WO2013187185A1 - Résine de polyhydroxypolyéther, procédé de fabrication de résine de polyhydroxypolyéther, composition de résine contenant de la résine de polyhydroxypolyéther et produit durci obtenu à partir de celle-ci - Google Patents

Résine de polyhydroxypolyéther, procédé de fabrication de résine de polyhydroxypolyéther, composition de résine contenant de la résine de polyhydroxypolyéther et produit durci obtenu à partir de celle-ci Download PDF

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Publication number
WO2013187185A1
WO2013187185A1 PCT/JP2013/063866 JP2013063866W WO2013187185A1 WO 2013187185 A1 WO2013187185 A1 WO 2013187185A1 JP 2013063866 W JP2013063866 W JP 2013063866W WO 2013187185 A1 WO2013187185 A1 WO 2013187185A1
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group
resin
polyhydroxy polyether
resin composition
epoxy resin
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PCT/JP2013/063866
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English (en)
Japanese (ja)
Inventor
雅男 軍司
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新日鉄住金化学株式会社
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Priority to JP2014521222A priority Critical patent/JP6183918B2/ja
Publication of WO2013187185A1 publication Critical patent/WO2013187185A1/fr

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    • 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
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • 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
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/02—Polyglycidyl ethers of bis-phenols
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive

Definitions

  • the present invention is used as an anisotropic conductive adhesive film, an electrical laminate, a magnetic tape binder, an insulating varnish, an electric / electronic field such as a self-bonding enameled electric wire varnish, an adhesive, an insulating paint, a film, etc.
  • a polyhydroxy polyether resin characterized by containing an indenyl group or ⁇ -methylbenzyl group excellent in water resistance, adhesion and dielectric properties, a method for producing the polyhydroxy polyether resin, The present invention relates to a resin composition containing a resin, an insulating resin film, and an electronic circuit board.
  • polyhydroxypolyether resins are generally known as phenoxy resins and have excellent flexibility, impact resistance, insulation, adhesion, mechanical properties, etc. Used as a base resin for molding, a fluidity modifier added to epoxy resin varnishes, or an additive for improving the toughness of cured products.
  • electrical machines such as magnetic tape binders and motors are used.
  • insulating varnishes adhesives and films for circuit boards.
  • printed wiring boards are becoming smaller, lighter, and more functional.
  • higher multilayers higher density, thinner, lighter weight, higher reliability, and more. Molding processability is required.
  • a new multilayer printed wiring board manufacturing method such as a build-up method has been developed, and a high-performance resin suitable for these methods is required.
  • a copper foil with a resin for a build-up wiring board and a resin for an adhesive film a polyhydroxy polyether resin has been studied because it is advantageous for film forming properties.
  • performance requirements for this polyhydroxypolyether resin there has been a strong demand for lower dielectric constant and lower dielectric loss of the resin in accordance with recent demands for higher transmission speed of electrical signals. There are also demands for high heat resistance and low water absorption from the viewpoint of improving reliability.
  • Patent Document 1 Patent Document 2, Patent Document 3, and Patent Document 4 Describes a thermoplastic polyhydroxy polyether resin having a fluorene skeleton introduced therein, but these resins cannot sufficiently satisfy the above-mentioned requirements for high reliability and low dielectric constant.
  • An object of the present invention is to provide a polyhydroxypolyether resin and a resin composition for an electronic circuit board that are necessary for obtaining a resin composition for an electronic circuit board having excellent properties, flexibility, impact resistance, and adhesiveness.
  • the present invention for solving the above problems is selected from the following inventions.
  • the polyhydroxy polyether resin represented by the following general formula (1) and having a weight average molecular weight of 10,000 to 200,000 has an indenyl group, an ⁇ -methylbenzyl group, or both substituents.
  • a polyhydroxy polyether resin characterized by (In the formula, A is a chemical structure represented by the following general formula (2) or the following general formula (3), and at least one of A has an indenyl group or an ⁇ -methylbenzyl group as a substituent.
  • R is a group selected from the group consisting of an indenyl group or an ⁇ -methylbenzyl group, a hydrocarbon group having 1 to 10 carbon atoms, a phenyl or naphthyl group optionally containing a hydrocarbon group, and a halogen element.
  • R 1 and R 2 are each independently an indenyl group or ⁇ -methylbenzyl group, a C 1-10 hydrocarbon group, a phenyl group or naphthyl group optionally containing a hydrocarbon group, or a halogen element) Each of which may be different or the same, and p and q independently represent an integer of 0 to 4.
  • X is a single bond and a divalent hydrocarbon having 1 to 7 carbon atoms.
  • the method for producing a polyhydroxy polyether resin as described in item (1) above wherein (3) In a method for producing a polyhydroxy polyether resin in which a bifunctional epoxy resin and a dihydric phenol compound are reacted in the presence of a catalyst, a bifunctional epoxy having a substituent of indenyl group, ⁇ -methylbenzyl group, or both Resin or at least any one of a dihydric phenol compound having a substituent of indenyl group, ⁇ -methylbenzyl group, or both is used as an essential component. A method for producing a hydroxy polyether resin. (4) An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the polyhydroxy polyether resin described in (1) above is an essential component.
  • Either an epoxy resin composition described in the above item (4) or a resin composition for electronic circuit boards described in the above item (5) is applied to a metal foil, and dried as necessary.
  • a glass cloth is impregnated with either the epoxy resin composition described in the above item (4) or the resin composition for an electronic circuit board described in the above item (5), and is obtained by drying as necessary.
  • Prepreg. (9) The epoxy resin composition according to (4), the resin composition for an electronic circuit board according to (5), the adhesive film according to (6), and the (7) A cured product obtained by curing either the metal foil with resin or the prepreg described in the above item (8).
  • the polyhydroxy polyether resin and the epoxy resin composition of the present invention are excellent in glass transition temperature, low dielectric constant ( ⁇ ), low dielectric loss (tan ⁇ ), low water absorption, and particularly an electronic circuit requiring low dielectric constant characteristics. Exhibits excellent effects in substrate applications.
  • the polyhydroxy polyether resin represented by the general formula (1) of the present invention has an indenyl group represented by the following general formula (4a) or an ⁇ -methylbenzyl group represented by the following general formula (4b) as a substituent. it is essential to have.
  • These groups are those in which indene or styrene is substituted on the benzene ring of the dihydric phenol compound by Friedel-Crafts reaction. By having these substituents, water absorption resistance, heat resistance, and dielectric properties are improved.
  • An indenyl group is preferable from the viewpoint of water absorption resistance and high heat resistance, and an ⁇ -methylbenzyl group is preferable from the viewpoint of low viscosity.
  • the properties such as adhesiveness originally possessed by the polyhydroxy polyether resin having no substituent are not impaired. The effect tends to improve in proportion to the number of these substituents.
  • the indenyl group or the ⁇ -methylbenzyl group may be the same or different. Since the polyhydroxy polyether resin of the present invention is effective if there are substituents of these essential components, its content is not particularly specified, but is preferably in the range of 5 to 50% by mass, more preferably. Is in the range of 8 to 40% by mass, more preferably in the range of 10 to 30% by mass.
  • the polyhydroxy polyether resin of the present invention has a weight average molecular weight (Mw) in the range of 10,000 to 200,000.
  • Mw weight average molecular weight
  • a weight average molecular weight means the polystyrene conversion weight average molecular weight by gel permeation chromatography. If Mw is less than 10,000, the thermoplasticity is lost and sufficient film performance cannot be obtained, and if it exceeds 200,000, the viscosity becomes extremely high and handling becomes difficult.
  • the range of the weight average molecular weight is preferably 10,000 to 100,000, more preferably 15,000 to 70,000, and still more preferably 20 , which is 000 to 50,000.
  • the epoxy equivalent of the polyhydroxy polyether resin of the present invention is not particularly limited, but may be 5,000 g / eq or more. If it is 5,000 g / eq or less, the performance as a film is not sufficiently exhibited. If it is 5,000 g / eq or more, the film performance is improved, which is preferable.
  • Introducing the substituent of the essential component into the polyhydroxy polyether resin of the present invention is a divalent phenol compound having an indenyl group, an ⁇ -methylbenzyl group, or both, an indenyl group, an ⁇ -methylbenzyl group, Alternatively, it is possible to use a bifunctional epoxy resin having both substituents, or both.
  • an epihalohydrin such as epichlorohydrin or epibromohydrin and a dihydric phenol compound having a substituent of indenyl group, ⁇ -methylbenzyl group, or both are contained as essential components.
  • the polyhydroxy polyether resin used in the present invention may be obtained by any production method.
  • the weight average molecular weight and epoxy equivalent of the polyhydroxy polyether resin of the present invention are the molar ratio of epihalohydrin and dihydric phenol compound in the one-stage method, and the molar ratio of bifunctional epoxy resin and dihydric phenol compound in the two-stage method.
  • the thing of the target range can be manufactured by adjusting.
  • the divalent phenol compound having an indenyl group, an ⁇ -methylbenzyl group, or both substituents is preferably a divalent phenol compound having a biphenol skeleton or a bisphenol skeleton represented by the following general formula (5).
  • R 1 and R 2 are each independently an indenyl group or ⁇ -methylbenzyl group, a hydrocarbon group having 1 to 10 carbon atoms, a phenyl group or naphthyl group which may contain a hydrocarbon group, or a halogen element Each of which may be different or the same, at least one of which represents an indenyl group or an ⁇ -methylbenzyl group, p and q each independently represents an integer of 0 to 4, and the sum of p + q Is an average value of 1 to 8.
  • X is a single bond, a divalent hydrocarbon group having 1 to 7 carbon atoms, a benzylidene group, an ⁇ -methylbenzylidene group, a 9H-fluorene-9-ylidene group, —O—, It is a group selected from —S—, —SO 2 —, or —CO—, and when X is an aromatic skeleton, it may contain a hydrocarbon group as a substituent.
  • the number of indenyl groups or ⁇ -methylbenzyl groups is preferably in the range of 0.5 to 3.0 as an average value, more preferably 0.5 to The range is 1.5, and more preferably the range is 0.5 to 1.0.
  • the properties of the substituent will not improve water absorption resistance, heat resistance, and dielectric properties.
  • the dihydric phenol compound is reacted with indene or styrene.
  • the amount of indene or styrene used at that time substantially corresponds to the desired number of substituted moles (number of moles of substituents relative to 1 mole of the dihydric phenol compound), and the amount used may be determined accordingly.
  • the reaction conditions in which any of the raw materials remain unreacted can also be adopted.
  • the amount of indene or styrene used in 1 mol of the dihydric phenol compound is in the range of 0.5 to 3.0 mol. It is preferable.
  • the reaction exceeds 3 mol, the effect of improving water absorption, heat resistance, dielectric properties, etc. is reduced despite the fact that the time required for the addition reaction is greatly increased. it is preferably controlled below. Further, when any raw material remains unreacted, it is desirable to separate it, but it may remain as long as it is in a small amount.
  • the purity of the dihydric phenol compound is preferably 96% by mass or more, and preferably 98% by mass or more.
  • a mixture of these may be used as indene or styrene to be reacted with the dihydric phenol compound, but those having styrene as the main component are preferable from the viewpoint of low viscosity, and those having indene as the main component from the viewpoint of heat resistance. Those are preferred.
  • the indene or styrene used for the reaction may contain an unsaturated bond-containing component such as ⁇ -methylstyrene, divinylbenzene, coumarone, benzothiophene, indole, or vinylnaphthalene as another reactive component.
  • the indene and styrene contents in all reaction components are 60% by mass or more, preferably 80% by mass or more.
  • the compound which has a substituent derived from these is contained in the dihydric phenol compound obtained.
  • the dihydric phenol compound used as a raw material for the polyhydroxy polyether resin of the present invention may contain a dihydric phenol compound having such a substituent.
  • the polyhydroxy polyether resin obtained by the method for producing a polyhydroxy polyether resin of the present invention may include a polyhydroxy polyether resin having such a substituent.
  • Indene or styrene may contain non-reactive compounds such as toluene, dimethylbenzene, trimethylbenzene, indane, naphthalene, methylnaphthalene, dimethylnaphthalene, acenaphthene, and the like. From the viewpoint of improving properties such as heat resistance and electrical properties, it is better to remove these non-reactive compounds out of the system. Preferably, it is removed until it becomes 5 mass% or less of the whole, More preferably, it becomes 2 mass% or less. As a removal method, generally, a method such as vacuum distillation is applied.
  • a reaction method using a known Friedel-Crafts catalyst such as an acid catalyst can be employed for the reaction between the dihydric phenol compound and indene or styrene.
  • a reaction method using a known Friedel-Crafts catalyst such as an acid catalyst can be employed.
  • a divalent phenol compound having an indenyl group, an ⁇ -methylbenzyl group, or both substituents on the benzene ring of the divalent phenol compound is obtained.
  • the catalyst or unreacted components are removed as necessary to obtain a synthetic raw material for polyhydroxy polyether resin.
  • the dihydric phenol compound used in the production of the one-stage method and the two-stage method of the polyhydroxy polyether resin of the present invention is a divalent phenol compound having a substituent of indenyl group, ⁇ -methylbenzyl group, or both.
  • a compound having two hydroxyl groups bonded to an aromatic ring in other molecules may be used in combination.
  • dihydric phenol compounds examples include bisphenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol E, bisphenol C, bisphenol Z, bisphenol acetophenone, bisphenol fluorenone, biphenols, catechol, And monocyclic dihydric phenols such as resorcin and hydroquinone. These may be substituted with a substituent that does not have an adverse effect such as an alkyl group or an aryl group. These dihydric phenol compounds can be used in combination of a plurality of types.
  • 0.985 to 1.015 mol of epihalohydrin preferably 0.99 to 1.012 mol, more preferably 1 mol of the dihydric phenol compound.
  • non-reactive solvent examples include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, dioxane, ethanol, isopropyl alcohol, butyl alcohol, methyl cellosolve, ethyl cellosolve, and cyclohexanone, but are not particularly limited thereto. These solvents may be used alone or in combination of two or more.
  • the reaction temperature is preferably 40 to 200 ° C, particularly preferably 60 to 170 ° C.
  • the reaction pressure is usually normal pressure.
  • the bifunctional epoxy resin having a substituent of indenyl group, ⁇ -methylbenzyl group, or both which is used as the raw material epoxy resin of the two-stage method in the production method of the polyhydroxy polyether resin of the present invention, preferably It is a bifunctional epoxy resin represented by the following general formula (6) obtained by reacting a dihydric phenol compound represented by the general formula (5) with epihalohydrin.
  • R 1 and R 2 are each independently an indenyl group or ⁇ -methylbenzyl group, a hydrocarbon group having 1 to 10 carbon atoms, a phenyl group or naphthyl group which may contain a hydrocarbon group, or a halogen element Each of which may be different or the same, at least one of which represents an indenyl group or an ⁇ -methylbenzyl group, p and q each independently represents an integer of 0 to 4, and the sum of p + q Is an average value of 1 to 8.
  • X is a single bond, a divalent hydrocarbon group having 1 to 7 carbon atoms, a benzylidene group, an ⁇ -methylbenzylidene group, a 9H-fluorene-9-ylidene group, —O—, It is a group selected from -S-, -SO2-, or -CO-, and the aromatic skeleton in X may contain a hydrocarbon group as a substituent, G represents a glycidyl group, n represents Indicates the number of repetitions.) R, R in general formula (2), general formula (3), general formula (5), and general formula (6) 1, R 2 Each independently represents an indenyl group or an ⁇ -methylbenzyl group, a hydrocarbon group having 1 to 10 carbon atoms, a phenyl group or naphthyl group which may contain a hydrocarbon group, or a halogen element.
  • the hydrocarbon group having 1 to 10 carbon atoms includes a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, Aralkyl groups having 7 to 10 carbon atoms are preferred, and examples of the phenyl group or naphthyl group which may contain a hydrocarbon group include phenyl groups having 6 to 12 carbon atoms or naphthyl groups having 10 to 16 carbon atoms. It is done.
  • a linear or branched alkyl group having 1 to 10 carbon atoms such as decyl group, a cyclic alkyl group having 3 to 10 carbon atoms such as cyclohexyl group and trimethylcyclohexyl group, benzyl group, phenethyl group, 2-methylbenzyl group, A hydrocarbon group having 1 to 10 carbon atoms such as an aralkyl group having 7 to 10 carbon atoms such as 3-methylbenzyl group, 4-methylbenzyl group, 2,6-dimethylbenzyl group and 3,5-dimethylbenzyl group;
  • substituent include a phenyl group or a naphthyl group which may
  • the metal hydroxide is used in the form of an aqueous solution, alcohol solution or solid.
  • an excessive amount of epihalohydrin is used with respect to the dihydric phenol compound.
  • 1.5 to 15 times mole of epihalohydrin is used per mole of hydroxyl group in the dihydric phenol compound, but preferably in the range of 2 to 8 times mole. If the amount is more than this, the production efficiency is lowered, and if it is less than this, the amount of the high molecular weight polymer of the epoxy resin increases, and it becomes unsuitable for the raw material of the polyhydroxy polyether resin.
  • the epoxidation reaction is usually performed at a temperature of 120 ° C. or lower.
  • the temperature is high during the reaction, the amount of so-called hardly hydrolyzable chlorine increases and it becomes difficult to achieve high purity.
  • it is 100 degrees C or less, More preferably, it is the temperature of 85 degrees C or less.
  • the bifunctional epoxy resin used as the raw material for the two-stage method is preferably the bifunctional epoxy resin represented by the general formula (6). Any other compound may be used in combination as long as it is a compound having two epoxy groups in the molecule, so long as the purpose is not impaired.
  • Examples of the bifunctional epoxy resin of the general formula (6) include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol acetophenone type epoxy resin, and bisphenol fluorenone type epoxy resin. include biphenol-type epoxy resin or the like.
  • bisphenol A type epoxy resin, bisphenol F type epoxy resin, diglycidyl ether of 4,4′-biphenol, 3,3 ′, 5,5′-tetramethyl-4, 4'-biphenol diglycidyl ether, bisphenol acetophenone diglycidyl ether, and bisphenol fluorenone diglycidyl ether are preferred.
  • the dihydric phenol compound does not have an indenyl group or an ⁇ -methylbenzyl group
  • at least one of the bifunctional epoxy resins to be used needs to contain an indenyl group or an ⁇ -methylbenzyl group.
  • other difunctional epoxy resins that may be used in combination are diglycidyl monocyclic dihydric phenol compounds such as catechol, resorcin, and hydroquinone. Examples include ether. These epoxy resins may be substituted with a substituent having no adverse effect such as an alkyl group or an aryl group. These epoxy resins can be used in combination of plural kinds.
  • a catalyst can be used, and any compound having a catalytic ability capable of promoting the reaction between an epoxy group and a phenolic hydroxyl group can be used.
  • alkali metal compounds, organic phosphorus compounds, tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles and the like can be mentioned.
  • alkali metal compound include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide, alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride and potassium chloride.
  • Alkali metal alkoxides such as sodium methoxide and sodium ethoxide, alkali metal phenoxides, sodium hydride, lithium hydride and the like, and alkali metal salts of organic acids such as sodium acetate and sodium stearate.
  • organic phosphorus compound examples include tri-n-propylphosphine, tri-n-butylphosphine, triphenylphosphine, tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphosphonium hydroxide, Trimethylcyclohexylphosphonium chloride, trimethylcyclohexylphosphonium bromide, trimethylbenzylphosphonium chloride, trimethylbenzylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethylphosphonium chloride, triphenylethylphosphonium bromide, Triphenylethylphosphonium iodai , Triphenyl benzyl phosphonium chloride, triphenyl benzyl phosphonium bromide, and the like.
  • tertiary amine examples include triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine and the like.
  • Specific examples of the quaternary ammonium salt include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium bromide, Tetrapropylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benz
  • imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like.
  • cyclic amines include 1,8-diazabicyclo (5,4,0) undecene-7,1,5-diazabicyclo (4,3,0) nonene-5. These catalysts can be used in combination. Usually, the amount of the catalyst used is 0.001 to 1% by mass with respect to the reaction solid content.
  • the alkali metal component When using an alkali metal compound as a catalyst, the alkali metal component remains in the polyhydroxy polyether resin, and the insulating properties of the printed wiring board using the alkali metal component deteriorate, so that lithium, sodium in the polyhydroxy polyether resin, And the total content of potassium is preferably 5 ppm or less, more preferably 4 ppm or less, and even more preferably 3 ppm or less. If it is 5 ppm or more, the insulating properties deteriorate, which is not preferable. Also, when an organic phosphorus compound is used as a catalyst, it remains as a catalyst residue in the polyhydroxypolyether resin and deteriorates the insulating properties of the printed wiring board. Therefore, the phosphorus content in the polyhydroxypolyether resin is preferable.
  • a solvent may be used in the reaction step, and any solvent can be used as long as it dissolves the polyhydroxy polyether resin and does not adversely affect the reaction. But it ’s okay.
  • aromatic hydrocarbons include aromatic hydrocarbons, ketones, amide solvents, glycol ethers and the like. Specific examples of the aromatic hydrocarbon include benzene, toluene, xylene and the like.
  • ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclohexanone, acetylacetone, and dioxane.
  • Specific examples of the amide solvent include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone and the like.
  • glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono -N-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate and the like. Two or more of these solvents can be used in combination.
  • the amount of the solvent to be used can be appropriately selected depending on the reaction conditions. For example, in the case of the two-stage production, it is preferable that the solid concentration is 35 to 95% by mass. Further, when a highly viscous product is produced during the reaction, the reaction can be continued by adding a solvent during the reaction. After completion of the reaction, the solvent can be removed by distillation or the like, if necessary, or further added.
  • the reaction temperature in the case of the two-stage method among the methods for producing the polyhydroxy polyether resin of the present invention is within a temperature range in which the catalyst used is not decomposed. The reaction temperature is preferably 50 to 230 ° C, more preferably 120 to 200 ° C.
  • reaction temperature can be ensured by carrying out the reaction under high pressure using an autoclave.
  • reaction heat it is usually carried out by evaporation / condensation / reflux method of solvent used by reaction heat, indirect cooling method, or a combination thereof.
  • a halogen may be introduced into the polyoxypolyether resin of the present invention to impart flame retardancy. When flame retardancy is imparted by halogen, sufficient flame retardancy cannot be imparted if the halogen content is less than 5% by mass.
  • the resin composition for an electronic circuit board containing the polyhydroxy polyether resin of the present invention as an essential component includes, in addition to the polyhydroxy polyether resin, an epoxy resin, a curing agent, a curing accelerator, a solvent, an inorganic filler, and a fiber group.
  • Various materials such as materials can be used in combination.
  • an epoxy resin that can be used in combination a normal epoxy resin having two or more epoxy groups in the molecule can be used.
  • a normal epoxy resin having two or more epoxy groups in the molecule can be used.
  • Glycidyl ether type epoxy resins such as epoxy resins, aralkyl type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, linear aliphatic epoxy resins, alicyclic rings obtained by reacting novolaks with epihalohydrins.
  • epoxy resins such as epoxy resins, heterocyclic epoxy resins, phosphorus-containing epoxy resins, urethane-modified epoxy resins, and oxazolidone ring-containing epoxy resins. It is, but not limited thereto. These epoxy resins may be used alone or in combination of two or more. Specific examples include Epototo YD-128, Epototo YD-8125, Epototo YD-825GS (bisphenol A type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epototo YDF-170, Epototo YDF-8170, YDF-870GS (Nippon Steel & Sumitomo Metal). Chemical Co., Ltd.
  • Bisphenol F type epoxy resin Bisphenol F type epoxy resin
  • YSLV-80XY (Nippon Steel & Sumikin Chemical Co., Ltd. Tetramethylbisphenol F type epoxy resin)
  • Epototo YDC-1312 Di-tert-butyl hydroquinone type epoxy resin
  • jERYX4000H Mitsubishi Chemical
  • Epototo YDPN-638 Phenol novolac type epoxy resin manufactured by Nippon Steel & Sumikin Co., Ltd.
  • Epotot YDCN-701 Neippon Steel & Sumikin Chemical Co., Ltd.) Renovolak type epoxy resin
  • Epototo ZX-1201 Bisphenol fluorene type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • TX-0710 Bisphenol S type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • Epicron EXA-1515 Bisphenol S type epoxy resin manufactured by Nippon Chemical Industry
  • alkylene glycol type epoxy resin alkylene glycol type epoxy resin
  • epihalohydrin Celoxide 2021 (aliphatic cyclic epoxy resin produced by Daicel Chemical Industries, Ltd.), Epototo YH-434, Epoxy resin produced from an amine compound such as diaminodiphenylmethanetetraglycidylamine) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • jER630 aminophenol type epoxy resin manufactured by Mitsubishi Chemical Corporation
  • Epototo FX-289B Epototo FX-305
  • Examples include phosphorus-containing epoxy resins obtained by reacting an epoxy resin such as TX-0932A (phosphorus-containing epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) with a modifier such as a phosphorus-containing phenol compound.
  • the curing agent that can be used in the resin composition of the present invention include various phenol compounds, acid anhydrides, amines, dicyandiamide, and the like.
  • phenol compounds for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, naphthalenediol and the like Represented by tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinylphenol, etc. There are trivalent or higher phenol compounds.
  • monohydric phenol compounds such as phenols and naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, naphthalenediol, etc.
  • polyhydric phenol compounds synthesized by a condensing agent such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, and p-xylylene glycol. You may use what made indene or styrene react with these phenolic compounds for a hardening
  • Acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl hymic anhydride, nadic anhydride, trimellitic anhydride, pyromellitic anhydride Acid, methyl nadic anhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3- Examples include dione, 1,2,3,4-butanetetracarboxylic dianhydride, hydrogenated pyromellitic acid anhydride, hydrogenated trimellitic acid anhydride, and the like.
  • amines examples include aromatic amines such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine. And aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine. These curing agents may be used alone or in combination of two or more. As the addition amount of the curing agent, 10 to 100 parts by mass is used as necessary with respect to 100 parts by mass of the epoxy resin in the resin composition of the present invention.
  • a known curing accelerator can be used in the resin composition of the present invention.
  • imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5,4 , 0) Tertiary amines such as undecene-7, phosphines such as triphenylphosphine, tricyclohexylphosphine and triphenylphosphine triphenylborane, metal compounds such as tin octylate, Lewis acids and the like.
  • These curing accelerators may be used alone or in combination of two or more.
  • the curing accelerator 0.02 to 5 parts by mass is used as necessary with respect to 100 parts by mass of the epoxy resin in the resin composition of the present invention.
  • a curing accelerator By using a curing accelerator, the curing temperature can be lowered and the curing time can be shortened.
  • the solvent include acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, methanol, ethanol, and the like. These solvents may be used alone or in combination of two or more.
  • a filler can be used as needed.
  • silica powder such as aluminum hydroxide, alumina, calcium carbonate, magnesium hydroxide, talc, calcined talc, clay, kaolin, boehmite, titanium oxide, glass powder, spherical or crushed fused silica, crystalline silica, silica inorganic filler balloons and the like.
  • metal hydroxides such as aluminum hydroxide and magnesium hydroxide, are used, it acts as a flame retardant adjuvant and can reduce the quantity of a flame retardant.
  • the blending amount is not 10 parts by mass or more with respect to 100 parts by mass of the epoxy resin in the resin composition of the present invention, the effect of impact resistance is small. However, if the blending amount exceeds 150 parts by mass, the adhesiveness, which is an item necessary for the use of laminates, is lowered.
  • fiber base materials such as fiber fillers such as glass fiber, pulp fiber, synthetic fiber, ceramic fiber, fine particle rubber, thermoplastic elastomer, inorganic fiber cloth such as glass cloth, glass fiber nonwoven fabric, organic fiber nonwoven fabric, etc.
  • an ultraviolet inhibitor, a plasticizer, and the like can be contained in the resin composition.
  • an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene coumarone resin, or phenoxy resin may be appropriately blended, or pigment.
  • additives such as a refractory agent, a thixotropic agent, a coupling agent, and a fluidity improver may be blended.
  • the pigment include organic or inorganic extender pigments and scaly pigments.
  • the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, polyethylene oxide wax, and organic bentonite.
  • the epoxy resin composition of the present invention includes a release agent such as carnauba wax and OP wax, a coupling agent such as ⁇ -glycidoxypropyltrimethoxysilane, a colorant such as carbon black, Flame retardants such as antimony trioxide, low stress agents such as silicone oil, lubricants such as calcium stearate, and the like can be used.
  • a release agent such as carnauba wax and OP wax
  • a coupling agent such as ⁇ -glycidoxypropyltrimethoxysilane
  • a colorant such as carbon black
  • Flame retardants such as antimony trioxide
  • low stress agents such as silicone oil
  • lubricants such as calcium stearate, and the like
  • these resin compositions can be used for new printed wiring boards such as conventional multilayer electronic circuit boards and build-up methods.
  • use in the form of a resin-coated copper foil, an adhesive film, or the like used as a build-up method printed wiring board material is preferable
  • the build-up method is a build-up layer that is an insulating layer made of a film (insulating layer) of 40 to 90 ⁇ m or a film with copper foil (copper foil: 9 to 18 ⁇ m) on an inner circuit board in which glass prepregs are laminated.
  • the circuit forming process includes a laminating press process, a drilling (laser or drill) process, and a desmear / plating process. And if it has the same performance as a conventional laminated board, both the mounting area and the mass are about 1/4, which is an excellent method for reducing the size and weight.
  • the polyhydroxy polyether resin of the present invention is suitable for film formation and can be suitably used as a build-up insulating layer.
  • the method for producing the adhesive film according to the present invention is not particularly limited.
  • the resin composition of the present invention is kneaded with an extruder and then extruded, and then formed into a sheet using a T die, a circular die, or the like.
  • the thickness of the adhesive film is not particularly limited, but is, for example, 10 to 300 ⁇ m, preferably 25 to 200 ⁇ m, and more preferably 40 to 180 ⁇ m. When used in the build-up method, 40 to 90 ⁇ m is most preferable.
  • the solvent content of the adhesive film is not particularly limited, but is preferably 0.01 to 5% by mass with respect to the entire resin composition. If the content of the solvent in the film is 0.01% by mass or more with respect to the entire resin composition, adhesion and adhesiveness can be obtained when laminating to the circuit board, and if the content is 5% by mass or less. flatness after heat curing can be obtained.
  • Weight average molecular weight It was measured as a standard polystyrene equivalent value by gel permeation chromatography. Specifically, the Tosoh Corporation HLC-8320 main body was used with a Tosoh Corporation column, TSK-gel GMHXL, TSK-gel GMHXL, and TSK-gel G2000HXL in series. The eluent was tetrahydrofuran and the flow rate was 1 ml / min. Column temperature was room 40 ° C.. Detection was carried out using an RI detector and determined using a standard polystyrene calibration curve.
  • Tg Extrapolated glass transition start temperature (Tig) of the DSC chart obtained in the second cycle of differential scanning calorimetry was defined as Tg [DSC]. Specifically, it was performed using DSC6200 manufactured by SII Nano Technology. A measurement sample was obtained by punching a resin film, laminating it, and packing it in an aluminum capsule. The measurement temperature range was from room temperature to 240 ° C. The temperature elevation rate was 10 ° C./min, and the measurement was performed for 2 cycles.
  • Synthesis example 1 A four-necked glass separable flask equipped with a stirrer, a thermometer, a condenser, a nitrogen gas introducing device, and a dropping device, and 684 parts of bisphenol A, diglyme 1800 Part The temperature was raised to charged 0.99 ° C.. After melting, stirring 48% sulfuric acid 19.5 Part And 348 parts of indene were added dropwise at 140 ° C. over about 3 hours. Further, the reaction was continued for 3 hours under total reflux.
  • the obtained dihydric phenol compound has a hydroxyl group equivalent of 135 g / eq. Met.
  • Synthesis example 3 Bisphenol F (4,4 'body (31%), 2,4' manufactured by Honshu Chemical Co., Ltd.) was added to a four-necked glass separable flask equipped with a stirrer, thermometer, condenser, nitrogen gas introducing device, and dropping device. 600 parts of the body (49%) and 2,2 'body (20%) were charged and the temperature was raised to 175 ° C. After melting, 0.44 part of p-toluenesulfonic acid was charged with stirring, and 624 parts of styrene was added dropwise at 175 ° C. over about 4 hours.
  • dihydric phenol compound C a styrene-added dihydric phenol compound
  • the obtained dihydric phenol compound had a hydroxyl group equivalent of 204 g / eq. Met.
  • the reaction rate of indene or styrene was almost 100%.
  • Synthesis example 4 Obtained in Synthesis Example 3 into a four-necked separable flask equipped with a stirrer, thermometer, continuous dripping device, and a device that cools and condenses the azeotropic vapor of epichlorohydrin and water under reduced pressure and returns only epichlorohydrin to the reaction system 2 450 parts of the phenol compound C, 918 parts of epichlorohydrin, and 138 parts of diethylene glycol dimethyl ether were added and dissolved by stirring. After uniformly dissolving, maintaining at 65 ° C.
  • bifunctional epoxy resin has an epoxy equivalent of 259 g / eq. Met.
  • Example 1 150 parts of dihydric phenol compound A, 82 parts of epichlorohydrin, 60 parts of toluene, 30 parts of n-butyl alcohol, 80 parts of 48.4% sodium hydroxide aqueous solution as a catalyst, stirrer, thermometer, condenser, nitrogen gas introduction device was added to a four-necked glass separable flask, and while maintaining the reaction temperature at 60 ° C. to 70 ° C., 80 parts of toluene and 40 parts of n-butyl alcohol were added to the reaction for 3 hours. 65 parts of toluene and 35 parts of n-butyl alcohol were added to each and reacted for a total of 10 hours.
  • Example 2 In a separable flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen blowing port, Nippon Steel & Sumikin Chemical Co., Ltd.
  • Epototo YD-128 (BPA type liquid epoxy resin, epoxy equivalent 187 g / eq, ⁇ diol concentration 7 meq / 100 g, Total chlorine concentration 0.16%) 175.3 parts, 124.7 parts of dihydric phenol compound B and 100 parts of cyclohexanone were charged, heated to 145 ° C., dissolved, and stirred for 1 hour. Thereafter, 0.12 part of 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., hereinafter abbreviated as 2E4MZ) was charged as a reaction catalyst, and the temperature was raised to 165 ° C.
  • 2E4MZ 2-ethyl-4-methylimidazole
  • the obtained polyhydroxy polyether resin was diluted with tetrahydrofuran to a non-volatile content of 30%, coated on a PET film degreased with methyl ethyl ketone, and heated at 150 ° C. in an air atmosphere using a hot air circulating oven. After drying for a time, it was peeled off from the PET film to obtain a resin film having a thickness of 60 ⁇ m.
  • the analysis similar to Example 1 was performed using the obtained resin film. The analysis results are as shown in Table 1.
  • Example 3 Implemented except that 146.4 parts of Epototo YD-128, 153.6 parts of dihydric phenol compound C and 0.6 parts of triphenylphosphine (made by Hokuko Chemical Co., Ltd., trade name: TPP) were used as catalysts.
  • a mixed resin varnish and a resin film were obtained in the same procedure as in Example 2.
  • the analysis similar to Example 1 was performed using the obtained resin film.
  • the analysis results are as shown in Table 1.
  • Example 4 A mixed resin varnish and a resin film were obtained in the same procedure as in Example 2 except that the raw material used was changed to 182 parts of bifunctional epoxy resin A, 118 parts of dihydric phenol compound A, and 0.12 part of 2E4MZ as a catalyst.
  • Example 5 ESF-300 (bisphenol fluorene type epoxy resin, epoxy equivalent 254 g / eq, ⁇ diol concentration 2 meq / 100 g, total chlorine concentration 0.12%) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. 206.5 parts, divalent phenol compound B
  • a mixed resin varnish and a resin film were obtained in the same procedure as in Example 2 except that 84.8 parts, resorcinol (special reagent grade) 8.7 parts, and TPP 0.6 parts as a catalyst were changed.
  • the analysis similar to Example 1 was performed using the obtained resin film. The analysis results are as shown in Table 1.
  • Comparative Example 1 A mixed resin varnish and a resin film were obtained in the same procedure as in Example 2, except that 197.5 parts of Epototo YD-128, 102.5 parts of bisphenol F, and 0.12 part of 2E4MZ were used as the catalyst. Moreover, the analysis similar to Example 1 was performed using the obtained resin film. The analysis results are as shown in Table 1. Comparative Example 2 A mixed resin varnish and a resin film were obtained in the same procedure as in Example 2, except that the raw materials used were changed to 188.1 parts of Epototo YD-128, 111.9 parts of bisphenol A, and 0.6 parts of TPP. Moreover, the analysis similar to Example 1 was performed using the obtained resin film. The analysis results are as shown in Table 1.
  • the polyhydroxy polyether resin containing an indenyl group or ⁇ -methylbenzyl group as a substituent in the resin has good heat resistance (high glass transition temperature) and good water resistance (water absorption). The electrical properties are good (low dielectric constant).
  • Examples 7-11, Comparative Examples 3-5 The polyhydroxy polyether resins obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were mixed with an epoxy resin, an epoxy resin curing agent, a curing accelerator, and a solvent so that the conditions shown in Table 2 were satisfied. An epoxy resin composition varnish having a content of 40% was obtained.
  • the dicyandiamide used was a dicyandiamide solution prepared by dissolving in a mixed solvent comprising 4 parts of dicyandiamide, 15 parts of N, N-dimethylformamide and 15 parts of 2-methoxyethanol. Other than that, 50 parts of 2-methoxyethanol and 50 parts of methyl ethyl ketone were mixed and used for 100 parts of resin.
  • As other epoxy resins in the table Epototo YD-128 and Nippon Steel & Sumikin Chemical Co., Ltd.
  • Epototo YDCN-700-5 (orthocresol novolac type epoxy resin, epoxy equivalent 202 g / eq., Softening point 86 ° C.)
  • epoxy resin curing agent dicyandiamide and phenol novolac resin (BRG-557, Showa Denko KK, phenolic hydroxyl group equivalent 105 g / eq., Softening point 86 ° C.) and 2E4MZ were used as the curing accelerator.
  • the epoxy resin composition varnish was impregnated into a glass cloth (WEA 116E 106S 136, 0.1 mm thickness, manufactured by Nittobo Co., Ltd.), and then the impregnated cloth was dried in a drying chamber at 150 ° C. for 8 minutes to obtain a B stage.
  • a prepreg was obtained. Eight prepregs obtained by cutting this prepreg are sandwiched between two copper foils (3EC-III, 35 ⁇ m manufactured by Mitsui Mining & Smelting Co., Ltd.), and a vacuum press of 2 MPa under a temperature condition of 130 ° C. ⁇ 15 minutes + 190 ° C. ⁇ 80 minutes. To obtain a laminate.
  • Table 2 shows the physical properties of the laminate produced using the resin composition containing the polyhydroxy polyether resin of the present invention shown in Table 2 and the properties of the laminate produced using the epoxy resin composition of the comparative example.
  • the laminated board produced from the resin composition of the present invention is remarkably excellent in heat resistance (glass transition temperature), water resistance (solder heat resistance after PCT) and adhesion.

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Abstract

L'invention porte sur une résine de polyhydroxypolyéther qui est nécessaire pour obtenir une composition de résine pour des cartes de circuit électronique, ladite composition de résine ayant une excellente résistance à la chaleur, une faible absorption d'eau, d'excellentes caractéristiques électriques (en particulier une faible constante diélectrique et une faible perte diélectrique), et d'excellentes caractéristiques en termes d'aptitude au moulage, de flexibilité, de résistance au choc et d'adhérence ; sur une composition de résine, pour des cartes de circuit électronique, qui contient la résine de polyhydroxypolyéther en tant que constituant essentiel. La résine de polyhydroxypolyéther est caractérisée en ce qu'elle possède une masse moléculaire moyenne en poids de 10 000 à 200 000 et en ce qu'elle possède un ou plusieurs constituants, à savoir un groupe indényle et/ou un groupe α-méthylbenzyle.
PCT/JP2013/063866 2012-06-12 2013-05-13 Résine de polyhydroxypolyéther, procédé de fabrication de résine de polyhydroxypolyéther, composition de résine contenant de la résine de polyhydroxypolyéther et produit durci obtenu à partir de celle-ci WO2013187185A1 (fr)

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CN105623238A (zh) * 2014-11-06 2016-06-01 江苏雅克科技股份有限公司 含磷官能化聚(亚芳基醚)及以其为原料制备组合物
WO2018061516A1 (fr) * 2016-09-28 2018-04-05 新日鉄住金化学株式会社 Matériau de moulage de matière plastique renforcée de fibres, son procédé de production, et produit moulé

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WO2018061516A1 (fr) * 2016-09-28 2018-04-05 新日鉄住金化学株式会社 Matériau de moulage de matière plastique renforcée de fibres, son procédé de production, et produit moulé
JPWO2018061516A1 (ja) * 2016-09-28 2019-07-04 日鉄ケミカル＆マテリアル株式会社 繊維強化プラスチック成形用材料、その製造方法及び成形物

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