WO2023167019A1 - リン含有（メタ）アクリロイル化合物、その製造方法、これを含む難燃性術組成物および電子回路基板用積層板 - Google Patents

リン含有（メタ）アクリロイル化合物、その製造方法、これを含む難燃性術組成物および電子回路基板用積層板 Download PDF

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WO2023167019A1
WO2023167019A1 PCT/JP2023/005764 JP2023005764W WO2023167019A1 WO 2023167019 A1 WO2023167019 A1 WO 2023167019A1 JP 2023005764 W JP2023005764 W JP 2023005764W WO 2023167019 A1 WO2023167019 A1 WO 2023167019A1
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meth
phosphorus
compound
general formula
flame
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PCT/JP2023/005764
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French (fr)
Japanese (ja)
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次俊 和佐野
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日鉄ケミカル＆マテリアル株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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

Definitions

  • the present invention relates to reactive phosphorus compounds, particularly phosphorus-containing (meth)acryloyl compounds, which are useful as reactive flame retardants for plastic materials.
  • plastic materials Due to their excellent mechanical properties and moldability, plastic materials are used in a wide range of applications, from building materials to electrical and electronic equipment. However, since most plastic materials are flammable, they must be made flame-retardant for safety against heat generation, ignition, and fire in the applications where they are used, such as electrical/electronic products, OA equipment, and communication equipment.
  • additive-type flame retardants such as halogen-based flame retardants, inorganic flame-retardants, phosphorus-based flame retardants and the like is common regardless of resin type and application.
  • halogen-based flame retardants mainly brominated
  • Inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide have a flame retardant effect by absorbing heat, but they must be added in large amounts to achieve sufficient flame retardancy. This causes deterioration of the characteristics. Therefore, many phosphorus-based flame retardants that do not generate harmful substances and can be flame retarded with a relatively small amount of addition are often used. , the effect on the characteristics is inevitable.
  • reactive flame retardants containing phosphorus atoms which are flame-retardant components, and having reactive groups have been developed and have been widely used.
  • reactive flame retardants applicable to epoxy resin compositions that are frequently used in the electronic and electrical fields include, for example, Patent Document 1, as a curing agent for epoxy resins, reacting bisphenol A and formaldehyde to obtain hydroxymethylbisphenol.
  • a phenolic resin obtained by reacting A after obtaining 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as "DOPO") is disclosed, and patent documents 2 discloses a phosphorus-containing epoxy resin obtained by reacting DOPO with quinones and then with an epoxy resin.
  • DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • patent documents 2 discloses a phosphorus-containing epoxy resin obtained by reacting DOPO with quinones and then with an epoxy resin.
  • the resin composition used for circuit boards is required to be soluble in solvents because it is used by impregnating base materials such as glass cloth. It is preferable to use a non-polar solvent such as toluene because of its influence on the reaction, and it is essential that no precipitation is observed even in these solvents.
  • Patent Document 3 discloses a vinyl benzyl ether compound obtained from DOPO and chloromethylstyrene.
  • DOPO hydrolyzed with alkali
  • Patent Document 4 discloses a polyfunctional vinyl benzyl ether compound using an adduct of DOPO and quinones
  • Patent Document 5 and Non-Patent Document 1 disclose a polyfunctional ( Meta) acryloyl compounds are disclosed. These compounds have excellent properties in terms of heat resistance and dielectric properties, but have problems in handling such as strong crystallinity and precipitation in low-polarity solvents.
  • JP 2013-166938 Japanese Patent Laid-Open No. 11-279258 JP 2004-277322 JP 2004-331537 JP 2014-156426
  • the problem to be solved by the present invention is a phosphorus-containing compound that is useful as a reactive phosphorus-based flame retardant, has excellent solvent solubility, and has excellent heat resistance and dielectric properties in a cured product, and a curable resin composition containing the same. It is to provide a product and its cured product.
  • a phosphorus-containing (meth)acryloyl compound and a composition having a specific structure are excellent in flame retardancy, heat resistance, solubility and dielectric properties. reached.
  • the present invention is a phosphorus-containing (meth)acryloyl compound represented by the following general formula (1).
  • R1 and R2 are hydrogen, a hydroxyl group, a group represented by -OR or -R, and R is a hydrocarbon group having 2 to 40 carbon atoms.
  • R1 and R2 may be the same or different, and R1 and R2 may form a ring structure together with the phosphorus atom.
  • R3 is a C1-C20 hydrocarbon group.
  • X in the formula is a substituent represented by the following general formula (2).
  • R4 is hydrogen or a methyl group.
  • a flame-retardant resin composition characterized by comprising the phosphorus-containing (meth)acryloyl compound and at least one type of thermosetting resin or thermoplastic resin.
  • the phosphorus-containing (meth)acryloyl compound of the present invention has excellent solvent solubility, and the cured product obtained by curing a composition containing this compound as an essential component exhibits a low dielectric constant and dielectric loss tangent, and a decrease in heat resistance. It is very useful as a reactive phosphorus-based flame retardant because it can reduce transmission loss at high frequencies accompanying the increase in the amount of information processing in electronic equipment.
  • a hydroxyl group-containing phosphorus compound or a phosphorus-containing (meth)acryloyl compound includes not only a single compound but also a mixture (resin).
  • the phosphorus-containing (meth)acryloyl compound of the present invention is represented by the following general formula (1).
  • R1 and R2 are hydrogen, a hydroxyl group, a group represented by -OR or -R, and R is a hydrocarbon group having 2 to 40 carbon atoms.
  • R1 and R2 may be the same or different, and R1 and R2 may form a ring structure together with the phosphorus atom.
  • R is a benzene ring group, and the benzene ring may be substituted with an alkyl group having 1 to 3 carbon atoms.
  • X is a substituent represented by Formula (2) below.
  • the phosphorus-containing (meth)acryloyl compound of the present invention may be a mixture containing a compound in which X is a hydroxyl group as an unreacted raw material.
  • R4 is hydrogen or a methyl group.
  • R3 is a C1-C20 hydrocarbon group.
  • the C1-C20 hydrocarbon group includes an aliphatic hydrocarbon group having a linear or branched structure, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group having 6-20 carbon atoms.
  • Examples of aliphatic hydrocarbon groups include alkyl groups having 1 to 20 carbon atoms, and examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenyl and anthranyl groups.
  • R3 contains an aromatic hydrocarbon group, the aromatic ring may or may not have a substituent.
  • substituents examples include a carboxy group, an aliphatic hydrocarbon group, an acyl group, an alkoxy group, a cyano group, a hydroxyl group, a methacryloyloxy group, a vinylbenzyl ether group, and groups in which these substituents are linked.
  • aromatic hydrocarbon group has a substituent, the carbon number of the substituent is not included in the number of carbon atoms.
  • the phosphorus-containing (meth)acryloyl compound represented by the general formula (1) has a phosphorus content of preferably 1.0 to 10.0% by weight, more preferably 5.0 to 9.0% by weight, and still more preferably is 6.0 to 8.0% by weight.
  • the compound represented by the general formula (1) is obtained by reacting a hydroxyl group-containing phosphorus compound represented by the following general formula (3) with a compound containing one glycidyl group, followed by (meth)acrylic acid, (meth ) can be obtained by (meth)acryloylating with an acrylic anhydride or a (meth)acryloyl halide compound.
  • R1 and R2 have the same definitions as in general formula (1).
  • the phosphorus compound represented by the general formula (3) may be an organic phosphorus compound having an active hydrogen directly attached to a phosphorus atom.
  • dimethylphosphine oxide diethylphosphine oxide, diphenylphosphine oxide, methylphenylphosphinate, tert-butylphenylphosphine oxide, etc.; Dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by HCA Sanko) and the like, but are limited to these. However, two or more types may be used.
  • Examples of compounds containing one glycidyl ether group include ethyl glycidyl ether, butyl glycidyl ether, tert-butyl glycidyl ether, glycidyl isopropyl ether, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, lauryl alcohol (EO) 15 glycidyl ether, C12-13 mixed alcohol glycidyl ether, 3-glycidyloxypropyl(dimethoxy)methylsilane, glycidyl acrylate, allyl glycidyl ether, glycidyl methacrylate, 1,1,1,3,5,5,5-heptamethyl-3-(3- glycidyloxypropyl)trisiloxane, 1,2-epoxydecane glycidyl guaiacol ether, phenyl glycidy
  • 2-ethylhexyl glycidyl ether can be 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, and 4-tert-butylphenyl glycidyl ether are preferred because of their easy availability.
  • the reaction between the phosphorus compound having an active hydrogen represented by general formula (3) and epoxy resins containing one glycidyl group can be carried out by a known method. That is, an epoxy resin is added to a phosphorus compound having active hydrogen, and the reaction is carried out with stirring at a reaction temperature of 100°C to 200°C, more preferably 120°C to 180°C. If the rate of this reaction is slow, a catalyst can be used to improve productivity if desired.
  • catalysts include tertiary amines such as benzyldimethylamine; quaternary ammonium salts such as tetramethylammonium chloride; phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine; Various catalysts such as phosphonium salts such as phenylphosphonium bromide and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole can be used.
  • the reaction molar ratio of the phosphorus-containing compound represented by the general formula (3) and the epoxy resin containing one glycidyl group is 0.80 to 1.20 mol of the glycidyl group per 1 mol of the active hydrogen of the phosphorus compound. , preferably 0.9 to 1.10 mol, more preferably 0.95 to 1.05 mol.
  • the phosphorus compound having unreacted active hydrogen increases in the compound, and at 1.20 or more, the epoxy resin containing one unreacted glycidyl group increases in the compound, thereby lowering the heat resistance and further deteriorating the dielectric properties. I don't like it because I let it happen.
  • a phosphorus-containing compound containing an alcoholic hydroxyl group obtained from the reaction of a phosphorus compound having an active hydrogen represented by the general formula (3) and an epoxy resin containing one glycidyl group (hereinafter referred to as a hydroxyl-containing phosphorus compound)
  • the reaction of (meth)acrylic acid, (meth)acryloyl halide, or (meth)acrylic anhydride is not particularly limited, and can be carried out in the same manner as the usual (meth)acryloyl reaction of alcohol compounds and phenol compounds.
  • a hydroxyl group-containing phosphorus compound is added to the hydroxyl group in the presence of a strong acid catalyst such as sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, etc.
  • a strong acid catalyst such as sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, etc.
  • (meth) It can be produced by a condensation reaction with acrylic acid. Since this reaction must proceed while removing by-product condensed water out of the system, a hydrocarbon-based solvent such as toluene that is azeotropic with water is used as the reaction solvent. It is done by heating to about °C.
  • the phosphorus-containing (meth)acryloyl compound of the present invention can be obtained by reacting a hydroxyl group-containing phosphorus compound with a (meth)acryloyl halide or (meth)acrylic anhydride.
  • (Meth)acryloyl halides that can be used include acryloyl halides such as acryloyl fluoride, acryloyl chloride, acryloyl bromide and acryloyl iodide; Methacryloyl halides can be mentioned.
  • the (meth)acryloyl halide and (meth)acrylic anhydride may be used singly or as a mixture of two or more. In the present invention, among others, it is preferable to use (meth)acrylic chloride and/or (meth)acrylic anhydride from the viewpoint of easy availability.
  • the amount of (meth)acryloyl halide and/or (meth)acrylic anhydride to be used is 0.8 to 5 mol, preferably 0.95 to 1 mol, per 1 mol of the hydroxyl group of the phosphorus-containing phenol compound used as a raw material. 4 moles. If the amount of (meth)acrylic acid halide and/or (meth)acrylic anhydride used is less than the above range, the heat resistance of the obtained phosphorus-containing (meth)acryloyl compound is lowered and the amount of residual hydroxyl groups is increased. It is not preferable because the dielectric properties deteriorate, and if the amount used exceeds the above range, the pot efficiency decreases and the cost increases, which is not preferable.
  • the hydrogen halide corresponding to the (meth)acrylic acid halide used is generated as a by-product, so a basic compound is used in combination to remove the generated hydrogen halide. It is preferable to carry out the reaction while trapping.
  • the basic compound is not particularly limited, and trimethylamine, triethylamine, diisopropylethylamine, tri-n-propylamine, triisopropylamine, tributylamine, N-methyl-diethylamine, N-ethyl-dimethylamine, N-ethyl-diamylamine, etc.
  • aromatic amines such as N,N-dimethylaniline and diethylaniline; alicyclic amines such as N,N-dimethyl-cyclohexylamine and N,N-diethyl-cyclohexylamine; N,N-dimethylamino heterocyclic amines such as pyridine, N-methylmorpholine, diazabicycloundecene (DBU), diazabicyclononene (DBN), N-methylpyridine and N-methylpyrrolidine; diamines such as tetramethylethylenediamine and triethylenediamine; can be mentioned.
  • aliphatic amines such as trimethylamine and triethylamine, and pyridine are preferred because of their easy availability.
  • the amount of the basic compound used is, for example, about 0.8 to 7 mol, preferably about 0.95 to 5 mol, per 1 mol of the hydroxyl group of the hydroxyl group-containing phosphorus compound used as the raw material. If the amount of the tertiary amine used is below the above range, the hydrogen halide cannot be completely trapped, causing corrosion of the reactor.
  • ester catalysts include alkali metal salts of lower carboxylic acids such as sodium and potassium, such as sodium acetate, potassium propionate and sodium (meth)acrylate.
  • Examples of acid catalysts include inorganic acids such as sulfuric acid and boric acid; organic acids such as methanesulfonic acid and p-toluenesulfonic acid;
  • Examples of basic catalysts include organic bases such as nitrogen-containing aliphatic compounds such as triethylamine and triethylenediamine; and nitrogen-containing aromatic heterocyclic compounds such as pyridine and 4-(dimethylamino)pyridine.
  • Examples of Lewis acid catalysts include aluminum chloride and zinc chloride.
  • the amount of the catalyst used is preferably 10% or less, more preferably 5% or less, relative to the (meth)acrylic anhydride used. When the above range is exceeded when a catalyst is used, it takes a long time to remove the catalyst, and the catalyst tends to remain in the product, resulting in deterioration of properties.
  • reaction solvent In the reaction between the hydroxyl group-containing phosphorus compound and the (meth)acryloyl halide and/or (meth)acrylic anhydride, it is preferable to use an organic solvent as the reaction solvent and carry out the reaction in a solution.
  • the solvent that can be used is not particularly limited as long as it does not have reactivity with the hydroxyl group-containing compound and (meth)acrylic acid halide or/and (meth)acrylic anhydride, and includes tetrahydrofuran, dioxane, Solvents such as ethyl acetate, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexamethylphosphoric acid triamide, water, etc., may be used in combination if necessary. be able to.
  • the reaction temperature is preferably -50 to 150°C, and a polymerization reaction may occur if the reaction is carried out at a high temperature.
  • a temperature of -25 to 100° C. is more preferable since the temperature increases.
  • the reaction time is appropriately set according to the set reaction temperature, but is preferably set within the range of 1 to 48 hours.
  • the reaction between the hydroxyl group-containing phosphorus compound and (meth)acrylic acid, (meth)acryloyl halide or (meth)acrylic anhydride may be carried out in the presence of a polymerization inhibitor.
  • a polymerization inhibitor By adding a polymerization inhibitor, the (meth)acrylic acid, (meth)acryloyl halide or (meth)acrylic anhydride to be subjected to the reaction and the (meth)acrylic acid ester as the target product are polymerized to form an oligomer. can be prevented from being produced as a by-product.
  • Any known polymerization inhibitor can be used without limitation, and organic compounds such as hydroquinone, hydroxymonomethyl ether, t-butylcatechol, t-butylhydroquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and phenothiazine.
  • organic compounds such as hydroquinone, hydroxymonomethyl ether, t-butylcatechol, t-butylhydroquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and phenothiazine.
  • copper compounds such as copper chloride and copper sulfide, and these may be used in combination.
  • reaction mixture After completion of this reaction, the resulting reaction solution (reaction mixture) is subjected, if necessary, to distillation of the reaction solvent, solvent replacement, etc., washing with water, etc., treatment with activated carbon, silica gel chromatography, etc.
  • the (meth)acryloyl compound of the present invention which is the target product, can be isolated by purifying the reaction mixture with a
  • curable resins include unsaturated polyester resins, curable maleimide resins, epoxy resins, polycyanate resins, phenol resins, and one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule. etc., preferably epoxy resins and one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule.
  • the curable resin is an epoxy resin
  • it is preferably one or more epoxy resins selected from epoxy resins having two or more epoxy groups in one molecule.
  • epoxy resins include cresol novolak type epoxy resins, triphenylmethane type epoxy resins, biphenyl epoxy resins, naphthalene type epoxy resins, bisphenol A type epoxy resins and bisphenol F type epoxy resins. These may be used alone or in combination of two or more.
  • a curing agent may be used in addition to the epoxy resin.
  • the curing agent is not particularly limited, and includes, for example, phenol-based curing agents, amine-based compounds, amide-based compounds, acid anhydride-based compounds, naphthol-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, A cyanate ester-based curing agent and the like are included. These may be used singly or in combination of two or more.
  • a curing accelerator when blending an epoxy resin, a curing accelerator can be used as necessary.
  • examples include amines, imidazoles, organic phosphines, and Lewis acids.
  • the amount added is usually in the range of 0.2 to 5 parts by weight per 100 parts by weight of the epoxy resin.
  • the type is not particularly limited. That is, any vinyl compound may be used as long as it can be cured by forming crosslinks by reacting with the phosphorus-containing (meth)acryloyl compound of the present invention. More preferably, the polymerizable unsaturated hydrocarbon group is a carbon-carbon unsaturated double bond, more preferably a compound having two or more carbon-carbon unsaturated double bonds in the molecule.
  • the average number of carbon-carbon unsaturated double bonds (the number of vinyl groups (including substituted vinyl groups); also referred to as the number of terminal double bonds) per molecule of vinyl compounds as curable resins is For example, it is preferably 1 to 20, more preferably 2 to 18, depending on the Mw of the class. If the number of terminal double bonds is too small, it tends to be difficult to obtain a cured product with sufficient heat resistance. On the other hand, if the number of terminal double bonds is too large, the reactivity becomes too high, for example, the storage stability of the curable resin composition is lowered, the fluidity of the curable resin composition is lowered, and the like. Failure to do so may result in malfunction.
  • vinyl compounds include triallyl isocyanurate (TAIC) and other trialkenyl isocyanurate compounds, modified polyphenylene ethers (PPE) whose terminals are modified with (meth)acryloyl groups or styryl groups, and (meth)acryloyl groups in the molecule.
  • TAIC triallyl isocyanurate
  • PPE modified polyphenylene ethers
  • polyfunctional (meth) acrylate compounds having two or more vinyl compounds (polyfunctional vinyl compounds) having two or more vinyl groups in the molecule such as polybutadiene, and vinylbenzyl compounds such as styrene and divinylbenzene. be done.
  • those having two or more carbon-carbon double bonds in the molecule are preferred, and specific examples include TAIC, polyfunctional (meth)acrylate compounds, modified PPE resins, polyfunctional vinyl compounds, divinylbenzene compounds, and the like. is mentioned. It is believed that the use of these compounds will more favorably form crosslinks through the curing reaction, and the heat resistance of the cured product of the curable resin composition can be further enhanced. Moreover, these may be used independently and may be used in combination of 2 or more type. A compound having one carbon-carbon unsaturated double bond in the molecule may also be used in combination. Compounds having one carbon-carbon unsaturated double bond in the molecule include compounds having one vinyl group in the molecule (monovinyl compounds).
  • thermoplastic resins include polystyrene, polyphenylene ether resins, polyetherimide resins, polyether sulfone resins, PPS resins, polycyclopentadiene resins, polycycloolefin resins, and known thermoplastic elastomers (e.g., styrene- ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, etc.) and , or rubbers (eg, polybutadiene, polyisoprene).
  • Preferred are unmodified or modified polyphenylene ether resins and hydrogenated styrene-butadiene copolymers.
  • the flame-retardant resin composition of the present invention may contain a radical polymerization initiator (polymerization catalyst or cross-linking agent) that generates radicals by light or/and heat.
  • a radical polymerization initiator polymerization catalyst or cross-linking agent
  • photopolymerization initiators include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2- Diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl Acetophenones such as phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; 2-ethylanthr
  • Thermal radical initiators include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy) Hexyne-3, di-t-butyl peroxide, t-butyl cumyl peroxide, 1,3-bis(butylperoxyisopropyl)benzene, ⁇ , ⁇ '-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(benzo
  • 2,3-dimethyl-2,3-diphenylbutane can also be used as a radical polymerization initiator.
  • the content of the radical polymerization initiator is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the phosphorus-containing (meth)acryloyl compound.
  • the flame-retardant resin composition of the present invention essentially contains a phosphorus-containing (meth)acryloyl compound represented by the general formula (1) as a reactive flame retardant, and the phosphorus content of the composition is preferably is 0.5 to 5.0% by weight, more preferably 1.0 to 4.0% by weight.
  • a filler can be added to the flame-retardant resin composition of the present invention.
  • fillers include those added to improve the heat resistance and flame retardancy of the cured product of the curable resin composition, and known fillers can be used, but are not particularly limited.
  • heat resistance, dimensional stability, flame retardancy, etc. can be further improved by incorporating a filler.
  • silica such as spherical silica, metal oxides such as alumina, titanium oxide and mica, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, talc, aluminum borate, barium sulfate, and calcium carbonate etc.
  • a metal hydroxide such as aluminum hydroxide or magnesium hydroxide
  • it acts as a flame retardant aid, and flame retardancy can be ensured even if the phosphorus content is low.
  • silica, mica, and talc are preferred, and spherical silica is more preferred.
  • these 1 type may be used independently and may be used in combination of 2 or more type.
  • the filler may be used as it is, or may be surface-treated with a silane coupling agent such as epoxysilane type or aminosilane type.
  • a silane coupling agent such as epoxysilane type or aminosilane type.
  • vinylsilane-type, methacryloxysilane-type, acryloxysilane-type, and styrylsilane-type silane coupling agents are preferable as the silane coupling agent.
  • the silane coupling agent may be added by an integral blend method instead of the method of surface-treating the filler in advance.
  • the content of the filler is preferably 10 to 200 parts by mass with respect to a total of 100 parts by mass of the solid content excluding the filler (including organic components such as monomers and flame retardants, excluding solvents). It is preferably 30 to 150 parts by mass.
  • the flame-retardant resin composition of the present invention may further contain additives other than the above.
  • additives include antifoaming agents such as silicone antifoaming agents and acrylic acid ester antifoaming agents, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes and pigments, lubricants, dispersants such as wetting and dispersing agents. agents and the like.
  • the cured product obtained by curing the flame-retardant resin composition of the present invention can be used as moldings, laminates, castings, adhesives, coatings, and films.
  • a cured product of a semiconductor encapsulating material is a cast or molded product, and methods for obtaining a cured product for such applications include casting a curable resin composition, or using a transfer molding machine, an injection molding machine, or the like.
  • a cured product can be obtained by molding using the resin and heating at 80 to 230° C. for 0.5 to 10 hours.
  • the flame-retardant resin composition of the present invention can also be used as a prepreg.
  • a prepreg When producing a prepreg, it is prepared in the form of a varnish for the purpose of impregnating a base material (fibrous base material) for forming a prepreg, or for the purpose of being used as a circuit board material for forming a circuit board, and then mixed with a resin varnish. can do.
  • This resin varnish is suitable for circuit boards and can be used as a varnish for circuit board materials.
  • the use of the circuit board material here specifically includes a printed wiring board, a printed circuit board, a flexible printed wiring board, a build-up wiring board, and the like.
  • the organic solvent used for the above resin varnish is not particularly limited as long as it does not inhibit the curing reaction.
  • ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate, propyl acetate and butyl acetate; polar solvents such as dimethylacetamide and dimethylformamide; aromatic hydrocarbon solvents such as toluene and xylene. It is also possible to use these alone or in combination of two or more. From the viewpoint of dielectric properties, aromatic hydrocarbons such as benzene, toluene and xylene are preferred.
  • the amount of the organic solvent used is preferably 5 to 900 parts by weight, more preferably 10 to 700 parts by weight, and particularly preferably 100 parts by weight of the curable resin composition of the present invention. is 20 to 500 parts by weight.
  • base materials such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. Used in conjunction with more than one species.
  • a coupling agent can be used for these base materials for the purpose of improving the adhesiveness at the interface between the resin and the base material, if necessary.
  • Common coupling agents such as silane coupling agents, titanate coupling agents, aluminum coupling agents and zircoaluminate coupling agents can be used as the coupling agent.
  • the prepreg As a method for obtaining the prepreg, there is a method of impregnating the base material with the above resin varnish and then drying it. Impregnation is performed by immersion (dipping), coating, or the like. The impregnation can be repeated multiple times as necessary, and at this time, the impregnation can be repeated using a plurality of solutions with different compositions and concentrations to finally adjust the desired resin composition and resin amount. It is possible. After impregnation, a prepreg can be obtained by drying by heating at 100 to 180° C. for 1 to 30 minutes.
  • the resin content in the prepreg is preferably 30 to 80% by weight.
  • the curable resin composition of the present invention can also be used as a laminate.
  • a laminate using prepreg one or more prepregs are laminated, metal foil is placed on one side or both sides to form a laminate, and this laminate is heated and pressed to be laminated and integrated.
  • the metal foil copper, aluminum, brass, nickel, or the like can be used alone, as an alloy, or as a composite metal foil.
  • the conditions for heating and pressurizing the laminate may be appropriately adjusted so as to cure the curable resin composition, but if the pressurization pressure is too low, air bubbles may form inside the resulting laminate. Since it may remain and the electrical characteristics may deteriorate, it is preferable to apply pressure under conditions that satisfy moldability.
  • the temperature can be set to 180 to 250° C.
  • the pressure to 49.0 to 490.3 N/cm 2 (5 to 50 kgf/cm 2 ), and the heating/pressurizing time to 40 to 240 minutes.
  • a multi-layer board can be produced by using the single-layer laminate board thus obtained as an inner layer material.
  • a circuit is formed on the laminate by an additive method, a subtractive method, or the like, and the surface of the formed circuit is treated with an acid solution for blackening to obtain an inner layer material.
  • An insulating layer is formed on one or both sides of the inner layer material with a resin sheet, a resin-coated metal foil, or a prepreg, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board. It is a thing.
  • the curable composition of the present invention can also be used for build-up films.
  • a method for producing a build-up film from the resin composition of the present invention includes, for example, a method of applying the above resin varnish onto a support film and drying to form a film-like insulating layer.
  • the film-like insulating layer thus formed can be used as a build-up film for multilayer printed wiring boards.
  • Phenyl glycidyl ether of the following structural formula 105 parts were charged into a separable glass flask equipped with a stirrer, thermometer, Dean-Stark device, and nitrogen gas introduction device, heated to 110°C, added 0.51 parts of triphenylphosphine, and toluene was removed. The temperature was further increased to 160° C. while the reaction was continued for 5 hours. Thereafter, the pressure is reduced to 1 kPa with a vacuum pump, toluene is completely distilled off, and the hydroxyl group-containing phosphorus compound A of the following structural formula is obtained. 250 parts of As a result of measuring the phosphorus content, it was 8.4%.
  • Synthesis Example 2 Synthesis of hydroxyl-containing phosphorus compound B Instead of phenyl glycidyl ether, 4-tert-butylphenyl glycidyl ether of the following structural formula The same procedure as in Synthesis Example 1 was carried out, except that 143 parts of triphenylphosphine was used and the amount of triphenylphosphine used was changed to 0.59 parts, and a hydroxyl group-containing phosphorus compound B of the following structural formula 290 parts of As a result of measuring the phosphorus content, it was 7.2%.
  • Example 1 Synthesis of phosphorus-containing methacryloyl compound A 160 parts of hydrogen group-containing phosphorus compound A, 160 parts of tetrahydrofuran, and 75 parts of triethylamine were placed in a separable glass flask equipped with a stirrer, thermometer, condenser, and dropping funnel. After preparation and dissolution, the mixture was cooled to 5°C or less in an ice bath. In a nitrogen atmosphere, methacryloyl chloride of the following structural formula 70 parts was added dropwise over 1 hour, and the reaction was further continued for 2 hours.
  • reaction solution was concentrated, dissolved in 442 parts of toluene, and then washed with an aqueous sodium carbonate solution and then with water. After washing with water, dehydration, filtration, and concentration of the solvent to adjust the solid content concentration to 50%, phosphorus-containing methacryloyl compound A of the following structural formula 340 parts of a toluene solution of The phosphorus content was 7.2%.
  • Example 2 Synthesis of phosphorus-containing methacryloyl compound B 150 parts of hydrogen group-containing phosphorus compound B, 150 parts of tetrahydrofuran, 36 parts of triethylamine, 4 are added to a separable glass flask equipped with a stirrer, thermometer, condenser, and dropping funnel. - 2.7 parts of dimethylaminopyridine was charged and dissolved at room temperature. In a nitrogen atmosphere, methacrylic anhydride of the following structural formula 67 parts was added dropwise over 1 hour, and the reaction was further continued at 50°C for 6 hours.
  • reaction solution was concentrated, dissolved in 422 parts of toluene, washed and concentrated in the same manner as in Example 1, and a phosphorus-containing methacryloyl compound B (the following structural formula) having a solid concentration of 50% was obtained. 314 parts of a toluene solution of The phosphorus content was 6.5%.
  • reaction solution was concentrated, dissolved in 444 parts of toluene, washed and concentrated in the same manner as in Example 1, and a phosphorus-containing methacryloyl compound C (the following structural formula) having a solid content concentration of 50% was obtained. 316 parts of a toluene solution of The phosphorus content was 6.8%.
  • reaction solution was concentrated, dissolved in 318 parts of toluene, washed and concentrated in the same manner as in Example 1, adjusted to a toluene solution with a solid concentration of 50%, and phosphorus-containing methacryloyl compound E (the following structural formula ) 235 parts of a solution of The phosphorus content was 6.2%.
  • Examples 4-9, Comparative Examples 4-12 ⁇ Adjustment of curable resin composition and preparation of cured product> Various components were blended in the proportions shown in Tables 2 and 3, toluene was used to prepare a varnish having a solid content of 50%, which was applied on a PET film and dried in an oven at 130°C for 5 minutes to prepare a film of the resin composition. . Next, this film was pulverized to obtain a resin composition powder. Further, this powder was sandwiched between mirror plates made of stainless steel together with a spacer, and molded in a vacuum oven at 210° C. for 90 minutes to obtain a sample of a cured product.
  • the obtained 8 sheets of prepreg and copper foil (manufactured by Mitsui Kinzoku Mining Co., Ltd., 3EC-III, thickness 35 ⁇ m) are stacked on top and bottom, and vacuum pressed at 2 MPa under temperature conditions of 130 ° C. x 15 minutes + 190 ° C. x 80 minutes. , a laminate having a thickness of 1.6 mm was obtained.
  • a flame retardant test piece was obtained by etching and cutting the copper foil. Using the flame retardant test piece, flame retardancy was evaluated, and the results are shown in Tables 2 and 3.
  • the phosphorus-containing (meth)acryloyl compound of the present invention can be used in a wide range of applications from building materials to electrical and electronic equipment, and is particularly useful as a reactive phosphorus-based flame retardant in electrical and electronic products, OA equipment, communication equipment, etc. .

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PCT/JP2023/005764 2022-03-03 2023-02-17 リン含有（メタ）アクリロイル化合物、その製造方法、これを含む難燃性術組成物および電子回路基板用積層板 WO2023167019A1 (ja)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07189128A (ja) * 1991-08-05 1995-07-25 Inst Textile De France 繊維材料に不燃性を付与する方法
EP1544227A1 (de) * 2003-12-17 2005-06-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verwendung hydroxylgruppenhaltiger Phosphinate als und zur Herstellung von Flammschutzmitteln, die sich zur Einbindung in Polymerharze eignen, damit hergestellte neue Phosphinate mit organisch polymerisierbaren Gruppen sowie flammgeschützte Polymerharze
JP2016003216A (ja) * 2014-06-18 2016-01-12 三光株式会社 リン含有エポキシ化合物、ジアステレオマー混合物及びリン含有エポキシ化合物の製造方法
JP2016526084A (ja) * 2013-05-28 2016-09-01 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド 非ハロゲン難燃性ポリマー

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07189128A (ja) * 1991-08-05 1995-07-25 Inst Textile De France 繊維材料に不燃性を付与する方法
EP1544227A1 (de) * 2003-12-17 2005-06-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verwendung hydroxylgruppenhaltiger Phosphinate als und zur Herstellung von Flammschutzmitteln, die sich zur Einbindung in Polymerharze eignen, damit hergestellte neue Phosphinate mit organisch polymerisierbaren Gruppen sowie flammgeschützte Polymerharze
JP2016526084A (ja) * 2013-05-28 2016-09-01 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド 非ハロゲン難燃性ポリマー
JP2016003216A (ja) * 2014-06-18 2016-01-12 三光株式会社 リン含有エポキシ化合物、ジアステレオマー混合物及びリン含有エポキシ化合物の製造方法

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