての誘電特性、及び耐熱性、線膨張係数を向上させることができる。 As the 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.) and the like can be mentioned.
The production method of the active ester compound is not particularly limited and can be produced by a known method. For example, it 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. By making the compounding quantity of active ester compound (XE) into the said range, the dielectric property as a hardened | cured material, heat resistance, and a linear expansion coefficient can be improved.
本発明の硬化性複合材料には、必要に応じて樹脂と基材の界面における接着性を改善する目的でカップリング剤を用いることができる。カップリング剤としては、シランカップリング剤、チタネートカップリング剤、アルミニウム系カップリング剤、ジルコアルミネートカップリング剤等一般のものが使用できる。 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.
In the curable composite material of the present invention, a coupling agent can be used for the purpose of improving the adhesiveness at the interface between the resin and the substrate, if necessary. As 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.
本発明のフィルムを製造する方法としては特に限定されることはなく、例えば硬化性組成物と必要に応じて他の成分を芳香族系、ケトン系等の溶媒若しくはその混合溶媒中に均一に溶解又は分散させ、PETフィルムなどの樹脂フィルムに塗布した後乾燥する方法などが挙げられる。塗布は必要に応じて複数回繰り返すことも可能であり、またこの際組成や濃度の異なる複数の溶液を用いて塗布を繰り返し、最終的に希望とする樹脂組成及び樹脂量に調整することも可能である。 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 μm, more preferably 5 to 100 μm.
The method for producing the film of the present invention is not particularly limited. For example, the curable composition and other components as required are uniformly dissolved in an aromatic solvent, a ketone solvent, or a mixed solvent thereof. Alternatively, 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.
本発明の第二の態様に係る硬化性樹脂組成物は、(A)成分、(B)成分及び(C)成分を必須成分として含む。ここで、(A)成分は末端変性可溶性多官能ビニル芳香族共重合体であり、(B)成分は分子中に1個以上の分子中に1個以上の不飽和基を有する1種以上のビニル化合物であり、(C)成分はラジカル重合開始剤である。 Hereinafter, a 2nd aspect is demonstrated about curable resin composition of this invention. 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. Here, the component (A) is a terminal-modified soluble polyfunctional vinyl aromatic copolymer, and 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, and the component (C) is a radical polymerization initiator.
(B)成分は、分子中に1個以上の不飽和基を有する1種以上のビニル化合物である。そして、(B)成分は、(A)成分と同じであることはない。すなわち、(A)成分は(B)成分としては扱わない。
ここで、ビニル化合物はオレフィン性の二重結合(不飽和基)を有する重合性の化合物であればよく、不飽和基の位置には制限はなく、不飽和基の数は1つであっても、複数であってもよい。以下、不飽和基をビニル基ともいう。(B)成分のビニル基は、(A)成分が有するビニル基と共重合可能である。 Next, in the curable resin composition according to the second aspect, the component (B) will be described.
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).
Here, 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. Hereinafter, 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).
これらの化合物は、単独、又は2種類以上を組み合わせて用いることができる。 Among these, from the viewpoint of transparency and heat resistance, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate It is preferable that they are aliphatic (meth) acrylates; alicyclic (meth) acrylate; aromatic (meth) acrylate; heterocyclic (meth) acrylate.
These compounds can be used alone or in combination of two or more.
ここで、硬化型ビニル系ポリマーは、上記ビニル化合物を単独重合又は共重合して得られ、少なくとも1個のビニル基を有するものであればよい。 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.
Here, the curable vinyl polymer may be obtained by homopolymerizing or copolymerizing the vinyl compound and having at least one vinyl group.
これらの中でも、透明性及び耐熱性の点から、アルキレン基、シクロアルキレン基、フェニレン基、及びビフェニレン基が好ましい。 In the general formula (16) or (17), 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.
Among these, an alkylene group, a cycloalkylene group, a phenylene group, and a biphenylene group are preferable from the viewpoint of transparency and heat resistance.
これらの中でも、透明性、及び耐熱性の点から、アルキル基、シクロアルキル基、アリール基、及びアラルキル基が好ましい。 When 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) 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, arylthio group, It may be substituted with an amino group, a silyl group, a silyloxy group, or the like. Here, R is a hydrocarbon group.
Among these, an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group are preferable from the viewpoint of transparency and heat resistance.
これらの中でも、透明性及び耐熱性の観点から、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレートなどの脂肪族(メタ)アクリレート、あるいは2-ヒドロキシ-3-フェノキシプロピル(メタ)アクリレート、2-ヒドロキシ-3-(o-フェニルフェノキシ)プロピル(メタ)アクリレートなどの芳香族(メタ)アクリレートであることが好ましい。
これらの化合物は、単独で又は2種類以上を組み合わせて用いることができる。 In the case where the component (B) is one or more (meth) acrylates having one or more (meth) acryloyl groups in the molecule, the (meth) acrylate is not particularly limited. For example, 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.
Among these, from the viewpoint of transparency and heat resistance, 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.
これらの化合物は、単独で又は2種類以上を組み合わせて用いることができる。 In addition, after copolymerization of an acid anhydride of a vinyl compound having two or more carboxy groups and a (meth) acrylate compound having one or more (meth) acryloyl groups in the molecule, an appropriate alcohol such as methanol, ethanol or propanol is used. A partially esterified vinyl compound is also preferably used.
These compounds can be used alone or in combination of two or more.
(1)2官能アルコール化合物、2官能イソシアネート化合物、及び水酸基を有する(メタ)アクリレートを反応して得られるウレタン(メタ)アクリレート。
(2)2官能アルコール化合物、2官能イソシアネート化合物、及びイソシアネート基を有する(メタ)アクリレートを反応して得られるウレタン(メタ)アクリレート。
(3)多官能イソシアネート化合物及び水酸基を有する(メタ)アクリレートを反応して得られるウレタン(メタ)アクリレート。
(4)多官能アルコール化合物及びイソシアネート基を有する(メタ)アクリレートを反応して得られるウレタン(メタ)アクリレート。 The curable (meth) acrylate (B1) is not particularly limited, and examples thereof include the following urethane (meth) acrylates (1) to (4).
(1) Urethane (meth) acrylate obtained by reacting a bifunctional alcohol compound, a bifunctional isocyanate compound, and a (meth) acrylate having a hydroxyl group.
(2) Urethane (meth) acrylate obtained by reacting a bifunctional alcohol compound, a bifunctional isocyanate compound, and a (meth) acrylate having an isocyanate group.
(3) A urethane (meth) acrylate obtained by reacting a polyfunctional isocyanate compound and a (meth) acrylate having a hydroxyl group.
(4) Urethane (meth) acrylate obtained by reacting a polyfunctional alcohol compound and a (meth) acrylate having an isocyanate group.
これらのジオール化合物は、単独又は2種類以上組み合わせて用いることができる。 Examples of other diol compounds 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.
これらの化合物は、単独で又は2種類以上を組み合わせて用いることができる。 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. Compound: 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-bis (4-isocyanatocyclohexyl) hexafluoropropane, bicycloheptane triisocyanate Alicyclic bifunctional isocyanate compounds such as 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, and aromatic bifunctional isocyanate compounds such as o-xylylene diisocyanate and m-xylylene diisocyanate.
These compounds can be used alone or in combination of two or more.
これらの化合物は、単独で又は2種類以上を組み合わせて用いることができる。 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) isocyanurate, ethoxylated forms thereof, propoxylated forms thereof, ethoxylated propoxylated forms thereof And their modified caprolactone; cyclohexanedimethanol type epoxy di (meth) acrylate, tricyclodecane dimethanol type epoxy di (meth) acrylate, hydrogenated bisphenol A type epoxy di (meth) acrylate, hydrogenated bisphenol F type epoxy di (meth) Acrylate, Hydroquinone type epoxy di (meth) acrylate, Resorcinol type epoxy di (meth) acrylate, Catechol type epoxy di (meth) acrylate, Bisphenol A type epoxy di (meth) acrylate, Bisphenol Bifunctional epoxy (meth) such as F type epoxy di (meth) acrylate, bisphenol AF type epoxy di (meth) acrylate, biphenol type epoxy di (meth) acrylate, fluorene bisphenol type epoxy di (meth) acrylate, isocyanuric acid monoallyl type epoxy di (meth) acrylate ) Acrylate; pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and other trifunctional or more (meth) acrylates, ethoxylated products thereof, propoxylated products thereof , These ethoxylated propoxy compounds, and their caprolactone modified products; phenol novolac epoxy (meth) acrylate, cresol novolac epoxy Shipori (meth) acrylate, trifunctional or more epoxy (meth) acrylates such as isocyanuric acid type epoxy tri (meth) acrylate.
These compounds can be used alone or in combination of two or more.
これらの化合物は、単独で又は2種類以上を組み合わせて用いることができる。 The (meth) acrylate having an isocyanate group is not particularly limited. For example, 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.
これらの化合物は、単独で又は2種類以上を組み合わせて用いることができる。 There is no restriction | limiting in particular as said polyfunctional isocyanate compound, For example, multimers, such as the said bifunctional isocyanate compound; The uretdione type dimer, isocyanurate type, biuret type trimer of the said bifunctional isocyanate compound, etc. are mentioned. . 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.
これらの化合物は、単独で又は2種類以上を組み合わせて用いることができる。 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.
上記カルボキシル基とウレタン結合を有する(メタ)アクリレートとしては、特に制限はなく、例えば、前述のウレタン(メタ)アクリレートを合成する際に、カルボキシル基含有ジオール化合物を前記ジオール化合物と併用して、又は前記ジオール化合物の代わりに用いて得られるウレタン(メタ)アクリレートなどが挙げられる。
カルボキシル基含有ジオール化合物としては、特に制限はなく、例えば、2,2-ジメチロールブタン酸、2,2-ジメチロールプロピオン酸、2,2-ジメチロール酪酸、2,2-ジメチロールペンタン酸などが挙げられる。
これらの化合物は、単独で又は2種類以上を組み合わせて用いることができる。 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. For example, when synthesizing the aforementioned urethane (meth) acrylate, 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.
5mgKOH/g以上であると、アルカリ現像液への溶解性が良好であり、200mgKOH/g以下であると、耐現像液性が良好である。 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.
多官能イソシアネート化合物としては、透明性及び耐熱性の観点から、その分子中に脂環構造及び脂肪族構造から選ばれる少なくとも1種を含む化合物が好ましく、中でも上記脂環式多官能イソシアネート化合物;上記脂肪族多官能イソシアネート化合物が好ましい。
なお、上記多官能イソシアネート化合物はウレトジオン型二量体、イソシアヌレート型三量体、又はビウレット型三量体などの多量体となっていてもよく、これらを構成する2つ又は3つの多官能イソシアネート化合物は、同一でも異なっていてもよい。また、異なる場合、例えば、脂環式多官能イソシアネート化合物と脂肪族多官能イソシアネート化合物の組合せのように、異なる種類の多官能イソシアネート化合物の組合せでもよい。
以上の多官能イソシアネート化合物は、単独又は2種類以上組み合わせて用いることができる。 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-trimethylhexamethylene diisocyanate, decamethylene diisocyanate And aliphatic polyfunctional isocyanate compounds such as dodecamethylene diisocyanate.
As 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. Moreover, when 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.
これらの中でも、透明性及び耐熱性の観点から、上記活性メチレン化合物;上記オキシム化合物;上記ラクタム化合物が好ましい。
以上のブロック剤は、単独又は2種類以上組み合わせて用いることができる。 As the blocking agent, 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. 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 γ-butyrolactam, δ-valerolactam, and ε-caprolactam Etc.
Among these, from the viewpoint of transparency and heat resistance, 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.
ラジカル重合開始剤としては、加熱又は紫外線、可視光線などの活性光線の照射によってラジカル重合を開始させるものであれば特に制限はなく、例えば、熱ラジカル重合開始剤、光ラジカル重合開始剤などが挙げられる。 In the curable resin composition of the present invention, 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. To start.
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.
それらの中でも、硬化性、透明性、及び耐熱性の観点から、ジアシルパーオキシド、パーオキシエステル、及びアゾ化合物であることが好ましい。 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; α, α′-bis (t-butyl Peroxy) diisopropylbenzene, dicumyl peroxide, t- Dialkyl peroxides such as tilcumyl peroxide and di-t-butyl peroxide; diacyl peroxides such as octanoyl peroxide, lauroyl peroxide, stearyl peroxide and benzoyl peroxide; bis (4-t-butylcyclohexyl) peroxide Peroxycarbonates such as oxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-3-methoxybutyl peroxycarbonate; t-butyl peroxypivalate, t- Hexyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, t -Hexilper Oxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxy-3,5 5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, Peroxyesters such as 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane and t-butylperoxyacetate; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2 , 4-Dimethylvaleronitrile), 2,2'-azobi (4-methoxy-2'-dimethylvaleronitrile) azo compounds and the like.
Among them, diacyl peroxide, peroxyester, and azo compound are preferable from the viewpoints of curability, transparency, and heat resistance.
以上のラジカル重合開始剤(熱ラジカル重合開始剤及び光ラジカル重合開始剤など)は、単独で又は2種類以上組み合わせて用いることができ、さらに適切な増感剤と組み合わせて用いることもできる。 Among the above radical photopolymerization initiators, α-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.
これらの有機溶剤は、単独で又は2種類以上を組み合わせて使用することができる。また、樹脂ワニス中の固形分濃度は、通常10~80質量%であることが好ましい。 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. For example, 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 acetate, methyl lactate, ethyl lactate and γ-butyrolactone; Carbonates such as tylene carbonate and propylene carbonate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, Bifunctional alcohol alkyl ethers such as propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether; ethylene glycol monomethyl Bifunctional alcohol alkyl ether acetates such as ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate; N, Examples thereof include amides such as N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.
These organic solvents can be used alone or in combination of two or more. Further, the solid content concentration in the resin varnish is usually preferably 10 to 80% by mass.
また、撹拌時間には特に制限はないが、1~24時間であることが好ましい。撹拌時間が1時間以上であると、各成分が十分に混合され、24時間以下であると、調合時間を短縮することができ、生産性が向上する。 When using the resin composition of this invention or the resin composition for optical waveguide formation as a varnish, it is preferable to mix by stirring. Although there is no restriction | limiting in particular in the stirring method, From the viewpoint of stirring efficiency, stirring using a propeller is preferable. There is no particular limitation on the rotation speed of the propeller during stirring, but it is preferably 10 to 1,000 rpm. When the rotation speed of the propeller is 10 rpm or more, the respective components are sufficiently mixed. When the rotation speed is 1,000 rpm or less, entrainment of bubbles due to rotation of the propeller is reduced. From the above viewpoint, 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.
この樹脂フィルムは、前記光導波路形成用の樹脂組成物を用いて形成される。例えば、光導波路形成用樹脂組成物を適当な支持フィルムに塗布することにより容易に製造することができる。また、この樹脂組成物が有機溶剤で希釈された樹脂ワニスである場合、樹脂ワニスを支持フィルムに塗布し、有機溶剤を除去することにより製造することができる。 Next, the resin film for forming an optical waveguide of the present invention will be described.
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 | coating a resin varnish to a support film and removing an organic solvent.
これらの中でも柔軟性及び強靭性の観点から、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリプロピレン、ポリカーボネート、ポリアミド、ポリイミド、ポリアミドイミド、ポリフェニレンエーテル、ポリフェニレンスルフィド、ポリアリレート、ポリスルホンであることが好ましい。
なお、樹脂層との剥離性向上の観点から、シリコーン系化合物、含フッ素化合物などにより離型処理が施されたフィルムを必要に応じて用いてもよい。 The support film is not particularly limited. For example, 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.
Among these, 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.
In addition, from the viewpoint of improving releasability from the resin layer, 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.
保護フィルムとしては、特に制限はないが、柔軟性及び強靭性の観点から、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレートなどのポリエステル;ポリエチレン、ポリプロピレンなどのポリオレフィンなどが好ましい。なお、樹脂層との剥離性向上の観点から、シリコーン系化合物、含フッ素化合物などにより離型処理が施されたフィルムを必要に応じて用いてもよい。
保護フィルムの厚みは、10~250μmであることが好ましく、15~200μmであることがより好ましく、20~150μmであることが特に好ましい。 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. In addition, from the viewpoint of improving releasability from the resin layer, 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 μm, more preferably 15 to 200 μm, and particularly preferably 20 to 150 μm.
このようにして得られた光導波路形成用樹脂フィルムは、例えばロール状に巻き取ることによって容易に保存することができる。また、ロール状のフィルムを所望のサイズに切り出して、シート状にして保存することもできる。 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 μm 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.
この場合の支持フィルムとしては、コアパターン形成に用いる露光用活性光線が透過するものであれば特に制限はなく、例えば、前述の光導波路形成用樹脂フィルムの支持フィルムの具体例として記載されたものと同様のものを好適に挙げることができる。
それらの中でも、露光用活性光線の透過率、柔軟性、及び強靭性の観点から、ポリエステル;ポリオレフィンであることが好ましい。さらに、露光用活性光線の透過率向上及びコアパターンの側壁荒れ低減の観点から、高透明タイプな支持フィルムを用いることがさらに好ましい。このような高透明タイプな支持フィルムとして、市販のものでは、例えば、東洋紡績(株)製「コスモシャインA1517」、「コスモシャインA4100」、東レ(株)製「ルミラーFB50」などが挙げられる。 Next, an application example in which the resin film for forming an optical waveguide of the present invention is a resin film for forming a core part will be described.
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. The same thing as can be mentioned suitably.
Among these, polyesters and polyolefins are preferable from the viewpoints of the transmittance of actinic rays for exposure, flexibility, and toughness. Furthermore, it is more preferable to use 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 core pattern. 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.
この場合の支持フィルムとしては、クラッド形成に用いる露光用活性光線が透過するものであれば特に制限はなく、例えば、前述の光導波路形成用樹脂フィルムの支持フィルムの具体例として記載されたものと同様のものを好適に挙げることができる。
それらの中でも、露光用活性光線の透過率、柔軟性、及び強靭性の観点から、ポリエステル;ポリオレフィンであることが好ましい。さらに、露光用活性光線の透過率向上及びクラッドパターンの側壁荒れ低減の観点から、高透明タイプな支持フィルムを用いることがさらに好ましい。このような高透明タイプな支持フィルムとして、市販のものでは、例えば、東洋紡績(株)製「コスモシャインA1517」、「コスモシャインA4100」、東レ(株)製「ルミラーFB50」などが挙げられる。 Next, the case where 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) will be described.
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. For example, it is described as a specific example of the support film of the resin film for forming an optical waveguide described above. The same thing can be mentioned suitably.
Among these, polyesters and polyolefins are preferable from the viewpoints of the transmittance of actinic rays for exposure, flexibility, and toughness. Furthermore, it is more preferable to use 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. 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.
図1の(a)~(d)はそれぞれ光導波路の断面図を示す。
図1の(a)において、光導波路1は基材5上に形成され、高屈折率であるコア部形成用樹脂組成物からなるコア部2、並びに低屈折率であるクラッド層形成用樹脂組成物からなる下部クラッド層4及び上部クラッド層3で構成されている。
図1の(b)~(d)はそれぞれ別の態様を示す。(b)は上部クラッド層3の外側に保護フィルムとして基材5が配置されている態様を示す。(c)は、下部クラッド層4及び上部クラッド層3の両方の外側に保護フィルムとして基材5が配置されていたる態様を示す。(d)のように、保護フィルム5としての基材が配置されていない態様を示す。 Next, the optical waveguide of the present invention will be described.
1A to 1D are sectional views of the optical waveguide.
In FIG. 1A, an
(B) to (d) of FIG. 1 show different embodiments. (B) shows a mode in which the
下部クラッド層形成用樹脂フィルムの厚みについては、特に制限はなく、硬化後の下部クラッド層4の厚みが上記の範囲となるように厚みが調整される。 The thickness of the
There is no restriction | limiting in particular about the thickness of the resin film for lower clad layer formation, and thickness is adjusted so that the thickness of the lower
なお、上記高温高湿放置試験とはJPCA規格(JPCA-PE02-05-01S)に準じた条件で実施する高温高湿放置試験のことを意味する。 In addition, 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).
なお、上記温度サイクル試験とはJPCA規格(JPCAPE02-05-01S)に準じた条件で実施する温度サイクル試験のことを意味する。 Further, 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).
なお、上記リフロー試験とはJEDEC規格(JEDEC JESD22A113E)に準じた条件で実施する鉛フリーはんだリフロー試験のことを意味する。 Further, 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.
In addition, the said reflow test means the lead-free solder reflow test implemented on the conditions according to JEDEC specification (JEDEC JESD22A113E).
なお、光電気複合基板において、複合化するプリント配線板としては、特に制限はなく、例えば、ガラスエポキシ基板、セラミック基板などのリジッド基板;ポリイミド基板、ポリエチレンテレフタレート基板などのフレキシブル基板などが挙げられる。 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. Examples of 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.
In the photoelectric composite substrate, 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.
光導波路を製造する方法としては、特に制限はなく、例えば、上記樹脂組成物又はフィルムを用いて、基材上に光導波路形成用樹脂層を形成して製造する方法などが挙げられる。 Hereinafter, 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.
There is no restriction | 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.
光導波路形成用樹脂組成物が、前記有機溶剤で希釈されて光導波路形成用樹脂ワニスとなっている場合、必要に応じて樹脂層を形成後に、乾燥する工程を入れてもよい。乾燥方法としては、特に制限はなく、例えば、加熱乾燥、減圧乾燥などが挙げられる。また、必要に応じてこれらを併用してもよい。 The method for forming the optical waveguide forming resin layer is not particularly limited. For example, using the optical waveguide forming resin composition, spin coating, dip coating, spraying, bar coating, roll coating, Examples of the coating method include a curtain coating method, a gravure coating method, a screen coating method, and an inkjet coating method.
When the resin composition for forming an optical waveguide is diluted with the organic solvent to form a resin varnish for forming an optical waveguide, a step of drying after forming a resin layer may be added as necessary. There is no restriction | limiting in particular as a drying method, For example, heat drying, vacuum drying, etc. are mentioned. Moreover, you may use these together as needed.
これらの中で、平坦性に優れ、線幅や線間の小さい微細パターンを有する光導波路が形成可能という観点から、光導波路形成用樹脂フィルムを用いて積層法により製造する方法が好ましい。 Other methods for forming the optical waveguide forming resin layer include a method of forming the optical waveguide forming resin film by a lamination method.
Among these, from the viewpoint that an optical waveguide having excellent flatness and having a fine pattern with a small line width and a small line pattern can be formed, a method of producing by a lamination method using a resin film for forming an optical waveguide is preferable.
下部クラッド層形成用樹脂層を光により硬化する際の活性光線の照射量は、特に制限はないが、0.1~5J/cm2とすることが好ましい。また、活性光線が基材を透過する場合、効率的に硬化させるために、両面から同時に活性光線を照射可能な両面露光機を使用することができる。また、加熱をしながら活性光線を照射してもよい。なお、光硬化前後の処理として、必要に応じて50~200℃の加熱処理を行ってもよい。
下部クラッド層形成用樹脂層を熱により硬化する際の加熱温度は、特に制限はないが、50~200℃とすることが好ましい。 The lower clad layer forming resin layer laminated on the
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 /
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.
なお、下部クラッド層形成用樹脂フィルムの保護フィルムは、硬化前に除去しても、硬化後に除去してもよい。 When the support film for the resin film for forming the lower clad layer functions as the
The protective film for the resin film for forming the lower cladding layer may be removed before curing or after curing.
活性光線の光源としては、特に制限はなく、例えば、超高圧水銀ランプ、高圧水銀ランプ、水銀蒸気アークランプ、メタルハライドランプ、キセノンランプ、カーボンアークランプなどの紫外線を有効に放射する光源;写真用フラッド電球、太陽ランプなどの可視光線を有効に放射する光源などが挙げられる。
コア部2を露光する際の活性光線の照射量は、0.01~10J/cm2であることが好ましく、より好ましくは0.03~5J/cm2であり、さらに好ましくは0.05~3J/cm2である。この範囲であると、硬化反応が十分に進行し、現像によりコア部が流失することがなく、一方、露光量過多によりコア部が太ることがなく、微細なパターンが形成でき好適である。コア部2の露光は、コア部形成用樹脂フィルムの支持フィルムを介して行っても、支持フィルムを除去してから行ってもよい。
また、露光後に、コア部2の解像度及び密着性向上の観点から、必要に応じて露光後加熱を行ってもよい。紫外線照射から露光後加熱までの時間は、10分以内であることが好ましいが、この条件には特に制限はない。露光後加熱温度は40~160℃であることが好ましく、時間は30秒~10分であることが好ましいが、これらの条件には特に制限はない。 As a third step, the
There is no particular limitation on 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
Moreover, you may perform post-exposure heating as needed from a viewpoint of the resolution of the
現像方法としては、特に制限はなく、例えば、スプレー法、ディップ法、パドル法、スピン法、ブラッシング法、スクラッピング法などが挙げられる。また、必要に応じてこれらの現像方法を併用してもよい。現像液としては、特に制限はなく、例えば、有機溶剤、有機溶剤と水からなる準水系現像液、アルカリ水溶液からなる水系アルカリ現像液、アルカリ水溶液と有機溶剤からなる準水系アルカリ現像液などが挙げられる。現像温度は、コア部形成用樹脂層の現像性に合わせて調節される。
有機溶剤としては、特に制限はなく、例えば、前記光導波路形成用樹脂組成物の希釈に用いる有機溶剤と同様のものを好適に挙げることができる。これらの化合物は、単独で又は2種類以上を組み合わせて使用することができる。また、有機溶剤中には、表面活性剤、消泡剤などを混入させてもよい。準水系現像液としては、1種類以上の有機溶剤と水からなるものであれば特に制限はない。有機溶剤の濃度は、5~90質量%であることが好ましい。また、準水系現像液中には、界面活性剤、消泡剤などを少量混入させてもよい。
アルカリ水溶液の塩基としては、特に制限はなく、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物;炭酸リチウム、炭酸ナトリウム、炭酸カリウムなどのアルカリ金属炭酸塩;炭酸水素リチウム、炭酸水素ナトリウム、炭酸水素カリウムなどのアルカリ金属重炭酸塩;リン酸カリウム、リン酸ナトリウムなどのアルカリ金属リン酸塩;ピロリン酸ナトリウム、ピロリン酸カリウムなどのアルカリ金属ピロリン酸塩;四ホウ酸ナトリウム、メタケイ酸ナトリウムなどのナトリウム塩;炭酸アンモニウム、炭酸水素アンモニウムなどのアンモニウム塩;水酸化テトラメチルアンモニウム、トリエタノールアミン、エチレンジアミン、ジエチレントリアミン、2-アミノ-2-ヒドロキシメチル-1,3-プロパンジオール、1,3-ジアミノプロパノール-2-モルホリンなどの有機塩基などが挙げられる。これらの化合物は、単独で又は2種類以上を組み合わせて使用することができる。
水系アルカリ現像液のpHは9~14であることが好ましい。また、水系アルカリ現像液には、界面活性剤、消泡剤などを混入させてもよい。
準水系アルカリ現像液としては、アルカリ水溶液と1種類以上の前記有機溶剤からなるものであれば特に制限はない。なお、有機溶剤としては、特に制限はなく、例えば、前記光導波路形成用樹脂組成物の希釈に用いる有機溶剤と同様のものを好適に挙げることができる。準水系アルカリ現像液のpHは、現像が十分にできる範囲でできるだけ小さくすることが好ましく、pH8~13であることが好ましく、pH9~12であることがさらに好ましい。有機溶剤の濃度は、通常、5~90質量%であることが好ましい。また、準水系アルカリ現像液中には、界面活性剤、消泡剤などを少量混入させてもよい。 As a 4th process, when exposed through the support film of the resin film for core part formation, this is removed and it develops using a developing solution.
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.
There is no restriction | limiting in particular as 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.
There is no restriction | limiting in particular as a base of aqueous alkali solution, For example, 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. These compounds can be used alone or in combination of two or more.
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 | limiting in particular as 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. 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. Further, a small amount of a surfactant, an antifoaming agent or the like may be mixed in the semi-aqueous alkaline developer.
現像又は洗浄後の処理として、コア部2の硬化性及び密着性向上の観点から、必要に応じて露光及び/又は加熱を行ってもよい。加熱温度は、特に制限はないが、40~200℃であることが好ましく、活性光線の照射量は、特に制限はないが、0.01~10J/cm2であることが好ましい。 As processing after development, you may wash | clean using an organic solvent, a semi-aqueous type washing | cleaning liquid, or water as needed. 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 | cleaning methods together as needed. An organic solvent can be used individually or in combination of 2 or more types. In the semi-aqueous cleaning liquid, 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
第1の工程と同様な方法で上部クラッド層形成用樹脂層を光及び/又は熱により硬化し、上部クラッド層3を形成する。上部クラッド層形成用樹脂層を光により硬化する際の活性光線の照射量は、特に制限はないが、0.1~30J/cm2とすることが好ましい。また、活性光線が基材を透過する場合、効率的に硬化させるために、両面から同時に活性光線を照射可能な両面露光機を使用することができる。また、必要に応じて加熱をしながら活性光線を照射してもよく、光硬化前後の処理として加熱処理を行ってもよい。活性光線照射中及び/又は照射後の加熱温度は、特に制限はないが、50~200℃であることが好ましい。上部クラッド層形成用樹脂層を熱により硬化する際の加熱温度は、特に制限はないが、50~200℃であることが好ましい。
なお、上部クラッド層形成用樹脂フィルムの支持フィルムの除去が必要な場合、硬化前に除去しても、硬化後に除去してもよい。
以上の工程で、光導波路1を作製することができる。 As a fifth step, an upper clad layer forming resin film is laminated on the lower
The upper clad layer forming resin layer is cured by light and / or heat to form the upper clad
In addition, when the removal of the support film of the resin film for upper clad layer formation is required, it may remove before hardening or after hardening.
The
分子量及び分子量分布測定は、GPC(東ソー製、HLC-8120GPC)を使用し、溶媒にテトラヒドロフラン、流量1.0ml/min、カラム温度38℃、単分散ポリスチレンによる検量線を用いて行った。 1) Molecular weight and molecular weight distribution of copolymer (soluble polyfunctional aromatic copolymer) For molecular weight and molecular weight distribution measurement, GPC (manufactured by Tosoh Corporation, HLC-8120 GPC) was used, tetrahydrofuran as a solvent, flow rate of 1.0 ml / min. The column temperature was 38 ° C., and a calibration curve using monodisperse polystyrene was used.
日本電子製JNM-LA600型核磁気共鳴分光装置を用い、13C-NMR及び1H-NMR分析により決定した。溶媒としてクロロホルム-d1を使用し、テトラメチルシランの共鳴線を内部標準として使用した。 2) Copolymer structure: Determined by 13 C-NMR and 1 H-NMR analysis using a JNM-LA600 nuclear magnetic resonance spectrometer manufactured by JEOL. Chloroform-d 1 was used as a solvent, and the tetramethylsilane resonance line was used as an internal standard.
末端基の算出は、上記のGPC測定より得られる数平均分子量と1H-NMR測定とガスクロマトグラフ(GC)分析の結果より得られるモノマー総量に対する末端基を導入するために使用した誘導体量とから、末端基を有する可溶性多官能ビニル芳香族共重合体1分子中に含まれる末端基数を算出した。 3) Analysis of end groups The end groups were calculated in order to introduce the end groups relative to the total amount of monomers obtained from the number average molecular weight obtained from the above GPC measurement, 1 H-NMR measurement and gas chromatograph (GC) analysis. From the amount of the derivative used, the number of terminal groups contained in one molecule of the soluble polyfunctional vinyl aromatic copolymer having terminal groups was calculated.
乾燥後の厚さが20μmになるように、ガラス基板に共重合体溶液を均一に塗布し、ホットプレートを用いて90分で30分間加熱し、乾燥させた。ガラス基板とともに得られた樹脂膜はTMA(熱機械分析装置)にセットし、窒素気流下、昇温速度10℃/分で220℃まで昇温し、更に220℃で20分間加熱処理することにより残存する溶媒を除去すると同時に、共重合体を硬化させた。ガラス基板を室温まで放冷した後、TMA測定装置中の試料に分析用プローブを接触させ、窒素気流下、昇温速度10℃/分で30℃から360℃までスキャン測定を行い、接線法で軟化温度を求めた。
ガラス転移温度については、上記の試験片を、DMA(動的粘弾性装置)測定装置にセットし、窒素気流下、昇温速度3℃/分で30℃から320℃までスキャンさせることにより測定を行い、tanδ曲線のピークトップによりTgを求めた。 4) Measurement of glass transition temperature (Tg) and softening temperature of cured product Copolymer solution was uniformly applied to a glass substrate so that the thickness after drying was 20 μm, 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. to 360 ° C. at a temperature rising rate of 10 ° C./min under a nitrogen stream. 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 δ curve.
共重合体の耐熱性評価は、試料をTGA(熱天秤)測定装置にセットし、窒素気流下、昇温速度10℃/分で30℃から400℃までスキャンさせることにより測定を行い、350℃における重量減少を耐熱性として求めた。一方、耐熱変色性の測定は、共重合体6.0g、ベンジルメタクリレート4.0g、及びt-ブチルパーオキシ-2-エチルヘキサノエート0.02gを混合し、窒素気流下で200℃、1時間加熱し、硬化物を得た。そして、得られた硬化物の変色量を目視にて確認し、○:熱変色なし、△:淡黄色、×:黄色に分類することにより耐熱変色性の評価を行った。 5) Evaluation of heat resistance and measurement of heat discoloration 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. On the other hand, 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 | cured material was confirmed visually, and heat-resistant discoloration property was evaluated by classifying into (circle): No thermal discoloration, (triangle | delta): Light yellow, and x: Yellow.
共重合体のエポキシ樹脂との相溶性の測定は、試料5.0gをエポキシ樹脂(液状ビスフェノールA型エポキシ樹脂:ジャパンエポキシレジン社製、エピコート828)3.0g、及び、フェノール樹脂(メラミン骨格系フェノール樹脂:群栄化学工業社製、PS-6492)2.0gをメチルエチルケトン(MEK)10gに溶解させ、溶解後の試料の透明性を目視にて確認し、○:透明、△:半透明、×:不透明もしくは溶解せず、に分類することにより相溶性の評価を行った。 6) Measurement of compatibility The measurement of the compatibility of the copolymer with the epoxy resin was carried out by using 5.0 g of a sample of 3.0 g of an epoxy resin (liquid bisphenol A type epoxy resin: Japan Epoxy Resin, Epicoat 828), and 2.0 g of phenol resin (melamine skeleton phenol resin: PS-6492, manufactured by Gunei Chemical Industry Co., Ltd.) was dissolved in 10 g of methyl ethyl ketone (MEK), and the transparency of the sample after dissolution was confirmed visually. , Δ: translucent, x: opaque or not dissolved, and the compatibility was evaluated.
ジビニルベンゼン(1,4-ジビニルベンゼン及び1,3-ジビニルベンゼンの混合物、以下の例も同様)1.28モル(182.7mL)、エチルビニルベンゼン(1-エチル-4-ビニルベンゼン、及び1-エチル-3-ビニルベンゼンの混合物、以下の例も同様)0.97モル(137.8mL)、メタクリル酸t-ブチル 2.00モル(323.2mL)、トルエン 300mLを2.0Lの反応器内に投入し、50℃で50ミリモルの三フッ化ホウ素のジエチルエーテル錯体を添加し、4時間反応させた。重合溶液を炭酸水素ナトリウム水溶液で停止させた後、純水で3回油層を洗浄し、60℃で減圧脱揮し、重合体を回収した。得られた重合体を秤量して、共重合体A 234.6gが得られたことを確認した。 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),
また、硬化物のTMA測定の結果、明確なTgは観察されなかった、軟化温度は300℃以上であった。TGA測定の結果、350℃における重量減少は2.80wt%、耐熱変色性は○であった。一方、エポキシ樹脂との相溶性は○であった。
共重合体Aはトルエン、キシレン、THF、ジクロロエタン、ジクロロメタン、クロロホルムに可溶であり、ゲルの生成は認められなかった。 Mn of the obtained copolymer A was 842, Mw was 3640, and Mw / Mn was 4.32. By performing 13C-NMR and 1H-NMR analyses, in the copolymer A, 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. Further, 60.1 mol% of structural units derived from divinylbenzene and 39.9 mol% in total of structural units derived from ethyl vinylbenzene were contained (excluding terminal structural units). The vinyl group content contained in the copolymer A was 36.2 mol% (excluding the terminal structural unit).
Moreover, clear Tg was not observed as a result of TMA measurement of hardened | cured material, and the softening temperature was 300 degreeC or more. As a result of TGA measurement, the weight loss at 350 ° C. was 2.80 wt%, and the heat discoloration resistance was ◯. On the other hand, the compatibility with the epoxy resin was ○.
Copolymer A was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was formed.
ジビニルベンゼン 1.28モル(182.7mL)、エチルビニルベンゼン 0.97モル(137.8mL)、アクリル酸t-ブチル 2.00モル(289.6mL)、トルエン 300mLを2.0Lの反応器内に投入し、50℃で50ミリモルの三フッ化ホウ素のジエチルエーテル錯体を添加し、4時間反応させた。重合溶液を炭酸水素ナトリウム水溶液で停止させた後、純水で3回油層を洗浄し、60℃で減圧脱揮し、重合体を回収した。得られた重合体を秤量して、共重合体B 215.3gが得られたことを確認した。 Synthesis example 2
Divinylbenzene 1.28 mol (182.7 mL), ethyl vinylbenzene 0.97 mol (137.8 mL), t-butyl acrylate 2.00 mol (289.6 mL),
また、硬化物のTMA測定の結果、明確なTgは観察されなかった、軟化温度は300℃以上であった。TGA測定の結果、350℃における重量減少は3.04wt%、耐熱変色性は○であった。一方、エポキシ樹脂との相溶性は○であった。
共重合体Bはトルエン、キシレン、THF、ジクロロエタン、ジクロロメタン、クロロホルムに可溶であり、ゲルの生成は認められなかった。 Mn of the obtained copolymer A was 952, Mw was 4490, and Mw / Mn was 4.72. By performing 13C-NMR and 1H-NMR analyses, in the copolymer B, end group resonance lines derived from t-butyl acrylate were observed. The amount (c1) of structural units derived from t-butyl acrylate of the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis results and the number average molecular weight in terms of standard polystyrene was 2.5 (pieces / molecule). It was. Further, it 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).
Moreover, clear Tg was not observed as a result of TMA measurement of hardened | cured material, and the softening temperature was 300 degreeC or more. As a result of TGA measurement, the weight loss at 350 ° C. was 3.04 wt%, and the heat discoloration resistance was ◯. On the other hand, the compatibility with the epoxy resin was ○.
Copolymer B was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was formed.
ジビニルベンゼン2.03モル(288.5mL)、エチルビニルベンゼン0.084モル(12.0mL)、スチレン2.11モル(241.7mL)、2-フェノキシエチルメタクリレート2.25モル(427.3mL)、酢酸ブチル100.0mL、トルエン1150mLを3.0Lの反応器内に投入し、50℃で300ミリモルの三フッ化ホウ素のジエチルエーテル錯体を添加し、4時間反応させた。重合溶液を炭酸水素ナトリウム水溶液で停止させた後、純水で3回油層を洗浄し、室温で反応混合液を大量のメタノールに投入し、重合体を析出させた。得られた重合体をメタノールで洗浄し、濾別、乾燥、秤量して、共重合体C 282.4gを得た。 Synthesis example 3 (comparative example)
Divinylbenzene 2.03 mol (288.5 mL), ethyl vinylbenzene 0.084 mol (12.0 mL), styrene 2.11 mol (241.7 mL), 2-phenoxyethyl methacrylate 2.25 mol (427.3 mL) Then, 100.0 mL of butyl acetate and 1150 mL of toluene were put into a 3.0 L reactor, 300 mmol of boron trifluoride diethyl ether complex was added at 50 ° C., and the mixture was reacted for 4 hours. After stopping the polymerization solution with an aqueous sodium hydrogen carbonate solution, the oil layer was washed three times with pure water, and the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a polymer. The obtained polymer was washed with methanol, filtered, dried and weighed to obtain 282.4 g of copolymer C.
また、硬化物のTMA測定の結果、明確なTgは観察されなかった、軟化温度は300℃以上であった。TGA測定の結果、350℃における重量減少は4.86wt%、耐熱変色性は○であった。一方、エポキシ樹脂との相溶性は△であった。
共重合体Cはトルエン、キシレン、THF、ジクロロエタン、ジクロロメタン、クロロホルムに可溶であり、ゲルの生成は認められなかった。 Mn of the obtained copolymer C was 2030, Mw was 5180, and Mw / Mn was 2.55. By performing 13 C-NMR and 1 H-NMR analyses, in the copolymer C, end group resonance lines derived from 2-phenoxyethyl methacrylate were observed. As a result of conducting an elemental analysis result of the copolymer C, it was C: 87.3 wt%, H: 7.4 wt%, and O: 5.2 wt%. 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). It was. Further, it contained 59.2 mol% of structural units derived from divinylbenzene and 40.8 mol% in total of structural units derived from styrene and ethylbenzene (excluding terminal structural units). The vinyl group content contained in the copolymer C was 35.3 mol% (excluding the terminal structural unit).
Moreover, clear Tg was not observed as a result of TMA measurement of hardened | cured material, and the softening temperature was 300 degreeC or more. As a result of TGA measurement, the weight loss at 350 ° C. was 4.86 wt%, and the heat discoloration resistance was ◯. On the other hand, the compatibility with the epoxy resin was Δ.
Copolymer C was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was formed.
ジビニルベンゼン1.92モル(273.5mL)、エチルビニルベンゼン0.08モル(11.4mL)、スチレン2.0モル(229.2mL)、2-フェノキシエチルアクリレート2.00モル(348.1mL)、酢酸ブチル250.0mL、トルエン1000mLを3.0Lの反応器内に投入し、70℃で80ミリモルの三フッ化ホウ素のジエチルエーテル錯体を添加し、6時間反応させた。重合溶液を炭酸水素ナトリウム水溶液で停止させた後、純水で3回油層を洗浄し、室温で反応混合液を大量のメタノールに投入し、重合体を析出させた。得られた重合体をメタノールで洗浄し、濾別、乾燥、秤量して、共重合体D 164.2gを得た。 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. After stopping the polymerization solution with an aqueous sodium hydrogen carbonate solution, the oil layer was washed three times with pure water, and the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a polymer. The obtained polymer was washed with methanol, filtered, dried, and weighed to obtain 164.2 g of copolymer D.
また、硬化物のTMA測定の結果、明確なTgは観察されなかった、軟化温度は300℃以上であった。TGA測定の結果、350℃における重量減少は5.50wt%、耐熱変色性は○であった。一方、エポキシ樹脂との相溶性は△であった。
共重合体Dはトルエン、キシレン、THF、ジクロロエタン、ジクロロメタン、クロロホルムに可溶であり、ゲルの生成は認められなかった。 Mn of the obtained copolymer D was 2330, Mw was 4940, and Mw / Mn was 2.12. By performing 13C-NMR and 1H-NMR analyses, in the copolymer D, end group resonance lines derived from 2-phenoxyethyl acrylate were observed. As a result of conducting an elemental analysis result of the copolymer D, it was C: 84.4 wt%, H: 7.3 wt%, and O: 7.9 wt%. The introduced amount (c1) of structural units derived from 2-phenoxyethyl acrylate of the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis results and the number average molecular weight in terms of standard polystyrene was 3.5 (pieces / molecule). It was. Further, it contained 54.3 mol% of structural units derived from divinylbenzene and 45.7 mol% in total of structural units derived from styrene and ethylbenzene (excluding terminal structural units). The vinyl group content contained in the copolymer D was 21.8 mol% (excluding the terminal structural unit).
Moreover, clear Tg was not observed as a result of TMA measurement of hardened | cured material, and the softening temperature was 300 degreeC or more. As a result of the TGA measurement, the weight loss at 350 ° C. was 5.50 wt%, and the heat discoloration resistance was ◯. On the other hand, the compatibility with the epoxy resin was Δ.
Copolymer D was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was observed.
ジビニルベンゼン 1.024モル(146.2mL)、エチルビニルベンゼン 0.776モル(110.2mL)、スチレン 0.45モル(51.7mL)、メタクリル酸t-ブチル 2.00モル(323.2mL)、トルエン 300mLを2.0Lの反応器内に投入し、50℃で50ミリモルの三フッ化ホウ素のジエチルエーテル錯体を添加し、4時間反応させた。重合溶液を炭酸水素ナトリウム水溶液で停止させた後、純水で3回油層を洗浄し、60℃で減圧脱揮し、重合体を回収した。得られた重合体を秤量して、共重合体E 225.7gが得られたことを確認した。 Synthesis example 5
Divinylbenzene 1.024 mol (146.2 mL), ethyl vinylbenzene 0.776 mol (110.2 mL), styrene 0.45 mol (51.7 mL), t-butyl methacrylate 2.00 mol (323.2 mL) Then, 300 mL of toluene was put into a 2.0 L reactor, 50 mmol of diethyl ether complex of boron trifluoride was added at 50 ° C., and reacted for 4 hours. After stopping the polymerization solution with an aqueous sodium hydrogen carbonate solution, the oil layer was washed three times with pure water, and devolatilized at 60 ° C. to recover the polymer. The obtained polymer was weighed to confirm that 225.7 g of copolymer E was obtained.
また、硬化物のTMA測定の結果、明確なTgは観察されなかった、軟化温度は300℃以上であった。TGA測定の結果、350℃における重量減少は3.37wt%、耐熱変色性は○であった。一方、エポキシ樹脂との相溶性は○であった。
共重合体Eはトルエン、キシレン、THF、ジクロロエタン、ジクロロメタン、クロロホルムに可溶であり、ゲルの生成は認められなかった。 Mn of the obtained copolymer E was 789, Mw was 3450, and Mw / Mn was 4.37. By performing 13C-NMR and 1H-NMR analyses, in the copolymer E, 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 2.4 (pieces / molecule). It was. Further, it 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).
Moreover, clear Tg was not observed as a result of TMA measurement of hardened | cured material, and the softening temperature was 300 degreeC or more. As a result of TGA measurement, the weight loss at 350 ° C. was 3.37 wt%, and the heat discoloration was ◯. On the other hand, the compatibility with the epoxy resin was ○.
Copolymer E was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was observed.
ジビニルベンゼン 1.024モル(146.2mL)、エチルビニルベンゼン 0.776モル(110.2mL)、ジビニルビフェニル 0.45モル(81.1g)、メタクリル酸t-ブチル 2.00モル(323.2mL)、トルエン 300mLを2.0Lの反応器内に投入し、50℃で50ミリモルの三フッ化ホウ素のジエチルエーテル錯体を添加し、4時間反応させた。重合溶液を炭酸水素ナトリウム水溶液で停止させた後、純水で3回油層を洗浄し、60℃で減圧脱揮し、重合体を回収した。得られた重合体を秤量して、共重合体F 318.7gが得られたことを確認した。 Synthesis Example 6
Divinylbenzene 1.024 mol (146.2 mL), ethylvinylbenzene 0.776 mol (110.2 mL), divinylbiphenyl 0.45 mol (81.1 g), t-butyl methacrylate 2.00 mol (323.2 mL) ), 300 mL of toluene was put into a 2.0 L reactor, and 50 mmol of boron trifluoride diethyl ether complex was added at 50 ° C. and reacted for 4 hours. After stopping the polymerization solution with an aqueous sodium hydrogen carbonate solution, the oil layer was washed three times with pure water, and devolatilized at 60 ° C. to recover the polymer. The obtained polymer was weighed to confirm that 318.7 g of copolymer F was obtained.
また、硬化物のTMA測定の結果、明確なTgは観察されなかった、軟化温度は300℃以上であった。TGA測定の結果、350℃における重量減少は2.92wt%、耐熱変色性は○であった。一方、エポキシ樹脂との相溶性は○であった。
共重合体Fはトルエン、キシレン、THF、ジクロロエタン、ジクロロメタン、クロロホルムに可溶であり、ゲルの生成は認められなかった。 Mn of the obtained copolymer F was 913, Mw was 4210, and Mw / Mn was 4.61. By performing 13C-NMR and 1H-NMR analyses, in the copolymer F, 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 2.2 (pieces / molecule). It was. Further, it 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).
Moreover, clear Tg was not observed as a result of TMA measurement of hardened | cured material, and the softening temperature was 300 degreeC or more. As a result of TGA measurement, the weight loss at 350 ° C. was 2.92 wt%, and the heat discoloration resistance was ◯. On the other hand, the compatibility with the epoxy resin was ○.
Copolymer F was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was formed.
硬化性樹脂組成物の溶液粘度は、E型粘度計を使用して、測定温度:25℃で測定を行った。 7) Solution viscosity The solution viscosity of the curable resin composition was measured using an E-type viscometer at a measurement temperature of 25 ° C.
曲げ試験に使用する試験片は、硬化性樹脂組成物を真空プレス成形機の下の金型上に硬化性樹脂組成物のワニスを乗せ、加熱真空下、溶剤を脱揮させた。その後、上型を乗せ、真空下、加熱プレスを行い、200℃で1時間保持することによって、厚さ:1.0mmの平板を成形した。成形して得られた平板より、幅:5.0mm、厚さ:1.0mm、長さ、120mmの試験片を作成し、曲げ試験を行った。作成した曲げ試験片の曲げ強度及び曲げ破断伸びは万能試験装置を用いて測定を行った。そして、曲げ強度及び曲げ破断伸びは、基準となる配合の測定値に対して±10%未満の値となるものを○、10%以上の値となるものを◎、-10~-20%の範囲の値となるものを△、-20%以下の値となるものを×として評価を行った。 8) Bending strength and bending elongation at break 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 Δ for the range value and x for the value of −20% or less.
硬化性樹脂組成物の線膨張係数及びガラス転移温度の試験に使用する試験片は、硬化性樹脂組成物を真空プレス成形機の下の平板形状の金型上に硬化性樹脂組成物のワニスを乗せ、加熱真空下、溶剤を脱揮させた。その後、0.2mmのスペーサーを挟んで、上型を乗せ、真空下、加熱プレスを行い、200℃で1時間保持することによって、厚さ:0.2mmの平板を成形した。成形して得られた平板より、幅:3.0mm、厚さ:0.2mm、長さ、40mmの試験片を作成し、TMA(熱機械分析装置)の上方のチャックのみにセットし、窒素気流下、昇温速度10℃/分で220℃まで昇温し、更に220℃で20分間加熱処理することにより残存する溶媒を除去するとともに、試験片中の成形歪みの除去を行った。TMAを室温まで放冷した後、TMA測定装置中の試験片の下側についても、分析用プローブにセットさせ、窒素気流下、昇温速度10℃/分で30℃から360℃までスキャン測定を行い、0~40℃に於ける寸法変化より、線膨張係数を算出した。
また、ガラス転移温度については、上記の試験片を、DMA(動的粘弾性装置)測定装置にセットし、窒素気流下、昇温速度3℃/分で30℃から320℃までスキャンさせることにより測定を行い、tanδ曲線のピークトップによりTgを求めた。 9) Linear expansion coefficient and glass transition temperature The test piece used for the test of the linear expansion coefficient and glass transition temperature of the curable resin composition was obtained by using the curable resin composition on a plate-shaped mold under a vacuum press molding machine. The varnish of the curable resin composition was placed on the substrate, and the solvent was devolatilized under heating vacuum. Thereafter, an upper mold was placed with a 0.2 mm spacer in between, a heat press was performed under vacuum, and the plate was held at 200 ° C. for 1 hour to form a flat plate having a thickness of 0.2 mm. 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. The linear expansion coefficient was calculated from the dimensional change at 0 to 40 ° C.
Regarding the glass transition temperature, 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 δ curve.
JIS C2565規格に準拠し、株式会社エーイーティー製、空洞共振器法誘電率測定装置により、絶乾後23℃、湿度50%の室内に24時間保管した後の硬化物平板試験片を使用して、18GHzでの誘電率及び誘電正接を測定した。
また、硬化物平板試験片を85℃、相対湿度85%で2週間放置した後、誘電率及び誘電正接の測定を行い、耐湿熱試験後の誘電率及び誘電正接を測定した。 10) 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 | cured material flat test piece to stand at 85 degreeC and 85% of relative humidity for 2 weeks, 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.
熱硬化性樹脂組成物のワニスにガラスクロス(Eガラス、目付71g/m2)を浸漬して含浸を行い、80℃のエアーオーブン中で10分間乾燥させた。その際、得られるプリプレグのレジンコンテンツ(R.C)が50wt%となるように調整した。
このプリプレグを使用して、成形後の厚みが約0.6mm~1.0mmになるように、上記の硬化性複合材料を必要に応じて複数枚重ね合わせ、その両面に厚さ18μmの銅箔(商品名F2-WS銅箔、Rz:2.0μm、Ra:0.3μm)を置いて真空プレス成形機により成形硬化させて評価用積層体を得た。硬化条件は、3℃/分で昇温し、圧力3MPaで、200℃で60分間保持し、評価用銅張積層板を得た。 11) Copper foil peel strength A glass cloth (E glass, weight per unit area: 71 g / m 2) was immersed in a varnish of a thermosetting resin composition, impregnated, and dried in an air oven at 80 ° C. for 10 minutes. At that time, the resin content (RC) of the obtained prepreg was adjusted to 50 wt%.
Using this prepreg, 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 μm on both sides thereof (Product name: F2-WS copper foil, Rz: 2.0 μm, Ra: 0.3 μm) 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.
耐湿熱性試験後の銅箔引き剥がし強さの試験は、上記の試験片を85℃、相対湿度85%で2週間放置した後、上記と同様にして測定した。 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.
・めっき銅付き積層板の作製
前項で作製した銅張り積層板を過硫酸アンモニウム150g/Lの水溶液に40℃で20分間浸漬して銅箔をエッチング除去した。 12) Copper plating peeling strength / Preparation of laminate with plated copper The copper-clad laminate prepared in the previous section was immersed in an aqueous solution of 150 g / L ammonium persulfate at 40 ° C. for 20 minutes to remove the copper foil by etching.
次いで、中和液としてMLBニュートライザー216(ローム&ハースジャパン株式会社製、商品名)を用いて、ディップ法で、40℃で5分間浸漬処理した。流水洗の室温-3分間処理後、コンディショナー液のCLC-501(商品名、日立化成工業株式会社製)を用いて60℃で5分間処理し、流水洗し、プリディップ液PD-201(商品名、日立化成工業株式会社製)水溶液中室温-3分間処理し、金属パラジウム液HS-202B(商品名、日立化成工業株式会社製)を含んだ水溶液中、室温で10分間処理し、水洗し、活性化処理液ADP-501(商品名、日立化成工業株式会社製)水溶液中で室温-5分間処理した。そして、無電解銅めっき液として、Cust-201を用いて、ディップ法にて室温―15分間浸漬処理により無電解銅厚0.5μmの下地銅を積層板の両面に形成し、さらに電解銅にて銅厚み20μmまでめっきアップした。 Next, 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. for 5 minutes by the dipping method using MLB Neutralizer 216 (Rohm & Haas Japan Co., Ltd., trade name) as a neutralizing solution. After washing with running water at room temperature for 3 minutes, using conditioner solution CLC-501 (trade name, manufactured by Hitachi Chemical Co., Ltd.) for 5 minutes at 60 ° C., washing with running water, pre-dip solution PD-201 (product) Name, manufactured by Hitachi Chemical Co., Ltd.) in aqueous solution at room temperature for 3 minutes, treated in aqueous solution containing metallic palladium solution HS-202B (trade name, manufactured by Hitachi Chemical Co., Ltd.) for 10 minutes at room temperature, and washed with water The solution was treated in an aqueous solution of activation treatment liquid ADP-501 (trade name, manufactured by Hitachi Chemical Co., Ltd.) at room temperature for 5 minutes. Then, by using Cust-201 as an electroless copper plating solution, a base copper having a thickness of 0.5 μm 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 μm.
前項で成形を行った評価用銅張積層板を用いて、格子状に線幅(L)が0.5mm、線間隔(S)が1.0mm(L/S=0.5/1.0mm)にパターニングしたコア材を作成した。このコア材を黒化処理し、次いで、その上に、さらにプリプレグを積層し、2次成形することで、内層が格子状パターンの評価用積層基板を作成した。その作成した評価用積層基板について、例えば、樹脂ワニスの流動性不足によるボイド等の欠陥が生じていないかを確認した。その後、この評価用積層基板を沸騰水に4時間浸漬した後、280℃のはんだ槽に浸漬させた。その際、ボイドの存在が確認できず、はんだ槽に浸漬した後も膨れ、層間剥離、ミーズリング(白斑)などの不良現象の発生が見られないものを「○」と評価し、ボイド、膨れ、層間剥離、ミーズリング(白斑)のいずれかの発生が確認できたものを「×」と評価した。 13) Formability Using the copper clad laminate for evaluation formed in the previous section, the line width (L) is 0.5 mm and the line interval (S) is 1.0 mm (L / S = 0.5) in a lattice shape. /1.0 mm), a core material patterned was prepared. This core material was subjected to blackening treatment, and then a prepreg was further laminated thereon, followed by secondary molding, thereby producing an evaluation laminated substrate having an inner layer of a lattice pattern. About the created laminated substrate for evaluation, for example, it was confirmed whether defects such as voids due to insufficient fluidity of the resin varnish occurred. Thereafter, 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”.
変性PPE-A:両末端にビニル基を有するポリフェニレンオリゴマー(Mn=1160、三菱瓦斯化学(株)製、2,2',3,3',5,5'-ヘキサメチルビフェニル-4,4'-ジオール・2,6-ジメチルフェノール重縮合物とクロロメチルスチレンとの反応生成物)
変性PPE-B:両末端にビニル基を有するポリフェニレンオリゴマー(Mn=2270、三菱瓦斯化学(株)製、2,2',3,3',5,5'-ヘキサメチルビフェニル-4,4'-ジオール・2,6-ジメチルフェノール重縮合物とクロロメチルスチレンとの反応生成物)
変性PPE-C:片末端にビニル基を有するポリフェニレンオリゴマー(Mn=2340、ポリフェニレンエーテル(SABICイノベーティブプラスチックス社製のSA120)とクロロメチルスチレンとの反応生成物)
TAIC:トリアリルイソシアヌレート(日本化成株式会社製)
DCP:トリシクロデカンジメタノールジメタクリレート(新中村化学工業株式会社製)
A-DCP:トリシクロデカンジメタノールジアクリレート (新中村化学工業株式会社製)o-クレゾールノボラック型エポキシ樹脂:エポトートYDCN-700-3(低粘度タイプ、新日鉄住金化学株式会社製)
ビスフェノールF型液状エポキシ樹脂:エピコート806L、Mw=370(ジャパンエポキシレジン社製)
ナフタレン骨格液状エポキシ樹脂:EPICLON HP-4032D、Mw=304(DIC社製)
ナフトール型エポキシ樹脂:ESN-475V、エポキシ当量:340(新日鉄住金化学社製)
ビスフェノールA型液状エポキシ樹脂:エピコート828US、Mw=370(ジャパンエポキシレジン社製)
変性PPE-D:両末端にエポキシ基を有するポリフェニレンオリゴマー(Mn=1180、三菱瓦斯化学(株)製、2,2',3,3',5,5'-ヘキサメチルビフェニル-4,4'-ジオール・2,6-ジメチルフェノール重縮合物とエピクロルヒドリンとの反応生成物)
ビフェニル骨格フェノール樹脂:明和化成社製、MEH-7851-S
メラミン骨格系フェノール樹脂:群栄化学工業社製、PS-6492
アリル基含有骨格フェノール樹脂:ジャパンエポキシレジン社製、YLH-903
脂環式骨格酸無水物:新日本理化社製、MH-700
芳香族骨格酸無水物:サートマー・ジャパン社製、SMAレジンEF60
スチレン系共重合体:KRATON A1535(Kraton Polymers LLC製)
フェノキシ樹脂:重量平均分子量37000、三菱化学(株)製「YL7553BH30」(不揮発分30質量%のMEKとシクロヘキサノンの1:1溶液)
アモルファス球状シリカ:アドマテックス社製、SE2050 SPE、平均粒子径0.5μm(フェニルシランカップリング剤により処理) <Explanation of symbols in the table>
Modified PPE-A: Polyphenylene oligomer having vinyl groups at both ends (Mn = 1160, manufactured by Mitsubishi Gas Chemical Co., Inc., 2,2 ′, 3,3 ′, 5,5′-hexamethylbiphenyl-4,4 ′ -Reaction product of diol, 2,6-dimethylphenol polycondensate and chloromethylstyrene)
Modified PPE-B: Polyphenylene oligomer having vinyl groups at both ends (Mn = 2270, manufactured by Mitsubishi Gas Chemical Co., Inc., 2,2 ′, 3,3 ′, 5,5′-hexamethylbiphenyl-4,4 ′ -Reaction product of diol, 2,6-dimethylphenol polycondensate and chloromethylstyrene)
Modified PPE-C: polyphenylene oligomer having vinyl group at one end (Mn = 2340, reaction product of polyphenylene ether (SA120 manufactured by SABIC Innovative Plastics) and chloromethylstyrene)
TAIC: triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.)
DCP: Tricyclodecane dimethanol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-DCP: Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) o-cresol novolac type epoxy resin: Epototo YDCN-700-3 (low viscosity type, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
Bisphenol F type liquid epoxy resin: Epicoat 806L, Mw = 370 (manufactured by Japan Epoxy Resin Co., Ltd.)
Naphthalene skeleton liquid epoxy resin: EPICLON HP-4032D, Mw = 304 (manufactured by DIC)
Naphthol type epoxy resin: ESN-475V, epoxy equivalent: 340 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
Bisphenol A type liquid epoxy resin: Epicoat 828US, Mw = 370 (manufactured by Japan Epoxy Resin Co., Ltd.)
Modified PPE-D: Polyphenylene oligomer having epoxy groups at both ends (Mn = 1180, manufactured by Mitsubishi Gas Chemical Co., Inc., 2,2 ′, 3,3 ′, 5,5′-hexamethylbiphenyl-4,4 ′ -Reaction product of 2-diol, 2,6-dimethylphenol polycondensate and epichlorohydrin)
Biphenyl skeleton phenol resin: MEH-7851-S manufactured by Meiwa Kasei Co., Ltd.
Melamine skeleton phenolic resin: manufactured by Gunei Chemical Industry Co., Ltd., PS-6492
Allyl group-containing skeleton phenol resin: YLH-903, manufactured by Japan Epoxy Resin Co., Ltd.
Alicyclic skeleton acid anhydride: manufactured by Shin Nippon Rika Co., Ltd., MH-700
Aromatic skeleton acid anhydride: SMA Resin EF60, manufactured by Sartomer Japan
Styrene copolymer: KRATON A1535 (manufactured by Kraton Polymers LLC)
Phenoxy resin: weight average molecular weight 37000, “YL7553BH30” manufactured by Mitsubishi Chemical Corporation (a 1: 1 solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass)
Amorphous spherical silica: manufactured by Admatechs, SE2050 SPE, average particle size 0.5 μm (treated with phenylsilane coupling agent)
合成例1で得られた共重合体-A 20gと、重合開始剤としてパークミルP 0.2g、硬化促進剤として、酸化防止剤としてAO-60 0.2gをトルエン8.6gに溶解し硬化性樹脂組成物(ワニスA)を得た。 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.
表1に示した配合処方としたこと以外は、実施例5と同じ方法で硬化性樹脂組成物(ワニス)を得た。そして、実施例5と同様にして硬化物平板試験片を作成し、実施例5と同じ項目について、試験・評価を行った。これらの試験により得られた結果を表1に示した。 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 | cured material flat plate test piece was created like Example 5, and it tested and evaluated about the same item as Example 5. FIG. The results obtained by these tests are shown in Table 1.
表2及び表3に示した配合処方としたこと以外は、実施例5と類似の方法で硬化性樹脂組成物(ワニス)を得た。そして、実施例5と同様にして硬化物平板試験片を作成し、実施例5と同じ項目について、試験・評価を行った。これらの試験により得られた結果を表1に示した。さらに、これらの実施例及び比較例で示したワニスを使用して、前述の試験方法11)~13)に記載の方法に従って、プリプレグ、試験用銅張積層板、及び、試験用めっき付き積層板を作成し、銅箔引き剥し強さ、銅めっき引き剥し強さ、並びに、成形性の評価を行った。試験結果を表2及び表3に示した。 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 | cured material flat plate test piece was created like Example 5, and it tested and evaluated about the same item as Example 5. FIG. The results obtained by these tests are shown in Table 1. Further, using the varnishes shown in these Examples and Comparative Examples, the prepreg, the test copper-clad laminate, and the test-coated laminate were made according to the methods described in the test methods 11) to 13) above. The copper foil peel strength, the copper plating peel strength, and the moldability were evaluated. The test results are shown in Tables 2 and 3.
合成例1~6で得られた共重合体A~Fを使用して、硬化性樹脂組成物とした。
表4及び5に示す共重合体、アクリレート、重合開始剤及び添加剤を、表4及び5に示す割合(重量比)で混合して、硬化性樹脂組成物とした。ここで、表4及び5に示す実施例及び比較例は、実施例29を除き、表中に記載の配合で混合して得られた樹脂組成物をそのままで評価用の試験片に成形した。実施例29については、安定剤及び開始剤の溶解を容易にするため、樹脂成分100重量部に対して、溶剤としてトルエンを30重量部添加して、各成分を溶解させた樹脂ワニスとし、成形を行う直前に樹脂ワニスを50℃で減圧脱揮を行い、溶剤を除去後の樹脂組成物を使用して試験片とした。 Examples 21 to 30 and Comparative Examples 11 to 12
Copolymers A to F obtained in Synthesis Examples 1 to 6 were used to obtain curable resin compositions.
Copolymers, acrylates, polymerization initiators and additives shown in Tables 4 and 5 were mixed at the ratios (weight ratios) shown in Tables 4 and 5 to obtain curable resin compositions. Here, in Examples and Comparative Examples shown in Tables 4 and 5, except for Example 29, the resin composition obtained by mixing with the formulation described in the table was molded into a test piece for evaluation as it was. In 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.
厚み1.0mmの硬化樹脂平板A1又はA2を所定の大きさにして得られる試験片を、試験片Aとする。
上記と同様にして得た厚み0.2mmの硬化樹脂平板B1又はB2を所定の大きさにして得られる試験片を、試験片Bとする。 The 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. . After the viscosity of the resin composition increases and becomes viscous, 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. On the other hand, in the formulations containing UV initiators (Examples 29 to 30), 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.
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.
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.
これらの測定の結果を表4及び5に示す。 Evaluation of the characteristics of these curable resin compositions and cured products was performed according to the following test methods.
The results of these measurements are shown in Tables 4 and 5.
硬化性樹脂組成物(溶剤不含)の溶液粘度は、E型粘度計を使用して、測定温度:25℃で測定を行った。 7) Solution viscosity The solution viscosity of the curable resin composition (without solvent) was measured at a measurement temperature of 25 ° C using an E-type viscometer.
幅:5.0mm、厚さ:1.0mm、長さ、120mmの試験片Aを用意した。曲げ強度及び曲げ破断伸びは万能試験装置を用いて測定を行った。そして、曲げ強度及び曲げ破断伸びは、基準となる配合の測定値に対して±10%未満の値となるものを○、10%以上の値となるものを◎、-10~-20%の範囲の値となるものを△、-20%以下の値となるものを×として評価を行った。 8) Bending strength and bending elongation at break A test piece A having a width of 5.0 mm, a thickness of 1.0 mm, a length of 120 mm was prepared. The bending strength and bending breaking elongation 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 Δ for the range value and x for the value of −20% or less.
幅:3.0mm、厚さ:0.2mm、長さ:40mmの試験片Bを用意した。TMA(熱機械分析装置)の上方のチャックのみにセットし、窒素気流下、昇温速度10℃/分で220℃まで昇温し、更に220℃で20分間加熱処理することにより、試験片中の成形歪みの除去を行った。TMAを室温まで放冷した後、TMA測定装置中の試験片の下側についても、分析用プローブにセットさせ、窒素気流下、昇温速度10℃/分で30℃から360℃までスキャン測定を行い、0~40℃に於ける寸法変化より、線膨張係数を算出した。また、接線法でガラス転移温度を求めた。
なお、ガラス転移温度は全ての実施例及び比較例において、観察されなかったので、記載を省略した。 9) Linear expansion coefficient and glass transition temperature 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. Set only on the chuck above the TMA (thermomechanical analyzer), raise the temperature to 220 ° C. at a rate of temperature increase of 10 ° C./min in a nitrogen stream, and heat-treat at 220 ° C. for 20 minutes. The molding distortion 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. The linear expansion coefficient was calculated from the dimensional change at 0 to 40 ° C. Moreover, the glass transition temperature was calculated | required by the tangent method.
In addition, since the glass transition temperature was not observed in all the Examples and the comparative examples, description was abbreviate | omitted.
厚み1.0mmの試験片Aを使用して、アッベ屈折率計(アタゴ(株)製)で屈折率及びアッベ数を測定した。 10) Measurement of refractive index Using the test piece A having a thickness of 1.0 mm, the refractive index and the Abbe number were measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).
厚み1.0mmの試験片Aを使用して、色彩色差計(商品名「MODEL TC-8600」、東京電色(株)製)で測定し、そのYI値を示した。 12) Hue Using a test piece A having a thickness of 1.0 mm, it was measured with a color difference meter (trade name “MODEL TC-8600”, manufactured by Tokyo Denshoku Co., Ltd.), and the YI value was shown.
厚み0.2mmの試験片Bを使用して、Haze(濁り度)と全光線透過率を、積分球式光線透過率測定装置(日本電色社製、SZ-Σ90)を用い測定した。 13) Haze (turbidity) and total light transmittance Using test piece B having a thickness of 0.2 mm, Haze (turbidity) and total light transmittance are measured using an integrating sphere light transmittance measuring device (Nippon Denshoku Co., Ltd.). Manufactured by SZ-Σ90).
熱開始剤のみを添加した配合(実施例21~28、比較例11~12)では、下型上に硬化性樹脂組成物を乗せ、加熱真空下、b-ステージ化を行った。樹脂組成物の粘度が上昇して、粘調となった後、上型を下型の上に乗せ、金型を真空プレス成形機の加熱板に乗せ、真空下、加熱プレスを行い、200℃で1時間保持することによって、一方、UV開始剤を含有する配合(実施例29~30)では、直径3.0mmの球面レンズの形状のキャビティを有する金型上に硬化性樹脂組成物を乗せ、ガラス製上型を下型の上に乗せ、このガラス製上型の上面から高圧水銀ランプにより、数秒間紫外線を照射して、1次硬化させた後、このガラス型を窒素ガス気流下のイナートガスオーブンに入れ、200℃で1時間加熱することによって、直径:3.0mmの球面レンズを成形した。かかる球面レンズの成形を5回繰り返し、硬化樹脂レンズを金型より離型させた時の難易度により離型性を評価した。
○・・・・金型からの離型性が良好
△・・・・離型がやや困難
×・・・・離型が困難或は型のこりがある 14) Releasability, mold reproducibility, and burrs, moles In formulations containing only a thermal initiator (Examples 21 to 28, Comparative Examples 11 to 12), a curable resin composition was placed on the lower mold and heated. B-Staging was performed under vacuum. After the viscosity of the resin composition increases and becomes viscous, 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. On the other hand, in the formulations containing UV initiator (Examples 29 to 30), 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.
○ ···································································································································
○・・・・再現性良好
×・・・・再現性が不良 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
○・・・・バリの大きさが0.05mm未満、樹脂の洩れこみが1.0mm未満
△・・・・バリの大きさが0.2mm未満、樹脂の洩れこみが3.0mm未満
×・・・・バリの大きさが0.2mm以上、樹脂の洩れこみが3.0mm以上 The 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
厚み1.0mmの試験片Aを使用として、分光測色計CM-3700d(コニカミノルタ社製)にて波長:400nmの分光透過率を測定した。測定タイミングは、190℃60分でのポストキュアを行った耐熱試験前と、エアーオーブン中、260℃、8分間の耐熱試験後とした。 15) Reflow heat resistance Using a test piece A having a thickness of 1.0 mm, a spectral transmittance at a wavelength of 400 nm was measured with a spectrocolorimeter CM-3700d (manufactured by Konica Minolta). The measurement timing was before the heat resistance test after post-cure at 190 ° C. for 60 minutes and after the heat resistance test at 260 ° C. for 8 minutes in an air oven.
ファンクリルFA-BZA;日立化成工業株式会社製、ベンジルアクリレート
ファンクリルFA-302A;日立化成工業株式会社製、o-フェニルフェノキシエチルアクリレート
ライトアクリレートPO-A:共栄社化学株式会社製、フェノキシエチルアクリレート
オグソールEA-0200:大阪ガスケミカル株式会社製、フルオレン骨格含有アクリレート
ライトアクリレートTMP-A:共栄社化学株式会社製、トリメチロルプロパントリアクリレート
アデカスタブAO-412S:株式会社アデカ製、ペンタエリスリトール-テトラキス(ドデシルチオプロピオネート)
アデカスタブAO-60:株式会社アデカ製、ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]
パーブチルO:日本油脂株式会社製、t-ブチル-パーオキシ-2-エチルヘキサノエート
イルガキュア184;チバ・スペシャリティ・ケミカルズ社製、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン <Explanation of symbols in the table>
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-butyl-4-hydroxyphenyl) propionate, manufactured by Adeka Corporation]
Perbutyl O: manufactured by Nippon Oil & Fat Co., Ltd., t-butyl-peroxy-2-ethylhexanoate irgacure 184; manufactured by Ciba Specialty Chemicals, 1-hydroxy-cyclohexyl-phenyl-ketone
撹拌機、冷却管、ガス導入管、滴下ろうと、及び温度計を備えたフラスコに、プロピレングリコールモノメチルエーテルアセテート50重量部及び乳酸メチル19重量部を加え、窒素ガスを導入しながら撹拌を行った。温度を65℃に上昇させ、メチルメタクリレート45重量部、ブチルアクリレート35重量部、2-ヒドロキシエチルメタクリレート17重量部、メタクリル酸13重量部、2,2’-アゾビス(2,4-ジメチルバレロニトリル)3重量部、プロピレングリコールモノメチルエーテルアセテート49重量部、及び乳酸メチル20重量部の混合物を3時間かけて滴下後、65℃で3時間撹拌し、さらに95℃で1時間撹拌を続けて、共重合体Gの溶液(固形分45質量%)を得た。得られた共重合体GのMnは16700、Mwは38100、Mw/Mnは2.28であり、酸価は79mgKOH/gであった。 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.
(A)成分として、共重合体A10重量部、(E)成分として前記共重合体Gの溶液(固形分45質量%)62重量部(固形分28質量部)、(B)成分として、ポリエステル骨格を有するウレタン(メタ)アクリレート(新中村化学工業(株)製「U-200AX」)33質量部、及びポリプロピレングリコール骨格を有するウレタン(メタ)アクリレート(新中村化学工業(株)製「UA-4200」)15質量部、(F)成分として、ヘキサメチレンジイソシアネートのイソシアヌレート型三量体をメチルエチルケトンオキシムで保護した多官能ブロックイソシアネート溶液(固形分75質量%)(住化バイエルウレタン(株)製「スミジュールBL3175」)20質量部(固形分15質量部)、(C)成分の光重合開始剤として、1-[4-(2-ヒドロキシエトキシ)フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン(チバ・ジャパン(株)製「イルガキュア2959」)1質量部、ビス(2,4,6-トリメチルベンゾイル)フェニルホスフィンオキシド(チバ・ジャパン(株)製「イルガキュア819」)1質量部、及び希釈用有機溶剤としてプロピレングリコールモノメチルエーテルアセテート23質量部を攪拌しながら混合した。孔径2μmのポリフロンフィルタを用いて加圧濾過後、減圧脱泡し、クラッド層形成用樹脂ワニスW-Iを得た。 Production Example 1
As the 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 (solid content 15 parts by mass), as a photopolymerization initiator of component (C), 1 part by mass of [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one (“Irgacure 2959” manufactured by Ciba Japan KK), bis (2,4 1,6-trimethylbenzoyl) phenylphosphine oxide (“Irgacure 819” manufactured by Ciba Japan Co., Ltd.) and 23 parts by mass of propylene glycol monomethyl ether acetate as an organic solvent for dilution were mixed. After pressure filtration using a polyflon filter having a pore size of 2 μm, degassing was performed under reduced pressure to obtain a resin varnish WI for forming a cladding layer.
上記ワニスW-Iを、PETフィルム(東洋紡績(株)製「コスモシャインA4100」、厚み50μm)の非処理面上に、前記塗工機を用いて塗布し、100℃で20分乾燥後、カバーフィルムとして表面離型処理PETフィルム(帝人デュポンフィルム(株)製「ピューレックスA31」、厚み25μm)を貼付け、クラッド層形成用樹脂フィルムF-Iを得た。このとき樹脂層の厚みは、硬化後の膜厚が、下部クラッド層形成用樹脂フィルムでは20μm、及び上部クラッド層形成用樹脂フィルムでは60μmとなるように調節した。 Production Example 2
The varnish WI was applied on the non-treated surface of a PET film (“Cosmo Shine A4100” manufactured by Toyobo Co., Ltd.,
共重合体A 15重量部、共重合体Gの溶液33.3重量部(固形分15重量部)、2-メタクリロイロキシエチルコハク酸(共栄社化学(株)製「ライトエステルHO-MS」)10重量部、ポリエステル骨格を有するウレタン(メタ)アクリレート(新中村化学工業(株)製「U-108A」)20重量部、ビスフェノールAのEO付加物ジアクリレート(日立化成工業(株)製「ファンクリルFA-321A」)20重量部、及び多官能ブロックイソシアネート溶液(固形分75重量%)(住化バイエルウレタン(株)製「スミジュールBL3175」)20重量部(固形分15重量部)を配合し、更に1-[4-(2-ヒドロキシエトキシ)フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン(BASFジャパン(株)製;イルガキュア2959)1重量部と、ビス(2,4,6-トリメチルベンゾイル)フェニルホスフィンオキシド(BASFジャパン(株)製;イルガキュア819)1重量部、及びプロピレングリコールモノメチルエーテルアセテート19重量部を加え、攪拌しながら混合した。孔径2μmのポリフロンフィルタを用いて加圧濾過後、減圧脱泡し、コア部形成用樹脂ワニスW-IIを得た。 Production Example 3
15 parts by weight of copolymer A, 33.3 parts by weight of solution of copolymer G (15 parts by weight of solid content), 2-methacryloyloxyethyl succinic acid (“light ester HO-MS” manufactured by Kyoeisha Chemical Co., Ltd.) 10 parts by weight, 20 parts by weight of urethane (meth) acrylate having a polyester skeleton (“U-108A” manufactured by Shin-Nakamura Chemical Co., Ltd.), EO adduct diacrylate of bisphenol A (“fan” manufactured by Hitachi Chemical Co., Ltd.) 20 parts by weight of “Cryl FA-321A”) and 20 parts by weight of polyfunctional blocked isocyanate solution (solid content: 75% by weight) (“Sumijour BL3175” manufactured by Sumika Bayer Urethane Co., Ltd.) In addition, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one (BASF Japan ); 1 part by weight of Irgacure 2959), 1 part by weight of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by BASF Japan Ltd .; Irgacure 819), and 19 parts by weight of propylene glycol monomethyl ether acetate Add and mix with stirring. After pressure filtration using a polyfluorone filter having a pore size of 2 μm, degassing was performed under reduced pressure to obtain a resin varnish W-II for forming a core.
コア部形成用樹脂ワニスW-IIを、PETフィルム(東洋紡績(株)製「コスモシャインA1517」、厚み16μm)の非処理面上に、塗工機を用いて塗布し、80℃で10分、100℃で10分乾燥後、保護フィルムとして表面離型処理PETフィルム(帝人デュポンフィルム(株)製;ピューレックスA31、厚み25μm)を貼付け、コア部形成用樹脂フィルムF-IIを得た。このとき樹脂層の厚みは、硬化後の膜厚が50μmとなるように調節した。 Production Example 4
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 μm) 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 μm) 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 μm.
ロールラミネータを用い、保護フィルムを除去した下部クラッド層形成用樹脂フィルムF-Iを、PETフィルム(厚み50μm)上に、圧力0.5MPa、温度80℃の条件で積層した。さらに、真空加圧式ラミネータを用い、圧力0.4MPa、温度80℃の条件で圧着した。
次に、紫外線露光機を用い、紫外線(波長365nm)を2000mJ/cm2照射後、支持フィルムを除去した。その後、160℃で1時間加熱硬化することによって、下部クラッド層4を形成した。
続いて、ロールラミネータを用い、保護フィルムを除去した前記コア部形成用樹脂フィルムF-IIを、下部クラッド層4上に、圧力0.5MPa、温度80℃の条件で積層した。さらに、上記真空加圧式ラミネータを用い、圧力0.4MPa、温度80℃の条件で圧着した。
次いで、幅50μmのネガ型フォトマスクを介し、紫外線露光機で紫外線(波長365nm)を1000mJ/cm2で照射して、コア部2(コアパターン)を露光した。80℃で露光後加熱を行った後、支持フィルムを除去し、プロピレングリコールモノメチルエーテルアセテート/N,N-ジメチルアセトアミド(70/30質量比)を用いて現像した。続いて、プロピレングリコールモノメチルエーテルアセテートを用いて洗浄後、さらに2-プロパノールを用いて洗浄した。乾燥後、160℃で1時間加熱硬化した。
次に、真空加圧式ラミネータを用い、保護フィルムを除去した上部クラッド層形成用樹脂フィルムF-Iを、コア部2及び下部クラッド層4上に、圧力0.4MPa、温度100℃の条件で積層した。紫外線(波長365nm)を2000mJ/cm2で照射し、支持フィルムを除去した後、160℃で1時間加熱硬化することによって、上部クラッド層3を形成した。その後、表面離型処理PETフィルムを除去し、図1(d)に示す光導波路1を得た。その後、ダイシングソーを用いて長さ10cmのフレキシブル光導波路を切り出した。 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 (
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
Subsequently, the core part-forming resin film F-II, from which the protective film was removed, was laminated on the lower
Next, the core part 2 (core pattern) 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 μm. After exposure at 80 ° C. and heating, 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
得られたフレキシブル光導波路の光伝搬損失を、光源に波長850nmの光を中心波長とするVCSEL(EXFO社製「FLS-300-01-VCL」)、受光センサ((株)アドバンテスト製「Q82214」)、入射ファイバ(GI-50/125マルチモードファイバ、NA=0.20)、及び出射ファイバ(SI-114/125、NA=0.22)を用いて測定した。光伝搬損失は、光損失測定値(dB)を光導波路長(10cm)で割ることにより算出し、表8に示す基準で評価した。 [Optical propagation loss measurement]
The optical propagation loss of the obtained flexible optical waveguide is determined based on the VCSEL (“FLS-300-01-VCL” manufactured by EXFO) whose light source is the light having a wavelength of 850 nm as a light source, and the light receiving sensor (“Q82214” manufactured by Advantest Corporation). ), An input fiber (GI-50 / 125 multimode fiber, NA = 0.20), and an output fiber (SI-114 / 125, NA = 0.22). The optical propagation loss was calculated by dividing the optical loss measurement value (dB) by the optical waveguide length (10 cm), and evaluated based on the criteria shown in Table 8.
得られたフレキシブル光導波路を、高温高湿試験機(エスペック(株)製「PL-2KT」)を用いて、JPCA規格(JPCA-PE02-05-01S)に準じた条件で温度85℃、湿度85%の高温高湿放置試験を1000時間実施した。
高温高湿放置試験実施後の光導波路の光伝搬損失を、前記と同様の光源、受光素子、入射ファイバ、及び出射ファイバを用いて測定し、表8に示す基準で評価した。 [High temperature and high humidity test]
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.
得られたフレキシブル光導波路を、温度サイクル試験機(楠本化成(株)製「ETAC WINTECH NT1010」)を用いて、JPCA規格(JPCA-PE02-05-01S)に準じた条件で温度-55℃と125℃の間の温度サイクル試験を1000サイクル実施した。詳細な温度サイクル試験条件を表6に示す。 [Temperature cycle test]
Using the temperature cycle tester (“ETAC WINTECH NT1010” manufactured by Enomoto Kasei Co., Ltd.), the obtained flexible optical waveguide was heated to −55 ° C. under the conditions in accordance with the JPCA standard (JPCA-PE02-05-01S). The temperature cycle test between 125 ° C. was performed 1000 cycles. Detailed temperature cycle test conditions are shown in Table 6.
得られたフレキシブル光導波路を、リフロー試験機(古河電気工業(株)製「サラマンダXNA-645PC」)を用いて、IPC/JEDEC J-STD-020Bに準じた条件で最高温度265℃のリフロー試験を窒素雰囲気下で3回実施した。詳細なリフロー条件を表7に示し、リフロー炉内の温度プロファイルを図2に示す。 [Reflow test]
The obtained flexible optical waveguide is subjected to a reflow test at a maximum temperature of 265 ° C. under a condition according to IPC / JEDEC J-STD-020B using a reflow test machine (“Salamanda XNA-645PC” manufactured by Furukawa Electric Co., Ltd.). Was carried out three times under a nitrogen atmosphere. Detailed reflow conditions are shown in Table 7, and the temperature profile in the reflow furnace is shown in FIG.
Claims (26)
- ジビニル芳香族化合物(a)単位及びモノビニル芳香族化合物(b)単位と、下記式(2)及び下記式(3)で表される末端基を有する共重合体であって、溶剤可溶性で、重合性を有することを特徴とする末端変性可溶性多官能ビニル芳香族共重合体。
(ここで、R1は炭素数1~18の炭化水素基又は水素を示し、R2~R3は炭素数1~18の炭化水素基を示し、R4は水素又はメチル基を示す。) 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), which is soluble in a solvent and polymerized A terminal-modified soluble polyfunctional vinyl aromatic copolymer characterized by having properties.
(Here, 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, and R 4 represents hydrogen or a methyl group.) - ジビニル芳香族化合物(a)単位が、ビニル基を有しない構造単位と、ビニル基を1つ有する構造単位を含むものである請求項1に記載の末端変性可溶性多官能ビニル芳香族共重合体。 The terminal-modified soluble polyfunctional vinyl aromatic copolymer according to claim 1, wherein the divinyl aromatic compound (a) unit comprises a structural unit having no vinyl group and a structural unit having one vinyl group.
- 数平均分子量(Mn)が300~100,000で、分子量分布(Mw/Mn)が100.0以下である請求項1に記載の末端変性可溶性多官能ビニル芳香族共重合体。 The terminal-modified soluble polyfunctional vinyl aromatic copolymer according to claim 1, having a number average molecular weight (Mn) of 300 to 100,000 and a molecular weight distribution (Mw / Mn) of 100.0 or less.
- 上記式(3)で表される末端基の導入量(c1)が下記式(4)
(c1)≧1.0(個/分子) (4)
を満足し、共重合体中のジビニル芳香族化合物由来の構造単位のモル分率(a)及びモノビニル芳香族化合物由来の構造単位のモル分率(b)が下記式(5)
0.05≦(a)/{(a)+(b)}≦0.95 (5)
を満足し、上記式(1)及び式(2)で表される末端基のモル分率(c)が下記式(6)
0.005≦(c)/{(a)+(b)}<2.0 (6)
を満足し、かつ、トルエン、キシレン、テトラヒドロフラン、ジクロロエタン又はクロロホルムに可溶である請求項1~3のいずれかに記載の末端変性可溶性多官能ビニル芳香族共重合体。 The introduction amount (c1) of the terminal group represented by the above formula (3) is the following formula (4)
(C1) ≧ 1.0 (pieces / molecule) (4)
And 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)
And 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 terminal-modified soluble polyfunctional vinyl aromatic copolymer according to any one of claims 1 to 3, which satisfies the following conditions and is soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. - ジビニル芳香族化合物(a)及びモノビニル芳香族化合物(b)と、下記式(1)で表される(メタ)アクリル酸エステル系化合物(c)を、ルイス酸触媒、無機強酸及び有機スルホン酸からなる群から選ばれる一種以上の触媒(d)の存在下で、重合させることを特徴とする請求項1に記載の末端変性可溶性多官能ビニル芳香族共重合体の製造方法。
(ここで、R1は炭素数1~18の炭化水素基又は水素を示し、R2~R3は炭素数1~18の炭化水素基を示し、R4は水素又はメチル基を示す。) A divinyl aromatic compound (a) and a monovinyl aromatic compound (b) and a (meth) acrylic acid ester compound (c) represented by the following formula (1) are prepared from a Lewis acid catalyst, an inorganic strong acid and an organic sulfonic acid. The method for producing a terminal-modified soluble polyfunctional vinyl aromatic copolymer according to claim 1, wherein the polymerization is carried out in the presence of at least one catalyst (d) selected from the group consisting of:
(Here, 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, and R 4 represents hydrogen or a methyl group.) - ジビニル芳香族化合物(a)とモノビニル芳香族化合物(b)の合計100モル%に対し、ジビニル芳香族化合物(a)5~95モル%、モノビニル芳香族化合物(b)95~5モル%、更に上記式(1)で表わされる(メタ)アクリル酸エステル系化合物(c)を全単量体100モルに対し0.5~500モル、触媒(d)を(メタ)アクリル酸エステル系化合物(c)1モルに対し0.001~10モル、それぞれ使用し、これらを含む重合原料を誘電率2.0~15.0の均一溶媒中で重合させる請求項5に記載の末端変性可溶性多官能ビニル芳香族共重合体の製造方法。 Divinyl aromatic compound (a) 5 to 95 mol%, monovinyl aromatic compound (b) 95 to 5 mol%, based on 100 mol% of the total of divinyl aromatic compound (a) and monovinyl aromatic compound (b), The (meth) acrylic acid ester compound (c) represented by the above formula (1) is 0.5 to 500 mol with respect to 100 mol of all monomers, and the catalyst (d) is a (meth) acrylic acid ester compound (c 6. The terminal-modified soluble polyfunctional vinyl according to claim 5, wherein 0.001 to 10 mol is used per 1 mol, and a polymerization raw material containing these is polymerized in a homogeneous solvent having a dielectric constant of 2.0 to 15.0. A method for producing an aromatic copolymer.
- 請求項1に記載の末端変性可溶性多官能ビニル芳香族共重合体と、ラジカル重合開始剤とを含有することを特徴とする硬化性組成物。 A curable composition comprising the terminal-modified soluble polyfunctional vinyl aromatic copolymer according to claim 1 and a radical polymerization initiator.
- 更に変性ポリフェニレンエーテル(XC)を含有することを特徴とする請求項7に記載の硬化性組成物。 Furthermore, modified | denatured polyphenylene ether (XC) is contained, The curable composition of Claim 7 characterized by the above-mentioned.
- 更に、1分子中に2以上のエポキシ基と芳香族構造を有するエポキシ樹脂、1分子中に2以上のエポキシ基とシアヌレート構造を有するエポキシ樹脂及び/又は1分子中に2以上のエポキシ基と脂環構造を有するエポキシ樹脂からなる群から選ばれる1種以上のエポキシ樹脂(XD)及び硬化剤(XE)を含有することを特徴とする請求項7又は8に記載の硬化性樹脂組成物。 Further, 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 epoxy groups and a fat in one molecule. The curable resin composition according to claim 7 or 8, comprising at least one epoxy resin (XD) selected from the group consisting of epoxy resins having a ring structure and a curing agent (XE).
- 請求項7~9のいずれかに記載の硬化性組成物を硬化してなる硬化物。 A cured product obtained by curing the curable composition according to any one of claims 7 to 9.
- 請求項7~9のいずれかに記載の硬化性組成物をフィルム状に成形してなるフィルム。 A film obtained by forming the curable composition according to any one of claims 7 to 9 into a film shape.
- 請求項7~9のいずれかに記載の硬化性組成物と基材からなる硬化性複合材料であって、基材を5~90重量%の割合で含有することを特徴とする硬化性複合材料。 A curable composite material comprising the curable composition according to any one of claims 7 to 9 and a base material, wherein the base material is contained in a proportion of 5 to 90% by weight. .
- 請求項12に記載の硬化性複合材料を硬化して得られたことを特徴とする硬化複合材料。 A cured composite material obtained by curing the curable composite material according to claim 12.
- 請求項12に記載の硬化複合材料の層と金属箔層とを有することを特徴とする積層体。 A laminate comprising the cured composite material layer according to claim 12 and a metal foil layer.
- 請求項7~9のいずれかに記載の硬化性組成物から形成された膜を金属箔の片面に有することを特徴とする樹脂付き金属箔。 A metal foil with a resin, comprising a film formed from the curable composition according to any one of claims 7 to 9 on one side of the metal foil.
- 請求項7~9のいずれかに記載の硬化性組成物を有機溶剤に溶解させてなる回路基板材料用ワニス。 A circuit board material varnish obtained by dissolving the curable composition according to any one of claims 7 to 9 in an organic solvent.
- (A)成分:ジビニル芳香族化合物(a)単位及びモノビニル芳香族化合物(b)単位と、下記式(2)及び下記式(3)で表される末端基を有する共重合体であって、溶剤可溶性で、重合性を有する末端変性可溶性多官能ビニル芳香族共重合体、
(ここで、R1は炭素数1~18の炭化水素基又は水素を示し、R2~R3は炭素数1~18の炭化水素基を示し、R4は水素又はメチル基を示す。)
(B)成分:分子中に1個以上の不飽和基を有する1種以上のビニル化合物、及び
(C)成分:ラジカル重合開始剤を含有し、
(A)成分の配合量が5~94.9wt%、(B)成分の配合量が5.0~85wt%、及び(C)成分の配合量が0.1~10wt%であることを特徴とする硬化性樹脂組成物。 (A) component: 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), Solvent-soluble, polymerizable terminal-modified soluble polyfunctional vinyl aromatic copolymer,
(Here, 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, and R 4 represents hydrogen or a methyl group.)
(B) component: one or more vinyl compounds having one or more unsaturated groups in the molecule, and (C) component: a radical polymerization initiator,
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%, and the blending amount of the component (C) is 0.1 to 10 wt%. A curable resin composition. - (B)成分が、分子中に1個以上の(メタ)アクリロイル基を有する1種以上の(メタ)アクリレートを含有することを特徴とする請求項17に記載の硬化性樹脂組成物。 The curable resin composition according to claim 17, wherein the component (B) contains one or more (meth) acrylates having one or more (meth) acryloyl groups in the molecule.
- (B)成分が、分子中に水酸基及び/又はカルボキシル基を有する(メタ)アクリレートを含有することを特徴とする請求項17に記載の硬化性樹脂組成物。 The curable resin composition according to claim 17, wherein the component (B) contains a (meth) acrylate having a hydroxyl group and / or a carboxyl group in the molecule.
- 請求項17に記載の硬化性樹脂組成物が、光導波路形成用であることを特徴とする光導波路形成用の硬化性樹脂組成物。 A curable resin composition for forming an optical waveguide, wherein the curable resin composition according to claim 17 is used for forming an optical waveguide.
- (C)成分が、光ラジカル重合開始剤を含むことを特徴とする請求項17に記載の硬化性樹脂組成物。 The curable resin composition according to claim 17, wherein the component (C) contains a radical photopolymerization initiator.
- (B)成分が、下記一般式(16)又は(17)で表される構造単位を有するビニル化合物、又はこのビニル化合物から生じる硬化型ビニル系ポリマーを含むことを特徴とする請求項17に記載の硬化性樹脂組成物。
(式中、R5は水素原子又はメチル基を示し、X1は単結合、又はエステル結合、エーテル結合、チオエステル結合、チオエーテル結合及びアミド結合からなる群から選ばれる1種以上の結合を含有していてもよい炭素数1~20の2価の有機基を示す。R6は水素原子又は炭素数1~20の1価の有機基を示す。)
(式中、R7は水素原子又は炭素数1~20の1価の有機基を示し、R8は水素原子又はメチル基を示し、X2は単結合、又はエステル結合、エーテル結合、チオエステル結合、チオエーテル結合及びアミド結合からなる群から選ばれる1種以上の結合を含有していてもよい炭素数1~20の2価の有機基を示す。R9は水素原子又は炭素数1~20の1価の有機基を示す。) The component (B) contains a vinyl compound having a structural unit represented by the following general formula (16) or (17), or a curable vinyl polymer produced from the vinyl compound. Curable resin composition.
(In the formula, R 5 represents a hydrogen atom or a methyl group, and X 1 contains a single bond or one or more bonds selected from the group consisting of an ester bond, an ether bond, a thioester bond, a thioether bond, and an amide bond. And optionally represents a divalent organic group having 1 to 20 carbon atoms, and R 6 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.)
(Wherein R 7 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, R 8 represents a hydrogen atom or a methyl group, and X 2 represents a single bond, an ester bond, an ether bond or a thioester bond. And a divalent organic group having 1 to 20 carbon atoms which may contain one or more bonds selected from the group consisting of a thioether bond and an amide bond, R 9 represents a hydrogen atom or a carbon atom having 1 to 20 carbon atoms. Represents a monovalent organic group.) - 請求項17~22のいずれかに記載の硬化性樹脂組成物を用いて形成される光導波路形成用樹脂フィルム。 An optical waveguide forming resin film formed using the curable resin composition according to any one of claims 17 to 22.
- 請求項17~22のいずれかに記載の硬化性樹脂組成物を用いて形成されるコア部及び/又はクラッド層を有する光導波路。 An optical waveguide having a core part and / or a clad layer formed using the curable resin composition according to any one of claims 17 to 22.
- 請求項23に記載の光導波路形成用樹脂フィルムを用いて形成されるコア部及び/又はクラッド層を有する光導波路。 An optical waveguide having a core part and / or a clad layer formed using the resin film for forming an optical waveguide according to claim 23.
- 波長850nmの光源における光伝搬損失が0.3dB/cm以下である請求項24又は25に記載の光導波路。 The optical waveguide according to claim 24 or 25, wherein a light propagation loss in a light source having a wavelength of 850 nm is 0.3 dB / cm or less.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016566542A JP6634029B2 (en) | 2014-12-26 | 2015-12-25 | Terminal-modified soluble polyfunctional vinyl aromatic copolymer, curable resin composition, and optical waveguide using the same |
KR1020177019810A KR102498471B1 (en) | 2014-12-26 | 2015-12-25 | Terminal-modified soluble polyfunctional vinyl aromatic copolymer, and curable resin composition and optical waveguide produced using same |
CN201580070594.6A CN107108782B (en) | 2014-12-26 | 2015-12-25 | Terminal-modified soluble polyfunctional vinyl aromatic co-polymer and its application |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-266419 | 2014-12-26 | ||
JP2014266419 | 2014-12-26 | ||
JP2015-159320 | 2015-08-12 | ||
JP2015159320 | 2015-08-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016104748A1 true WO2016104748A1 (en) | 2016-06-30 |
Family
ID=56150760
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/086343 WO2016104748A1 (en) | 2014-12-26 | 2015-12-25 | Terminal-modified soluble polyfunctional vinyl aromatic copolymer, and curable resin composition and optical waveguide produced using same |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP6634029B2 (en) |
KR (1) | KR102498471B1 (en) |
CN (1) | CN107108782B (en) |
TW (1) | TWI664199B (en) |
WO (1) | WO2016104748A1 (en) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018030113A1 (en) * | 2016-08-10 | 2018-02-15 | パナソニックIpマネジメント株式会社 | Acrylic composition for sealing, sheet material, multilayer sheet, cured product, semiconductor device and method for manufacturing semiconductor device |
WO2018061736A1 (en) * | 2016-09-27 | 2018-04-05 | パナソニックIpマネジメント株式会社 | Metal-clad laminate, printed wiring board and metal foil with resin |
WO2018084128A1 (en) * | 2016-11-01 | 2018-05-11 | 新日鉄住金化学株式会社 | Copolymer rubber and method for producing same, and crosslinked rubber composition |
CN108445714A (en) * | 2017-02-16 | 2018-08-24 | 住友化学株式会社 | Hardening resin composition, cured film and display device |
TWI665247B (en) * | 2017-08-04 | 2019-07-11 | 大陸商廣東生益科技股份有限公司 | Thermosetting resin composition and prepreg and metal foil-clad laminate produced by using same |
WO2019208471A1 (en) * | 2018-04-27 | 2019-10-31 | パナソニックIpマネジメント株式会社 | Resin composition, prepreg, resin-added film, resin-added metal foil, metal-clad layered plate, and wiring plate |
JP2019194307A (en) * | 2018-04-27 | 2019-11-07 | パナソニックIpマネジメント株式会社 | Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and wiring board |
WO2020017399A1 (en) * | 2018-07-19 | 2020-01-23 | パナソニックIpマネジメント株式会社 | Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate and wiring board |
JPWO2020203320A1 (en) * | 2019-03-29 | 2020-10-08 | ||
WO2021024924A1 (en) * | 2019-08-07 | 2021-02-11 | パナソニックIpマネジメント株式会社 | Resin composition, prepreg, resin-equipped film, resin-equipped metal foil, metal-cladded layered sheet, and wiring board |
WO2021040364A1 (en) * | 2019-08-26 | 2021-03-04 | 엘지이노텍 주식회사 | Circuit board |
WO2021079819A1 (en) * | 2019-10-25 | 2021-04-29 | パナソニックIpマネジメント株式会社 | Copper-clad laminate, wiring board, and copper foil with resin |
JPWO2020166288A1 (en) * | 2019-02-12 | 2021-12-16 | ナミックス株式会社 | A photocurable resin composition and a cured product obtained by curing the photocurable resin composition. |
CN114423602A (en) * | 2019-09-27 | 2022-04-29 | 松下知识产权经营株式会社 | Resin composition, prepreg, film with resin, metal foil with resin, metal-foil-clad laminate, and wiring board |
WO2022172759A1 (en) * | 2021-02-10 | 2022-08-18 | 三井金属鉱業株式会社 | Resin composition, copper foil with resin, and printed wiring board |
WO2023224746A1 (en) * | 2022-05-18 | 2023-11-23 | Canon Kabushiki Kaisha | Photocurable composition |
JP7507382B2 (en) | 2019-03-29 | 2024-06-28 | パナソニックIpマネジメント株式会社 | Resin composition, and prepreg, resin-coated film, resin-coated metal foil, metal-clad laminate, and wiring board using the same |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI751266B (en) * | 2017-03-24 | 2022-01-01 | 日商迪愛生股份有限公司 | Active ester composition |
JP7126493B2 (en) * | 2017-03-30 | 2022-08-26 | 日鉄ケミカル&マテリアル株式会社 | Soluble polyfunctional vinyl aromatic copolymer, production method thereof, curable resin composition and cured product thereof |
CN109385018A (en) * | 2017-08-04 | 2019-02-26 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin and prepreg and metal-clad laminate using its production |
JP2019178233A (en) * | 2018-03-30 | 2019-10-17 | 日鉄ケミカル&マテリアル株式会社 | Low dielectric fire retardant composition containing phosphorus-containing vinyl resin |
CN110045470B (en) * | 2019-04-08 | 2020-08-07 | 安徽长荣光纤光缆科技有限公司 | Preparation method of pressure-resistant and corrosion-resistant outdoor optical cable |
JP7338413B2 (en) * | 2019-11-11 | 2023-09-05 | 味の素株式会社 | resin composition |
TWI832318B (en) * | 2022-07-07 | 2024-02-11 | 台光電子材料股份有限公司 | Resin compositions and products thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002506478A (en) * | 1997-06-26 | 2002-02-26 | ザ ダウ ケミカル カンパニー | Improved acid-catalyzed polymerization method |
JP2006089641A (en) * | 2004-09-24 | 2006-04-06 | Fuji Xerox Co Ltd | Polymer, method for producing the same, and affinity molecule fixing material |
WO2009110453A1 (en) * | 2008-03-04 | 2009-09-11 | 新日鐵化学株式会社 | Polyfunctional vinyl aromatic copolymer, process for producing the same, and resin composition |
WO2014156778A1 (en) * | 2013-03-28 | 2014-10-02 | 新日鉄住金化学株式会社 | Curable resin composition, method for molding same, and molded article of same |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4338951B2 (en) | 2002-10-01 | 2009-10-07 | 新日鐵化学株式会社 | Soluble polyfunctional vinyl aromatic copolymer and polymerization method thereof |
CN1914239B (en) | 2004-01-30 | 2010-05-05 | 新日铁化学株式会社 | Curable resin composition |
JP4717358B2 (en) | 2004-01-30 | 2011-07-06 | 新日鐵化学株式会社 | Method for producing soluble polyfunctional vinyl aromatic polymer |
JP4547212B2 (en) | 2004-09-01 | 2010-09-22 | 太陽インキ製造株式会社 | Photocurable / thermosetting dry film and optical / electrical hybrid substrate |
JP4894995B2 (en) | 2004-10-21 | 2012-03-14 | Jsr株式会社 | Photosensitive resin composition for optical waveguide, optical waveguide and method for producing the same |
JP2006274169A (en) | 2005-03-30 | 2006-10-12 | Nippon Steel Chem Co Ltd | Curable resin composition |
JP4840586B2 (en) | 2005-09-29 | 2011-12-21 | Jsr株式会社 | Photosensitive resin composition for optical waveguide, optical waveguide and method for producing the same |
JP4842024B2 (en) | 2006-06-15 | 2011-12-21 | 新日鐵化学株式会社 | Soluble polyfunctional vinyl aromatic copolymer and method for producing the same |
JP4518089B2 (en) | 2006-07-05 | 2010-08-04 | Jsr株式会社 | Photosensitive resin composition for optical waveguide, dry film, optical waveguide and method for producing the same |
CN102718914B (en) * | 2007-03-26 | 2015-04-22 | 新日铁住金化学株式会社 | Soluble polyfunctional vinyl aromatic copolymer, and method for production thereof |
TWI491623B (en) * | 2007-03-26 | 2015-07-11 | Nippon Steel & Sumikin Chem Co | Soluble polyfunctional vinyl aromatic copolymer and method for producing the same |
JP5249095B2 (en) | 2009-03-12 | 2013-07-31 | 新日鉄住金化学株式会社 | Terminal-modified soluble polyfunctional vinyl aromatic copolymer, process for producing the same, curable resin composition, and cured product |
JP5443806B2 (en) | 2009-03-26 | 2014-03-19 | 新日鉄住金化学株式会社 | Terminal-modified soluble polyfunctional vinyl aromatic copolymer, curable resin composition, and cured product |
TWI605066B (en) * | 2010-03-29 | 2017-11-11 | Nippon Steel & Sumikin Chem Co | Soluble polyfunctional (meth) acrylate copolymer, its manufacturing method, curable resin composition, and hardened | cured material |
TWI529182B (en) * | 2011-03-07 | 2016-04-11 | Nippon Steel & Sumikin Chem Co | Acluble polyfunctional (meth) acrylate copolymer having an alicyclic structure, a hardened resin composition and a hardened product |
CN103917594B (en) * | 2011-11-07 | 2016-05-11 | 新日铁住金化学株式会社 | The manufacture method of the styrene resin composite that contains high branching type Superhigh Molecular Polymer and composition thereof |
JP5841835B2 (en) * | 2011-12-26 | 2016-01-13 | 新日鉄住金化学株式会社 | Curable resin composition, cured product and optical article |
-
2015
- 2015-12-25 WO PCT/JP2015/086343 patent/WO2016104748A1/en active Application Filing
- 2015-12-25 TW TW104143682A patent/TWI664199B/en active
- 2015-12-25 KR KR1020177019810A patent/KR102498471B1/en active IP Right Grant
- 2015-12-25 CN CN201580070594.6A patent/CN107108782B/en active Active
- 2015-12-25 JP JP2016566542A patent/JP6634029B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002506478A (en) * | 1997-06-26 | 2002-02-26 | ザ ダウ ケミカル カンパニー | Improved acid-catalyzed polymerization method |
JP2006089641A (en) * | 2004-09-24 | 2006-04-06 | Fuji Xerox Co Ltd | Polymer, method for producing the same, and affinity molecule fixing material |
WO2009110453A1 (en) * | 2008-03-04 | 2009-09-11 | 新日鐵化学株式会社 | Polyfunctional vinyl aromatic copolymer, process for producing the same, and resin composition |
WO2014156778A1 (en) * | 2013-03-28 | 2014-10-02 | 新日鉄住金化学株式会社 | Curable resin composition, method for molding same, and molded article of same |
Cited By (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20190039104A (en) * | 2016-08-10 | 2019-04-10 | 파나소닉 아이피 매니지먼트 가부시키가이샤 | Patent application title: Acrylic composition for sealing, sheet material, laminated sheet, cured product, semiconductor device, and manufacturing method of semiconductor device |
JP2018029176A (en) * | 2016-08-10 | 2018-02-22 | パナソニックIpマネジメント株式会社 | Acrylic composition for sealing, sheet material, multilayer sheet, cured product, semiconductor device and method for manufacturing semiconductor device |
KR102321555B1 (en) | 2016-08-10 | 2021-11-03 | 파나소닉 아이피 매니지먼트 가부시키가이샤 | Acrylic composition for sealing, sheet material, laminated sheet, hardened|cured material, semiconductor device, and manufacturing method of a semiconductor device |
WO2018030113A1 (en) * | 2016-08-10 | 2018-02-15 | パナソニックIpマネジメント株式会社 | Acrylic composition for sealing, sheet material, multilayer sheet, cured product, semiconductor device and method for manufacturing semiconductor device |
WO2018061736A1 (en) * | 2016-09-27 | 2018-04-05 | パナソニックIpマネジメント株式会社 | Metal-clad laminate, printed wiring board and metal foil with resin |
WO2018084128A1 (en) * | 2016-11-01 | 2018-05-11 | 新日鉄住金化学株式会社 | Copolymer rubber and method for producing same, and crosslinked rubber composition |
JPWO2018084128A1 (en) * | 2016-11-01 | 2019-09-26 | 日鉄ケミカル&マテリアル株式会社 | Copolymer rubber, method for producing the same, and crosslinked rubber composition |
JP7079204B2 (en) | 2016-11-01 | 2022-06-01 | 日鉄ケミカル&マテリアル株式会社 | Copolymer rubber and its production method, and crosslinked rubber composition |
CN108445714A (en) * | 2017-02-16 | 2018-08-24 | 住友化学株式会社 | Hardening resin composition, cured film and display device |
CN108445714B (en) * | 2017-02-16 | 2022-12-09 | 住友化学株式会社 | Curable resin composition, cured film, and display device |
TWI665247B (en) * | 2017-08-04 | 2019-07-11 | 大陸商廣東生益科技股份有限公司 | Thermosetting resin composition and prepreg and metal foil-clad laminate produced by using same |
US11390735B2 (en) | 2017-08-04 | 2022-07-19 | Shengyi Technology Co., Ltd. | Thermosetting resin composition and prepreg and metal foil-covered laminate made using same |
EP3663352A4 (en) * | 2017-08-04 | 2021-04-28 | Shengyi Technology Co., Ltd. | Thermosetting resin composition and prepreg and metal foil-covered laminate made using same |
WO2019208471A1 (en) * | 2018-04-27 | 2019-10-31 | パナソニックIpマネジメント株式会社 | Resin composition, prepreg, resin-added film, resin-added metal foil, metal-clad layered plate, and wiring plate |
JP7145441B2 (en) | 2018-04-27 | 2022-10-03 | パナソニックIpマネジメント株式会社 | Resin composition, prepreg, resin-coated film, resin-coated metal foil, metal-clad laminate, and wiring board |
JP7190649B2 (en) | 2018-04-27 | 2022-12-16 | パナソニックIpマネジメント株式会社 | Resin composition, prepreg, resin-coated film, resin-coated metal foil, metal-clad laminate, and wiring board |
JP2019194307A (en) * | 2018-04-27 | 2019-11-07 | パナソニックIpマネジメント株式会社 | Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and wiring board |
JPWO2019208471A1 (en) * | 2018-04-27 | 2021-07-01 | パナソニックIpマネジメント株式会社 | Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and wiring board |
JPWO2020017399A1 (en) * | 2018-07-19 | 2021-08-19 | パナソニックIpマネジメント株式会社 | Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and wiring board |
US12024590B2 (en) | 2018-07-19 | 2024-07-02 | Panasonic Intellectual Property Management Co., Ltd. | Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and wiring board |
JP7378090B2 (en) | 2018-07-19 | 2023-11-13 | パナソニックIpマネジメント株式会社 | Resin compositions, prepregs, resin-coated films, resin-coated metal foils, metal-clad laminates, and wiring boards |
CN112368311B (en) * | 2018-07-19 | 2023-11-03 | 松下知识产权经营株式会社 | Resin composition, prepreg, resin-coated film, resin-coated metal foil, metal foil-clad laminate, and wiring board |
US20210269595A1 (en) * | 2018-07-19 | 2021-09-02 | Panasonic Intellectual Property Management Co., Ltd. | Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and wiring board |
WO2020017399A1 (en) * | 2018-07-19 | 2020-01-23 | パナソニックIpマネジメント株式会社 | Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate and wiring board |
CN112368311A (en) * | 2018-07-19 | 2021-02-12 | 松下知识产权经营株式会社 | Resin composition, prepreg, film with resin, metal foil with resin, metal-foil-clad laminate, and wiring board |
JPWO2020166288A1 (en) * | 2019-02-12 | 2021-12-16 | ナミックス株式会社 | A photocurable resin composition and a cured product obtained by curing the photocurable resin composition. |
JP7401917B2 (en) | 2019-02-12 | 2023-12-20 | ナミックス株式会社 | Photocurable resin composition and cured product obtained by curing it |
EP3925993A4 (en) * | 2019-02-12 | 2022-11-09 | Namics Corporation | Photocurable resin composition and cured product obtained by curing same |
JPWO2020203320A1 (en) * | 2019-03-29 | 2020-10-08 | ||
JP7507382B2 (en) | 2019-03-29 | 2024-06-28 | パナソニックIpマネジメント株式会社 | Resin composition, and prepreg, resin-coated film, resin-coated metal foil, metal-clad laminate, and wiring board using the same |
WO2021024924A1 (en) * | 2019-08-07 | 2021-02-11 | パナソニックIpマネジメント株式会社 | Resin composition, prepreg, resin-equipped film, resin-equipped metal foil, metal-cladded layered sheet, and wiring board |
CN114174433A (en) * | 2019-08-07 | 2022-03-11 | 松下知识产权经营株式会社 | Resin composition, prepreg, film with resin, metal foil with resin, metal-foil-clad laminate, and wiring board |
WO2021040364A1 (en) * | 2019-08-26 | 2021-03-04 | 엘지이노텍 주식회사 | Circuit board |
CN114423602A (en) * | 2019-09-27 | 2022-04-29 | 松下知识产权经营株式会社 | Resin composition, prepreg, film with resin, metal foil with resin, metal-foil-clad laminate, and wiring board |
CN114555360A (en) * | 2019-10-25 | 2022-05-27 | 松下知识产权经营株式会社 | Copper-clad laminate, wiring board, and resin-attached copper foil |
WO2021079819A1 (en) * | 2019-10-25 | 2021-04-29 | パナソニックIpマネジメント株式会社 | Copper-clad laminate, wiring board, and copper foil with resin |
WO2022172759A1 (en) * | 2021-02-10 | 2022-08-18 | 三井金属鉱業株式会社 | Resin composition, copper foil with resin, and printed wiring board |
WO2023224746A1 (en) * | 2022-05-18 | 2023-11-23 | Canon Kabushiki Kaisha | Photocurable composition |
US11981759B2 (en) | 2022-05-18 | 2024-05-14 | Canon Kabushiki Kaisha | Photocurable composition |
Also Published As
Publication number | Publication date |
---|---|
JP6634029B2 (en) | 2020-01-22 |
TWI664199B (en) | 2019-07-01 |
KR102498471B1 (en) | 2023-02-10 |
TW201625703A (en) | 2016-07-16 |
CN107108782A (en) | 2017-08-29 |
JPWO2016104748A1 (en) | 2017-10-05 |
KR20170099952A (en) | 2017-09-01 |
CN107108782B (en) | 2019-12-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6634029B2 (en) | Terminal-modified soluble polyfunctional vinyl aromatic copolymer, curable resin composition, and optical waveguide using the same | |
JP2018039995A (en) | Soluble polyfunctional vinyl aromatic copolymer, method for producing the same, curable resin composition, and cured product of the same | |
JP6580849B2 (en) | Terminal-modified soluble polyfunctional vinyl aromatic copolymer and process for producing the same | |
TW201936774A (en) | Resin composition for multilayer electronic components, dry film, cured product, multilayer electronic component, and printed wiring board | |
JP2011027903A (en) | Resin composition for forming clad layer, optical waveguide and optical module | |
WO2007105795A1 (en) | Phenoxy resin for optical material, resin composition for optical material, resin film for optical material, and optical waveguide using those | |
WO2017115813A1 (en) | Soluble polyfunctional vinyl aromatic copolymer, method for producing same and curable composition | |
JP5892066B2 (en) | Optical waveguide forming resin composition, optical waveguide forming resin film using the same, and optical waveguide using the same | |
JP2009300688A (en) | Resin composition for forming cladding layer, resin film for forming cladding layer using the same, and optical waveguide and optical module using these | |
JP5387370B2 (en) | Optical waveguide forming resin composition, optical waveguide forming resin film using the same, and optical waveguide using the same | |
JP5526740B2 (en) | Optical waveguide forming resin composition, optical waveguide forming resin film using the same, and optical waveguide using the same | |
JP6705412B2 (en) | Photosensitive resin composition | |
JP5771978B2 (en) | Optical waveguide forming resin composition, optical waveguide forming resin film using the same, and optical waveguide using the same | |
JP2010091734A (en) | Resin composition for forming core part and resin film for forming core part using the same, and optical waveguide using these | |
JP5115135B2 (en) | Curable resin composition and cured product | |
JP5630145B2 (en) | Optical waveguide forming resin composition, optical waveguide forming resin film using the same, and optical waveguide using the same | |
JP2017187654A (en) | Method for manufacturing optical waveguide | |
JP2015145999A (en) | Resin composition for optical waveguide formation, resin film for optical waveguide formation, optical waveguide using the resin composition and the resin film, and method for manufacturing the same | |
JP5904362B2 (en) | Resin composition for optical material, resin film for optical material, and optical waveguide | |
KR20240062117A (en) | Photoresist resin composition | |
JP2015146000A (en) | Resin composition for optical waveguide formation, resin film for optical waveguide formation, and optical waveguide using the resin composition and the resin film | |
JP2018048277A (en) | Resin composition for optical material, resin film for optical material using the same, and optical waveguide and production method of the optical waveguide | |
JP2017138495A (en) | Method for producing optical waveguide using photosensitive resin composition | |
KR20230150741A (en) | Photosensitive resin composition | |
WO2017022055A1 (en) | Optical waveguide forming resin composition, optical waveguide forming resin film, and optical waveguide using these, and method for producing same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15873316 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016566542 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20177019810 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15873316 Country of ref document: EP Kind code of ref document: A1 |