WO2024070886A1 - Composé phénolique contenant du phosphore, composition de résine durcissable contenant ledit composé phénolique contenant du phosphore, produit durci et procédé de production dudit composé phénolique contenant du phosphore - Google Patents

Composé phénolique contenant du phosphore, composition de résine durcissable contenant ledit composé phénolique contenant du phosphore, produit durci et procédé de production dudit composé phénolique contenant du phosphore Download PDF

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WO2024070886A1
WO2024070886A1 PCT/JP2023/034269 JP2023034269W WO2024070886A1 WO 2024070886 A1 WO2024070886 A1 WO 2024070886A1 JP 2023034269 W JP2023034269 W JP 2023034269W WO 2024070886 A1 WO2024070886 A1 WO 2024070886A1
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phosphorus
general formula
phenol compound
compound
containing phenol
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PCT/JP2023/034269
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English (en)
Japanese (ja)
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次俊 和佐野
和男 藤本
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日鉄ケミカル＆マテリアル株式会社
大八化学工業株式会社
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Publication of WO2024070886A1 publication Critical patent/WO2024070886A1/fr

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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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus

Definitions

  • the present invention relates to a reactive phosphorus compound, in particular a phosphorus-containing phenolic compound, which is useful as a flame retardant for thermosetting resins such as epoxy resins.
  • the present invention also relates to a curable resin composition containing the phosphorus-containing phenolic compound and a curable resin composition, and a method for producing the phosphorus-containing phenolic compound.
  • Plastic materials have excellent mechanical properties and moldability, making them suitable for a wide range of applications, from building materials to electrical and electronic equipment. However, most plastic materials are flammable, so flame retardancy is essential for their use in applications such as electrical and electronic products, office automation equipment, and communications equipment, to ensure safety against heat generation and ignition.
  • Additive flame retardants such as halogen-based flame retardants, inorganic flame retardants, and phosphorus-based flame retardants are commonly used as flame retardant technology for plastic materials, regardless of the type of resin or application.
  • halogen-based flame retardants mainly bromine-based
  • inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide have a flame retardant effect due to endothermic heat, but they must be added in large quantities to achieve sufficient flame retardancy, which causes a decrease in various properties of plastic molded products.
  • phosphorus-based flame retardants are widely used, which do not generate harmful substances and can be flame retarded with the addition of relatively small amounts, but they still have unavoidable effects on properties, such as a decrease in processability due to bleed-out, a decrease in glass transition temperature, etc.
  • Patent Document 1 discloses a phosphorus-containing epoxy resin obtained by reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as "DOPO") with quinones and then reacting with an epoxy resin.
  • DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • Patent Document 2 discloses a phenolic resin obtained by reacting bisphenol A with formaldehyde as a curing agent for epoxy resins, to obtain hydroxymethylbisphenol A, and then reacting with DOPO
  • Patent Document 3 discloses a phenolic resin to which phosphorus atoms have been introduced by reacting DOPO with anisaldehyde and then reacting with a triazine skeleton-containing phenolic resin.
  • Patent Document 4 discloses that phosphorus-containing active esters that have been introduced with a DOPO skeleton exhibit flame retardancy and low dielectric properties.
  • epoxy resins and phosphorus-containing curing agents that can be imparted with flame retardancy without reducing general properties such as heat resistance by introducing DOPO into the structure are widely known, but there is a problem that the DOPO skeleton is easily hydrolyzed, and the hydroxyl groups generated by hydrolysis cause a large change in dielectric properties after moisture absorption and water absorption.
  • Patent Document 5 discloses a phosphate ester-type phenolic compound that exhibits minimal change in dielectric properties after absorbing water, but the dielectric properties and heat resistance are insufficient, and there are still no flame retardants that are sufficient to meet high-level requirements.
  • the problem that the present invention aims to solve is to provide a phosphorus-containing phenolic compound that has excellent flame retardancy, heat resistance, and dielectric properties in the cured product, has a small water absorption rate, and exhibits little change in dielectric properties after absorbing water, a curable resin composition that contains the phosphorus-containing phenolic compound and a curable resin, an epoxy resin composition that uses the compound as a curing agent, a cured product thereof, and a method for producing the phosphorus-containing phenolic compound.
  • a phosphorus-containing phenolic compound with a specific structure has excellent heat resistance and dielectric properties, and undergoes little change in dielectric properties after absorbing water, which led to the invention.
  • the present invention relates to a phosphorus-containing phenol compound represented by the following formula (1).
  • Ar is an aromatic ring group having 6 to 30 carbon atoms which may have a substituent
  • R1 is independently hydrogen or a substituent represented by the following general formula (2), with at least one R1 containing a substituent represented by general formula (2).
  • m is an integer of 3 to 6.
  • R2 and R3 each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms, and n2 and n3 each independently represent an integer of 0 to 5.
  • phosphorus-containing phenol compounds in which Ar is an aromatic ring group selected from the group consisting of a benzene skeleton, a naphthalene skeleton, a biphenyl skeleton, and an anthracene skeleton are preferred, and phosphorus-containing phenol compounds in which Ar is a benzene skeleton are more preferred.
  • a phosphorus-containing phenolic compound in which m is 3 is more preferred.
  • Particularly preferred are phosphorus-containing phenolic compounds in which m is 3 and, for three OR1 groups in general formula (1), the compounds contain 10 to 80 mol % of a compound in which two R1s are hydrogen and one R1 is a substituent represented by general formula (2) (monosubstitution), 5 to 50 mol % of a compound in which one R1 is hydrogen and two R1s are substituents represented by general formula (2) (disubstitution), and 1 to 50 mol % of a compound in which three R1s are substituents represented by general formula (2) (trisubstitution).
  • the present invention is a method for producing a phosphorus-containing phenol compound, which comprises reacting 0.1 to 0.9 moles of a compound represented by general formula (4) with 1 mole of a hydroxyl group of a compound represented by general formula (3).
  • Ar and m are the same as those in formula (1).
  • X represents a halogen atom
  • R2, R3, n2, and n3 are each defined as in formula (2).
  • the present invention is a curable resin composition containing the above-mentioned phosphorus-containing phenolic compound and a curable resin.
  • a cured product is obtained by curing the above-mentioned curable resin composition.
  • the phosphorus-containing phenolic compound of the present invention exhibits minimal change in dielectric properties after absorbing water, making it extremely useful as a flame-retardant material for reducing transmission loss at higher frequencies associated with the increased amount of information processed by electronic devices.
  • Example 1 shows a GPC chart of the phosphorus-containing phenol compound obtained in Example 2. (The dotted line is the raw material, and the solid line is the product.)
  • the phosphorus-containing phenol compound of the present invention is represented by the following general formula (1).
  • Ar is an aromatic ring group having 6 to 30 carbon atoms which may have a substituent.
  • the aromatic ring group is not particularly limited, and examples thereof include monocyclic aromatic compounds such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine from which m hydrogen atoms have been removed; and condensed aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and a
  • the aromatic ring group may be a combination of a plurality of these aromatic compounds, and examples thereof include ring-assembled aromatic compounds such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl from which m hydrogen atoms have been removed.
  • ring-assembled aromatic compounds such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl from which m hydrogen atoms have been removed.
  • Preferred are benzene, naphthalene, biphenyl and anthracene, and more preferred is benzene.
  • the aromatic ring represented by Ar may contain a substituent other than -OR1.
  • substituents include an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms.
  • the alkyl group having 1 to 10 carbon atoms is not particularly limited, but includes methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, n-nonyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclononyl groups, of which methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups are preferred, and methyl and ethyl groups are even more preferred.
  • Alkoxy groups having 1 to 10 carbon atoms are not particularly limited, but examples include methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, butoxy groups, pentyloxy groups, hexyloxy groups, 2-ethylhexyloxy groups, octyloxy groups, and nonyloxy groups. These substituents may be used alone or in combination of two or more types.
  • m is an integer of 3 to 6, preferably 3 or 4, and more preferably 3.
  • R1 is independently hydrogen or a substituent represented by the following formula (2).
  • R2 and R3 each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms.
  • alkyl groups having 1 to 5 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, etc.
  • methyl, ethyl, propyl, and isopropyl are preferred from the viewpoint of reactivity in production and ease of availability, with the methyl group being particularly preferred.
  • n2 and n3 are each independently an integer of 0 to 5, preferably 0 or an integer of 2 or more, and more preferably 2.
  • the substitution positions of R2 and R3 on the benzene ring are not particularly limited, but it is preferable that each is independently present at the ortho or meta position with respect to the phosphate ester bond.
  • the presence of an alkyl group at the ortho position hydrophobically blocks the phosphate ester, reducing water absorption and suppressing hydrolysis, thereby further improving the properties of the phosphorus-containing phenol compound of the present invention.
  • alkyl groups are substituted at two ortho positions with respect to the phosphate ester bond, and n2 and n3 are preferably 2 or more.
  • the ratio of hydrogen in R1 and the substituent represented by general formula (2) in the phosphorus-containing phenol compound of the present invention is not particularly limited, but at least one R1 contains a substituent represented by general formula (2).
  • the phosphorus-containing phenol compound of the present invention can exhibit excellent flame retardancy.
  • the ratio of the substituent represented by general formula (2) in R1 as a compound (mixture) is preferably 10 mol % or more, more preferably 30 mol % or more, and even more preferably 50 mol % or more.
  • Examples of phosphorus-containing phenolic compounds of the present invention include, but are not limited to, compounds of the following structures and mixtures thereof:
  • the phosphorus-containing phenol compound of the present invention does not need to be used as a single compound, but may be a mixture containing multiple compounds with different numbers of substituents represented by general formula (2).
  • the phosphorus-containing phenol compound of the present invention can be obtained by reacting a polyhydric phenol compound represented by the general formula (3) described below with a phosphorus compound represented by the general formula (4). Since the raw material polyhydric phenol compound does not contain phosphorus, the introduction of the substituent represented by the general formula (2) can be determined by measuring the phosphorus content of the compound after the reaction.
  • the introduction of the substituent represented by the general formula (2) can be judged by the phosphorus content. If the phosphorus content is not 0, the introduction of the substituent represented by the general formula (2) can be judged, but if the phosphorus content is low, flame retardancy is not expressed, and from the viewpoint of flame retardancy, the higher the phosphorus content, the better. However, as the phosphorus content increases, the number of hydroxyl groups decreases, and heat resistance may be insufficient or bleed-out may occur. Therefore, the phosphorus content of the phosphorus-containing phenolic compound is preferably 1.5 to 15.0 mass%, more preferably 3.0 to 12.0 mass%, and even more preferably 5.0 to 10.0 mass%.
  • the hydroxyl equivalent of the phosphorus-containing phenol compound is in the range of 50 to 1000 g/eq, preferably 80 to 800 g/eq, and more preferably 100 to 600 g/eq.
  • the phosphorus-containing phenol compound of the present invention is preferably a mixture of the following general formulas (5), (6), and (7). More preferably, the compound contains 10 to 80 mol% of a compound (monosubstitution) represented by the following general formula (5) in which two R1s are hydrogen and one R1 is a substituent represented by general formula (2), 5 to 50 mol% of a compound (disubstitution) represented by the following general formula (6) in which one R1 is hydrogen and two R1s are substituents represented by general formula (2), and 1 to 50 mol% of a compound (trisubstitution) represented by the following general formula (7) in which three R1s are substituents represented by general formula (2), thereby obtaining a cured product with excellent balance of flame retardancy, heat resistance, and dielectric properties.
  • a compound (monosubstitution) represented by the following general formula (5) in which two R1s are hydrogen and one R1 is a substituent represented by general formula (2)
  • the monosubstitution is 20 to 70 mol%
  • the disubstitution is 10 to 40 mol%
  • the trisubstitution is 2 to 40 mol%. It is acceptable for unreacted raw material phenols to remain, but it is desirable that the amount is less than 30 mol%.
  • R2, R3, n2, and n3 are defined as in general formula (2).
  • compositions of the above general formulas (5), (6), and (7) can be confirmed by liquid chromatography, size exclusion chromatography, etc.
  • the phosphorus-containing phenolic compound of the present invention is an aromatic phosphate ester having one or more phenolic hydroxyl groups, and its production method conforms to a general method for producing an aromatic phosphate ester. That is, one example of the reaction form is an esterification reaction using phosphorus oxyhalide (phosphoryl halide) and phenols as raw materials, and the corresponding phosphate ester can be obtained by a dehydrohalogenation reaction.
  • phosphorus oxyhalide phosphoryl halide
  • this esterification reaction is carried out using a catalyst and/or removing the released hydrogen halide from the reaction system.
  • the released hydrogen halide e.g., hydrogen chloride
  • the released hydrogen halide is a gas, and since its volume increases when it is gasified, it is easily released outside the reaction system in the case of a highly reactive raw material, but in the case of a less reactive raw material, the amount of hydrogen halide released is small and it tends to remain in the system, which may cause a hydrolysis reaction. In such cases, it is effective to capture the generated hydrogen halide to prevent the hydrolysis reaction from occurring, and amines are sometimes used as hydrogen halide scavengers.
  • the phosphorus-containing phenol compound of the present invention is a compound represented by the above general formula (1), it is necessary to react a polyhydric hydroxy compound represented by the following general formula (3) corresponding to the general formula (1) as a raw material with a phenol and a phosphorus oxyhalide, which are raw materials for the phosphorus halide compound represented by the following general formula (4) corresponding to the above general formula (2).
  • a polyhydric hydroxy compound represented by the following general formula (3) corresponding to the general formula (1) as a raw material with a phenol and a phosphorus oxyhalide, which are raw materials for the phosphorus halide compound represented by the following general formula (4) corresponding to the above general formula (2).
  • Ar and m are the same as those in formula (1).
  • the phosphorus oxyhalide for example, phosphorus oxychloride (POCl3) is reacted with the phenols first to obtain the halogenated phosphorus compound represented by the following general formula (4), and then the obtained halogenated phosphorus compound represented by the general formula (4) is reacted with the polyhydric hydroxy compound represented by the general formula (3), thereby making it possible to efficiently obtain the target compound.
  • the phosphorus oxyhalide for example, phosphorus oxychloride (POCl3) is reacted with the phenols first to obtain the halogenated phosphorus compound represented by the following general formula (4), and then the obtained halogenated phosphorus compound represented by the general formula (4) is reacted with the polyhydric hydroxy compound represented by the general formula (3), thereby making it possible to efficiently obtain the target compound.
  • the phenols are mixed in a ratio of 2 moles per mole of the phosphorus oxyhalide.
  • the phenols are preferably in the range of 1.8 to 2.2 moles, more preferably 1.9 to 2.1 moles.
  • R2, R3, n2, and n3 are the same as those in formula (2), and X represents a halogen atom.
  • the phosphorus-containing phenol compound of the present invention can be obtained by reacting the hydroxyl groups of a polyhydric hydroxy compound represented by general formula (3) with a halogenated phosphorus compound represented by general formula (4). Therefore, by adjusting the molar ratio of the halogenated phosphorus compound of general formula (4) to the hydroxyl groups, it is possible to control the hydroxyl group equivalent and phosphorus content.
  • the molar ratio of the reaction is preferably 0.1 to 0.9 moles, more preferably 0.2 to 0.8 moles, and even more preferably 0.3 to 0.7 moles of the halogenated phosphorus compound represented by general formula (4) per mole of hydroxyl groups of the polyhydric hydroxy compound represented by general formula (3).
  • a ratio of 0.1 moles or less is not preferred because the phosphorus content decreases and flame retardancy is insufficient, while a ratio of 0.9 moles or more is not preferred because the number of hydroxyl groups, which are reactive groups, decreases and heat resistance is insufficient.
  • the curable flame-retardant resin composition of the present invention contains the above-mentioned phosphorus-containing phenolic compound as an essential component, and can be obtained by mixing a curable resin with a phosphorus-containing phenolic compound.
  • a curable resin there are no limitations on the curable resin, so long as it reacts with the hydroxyl group of the phosphorus-containing phenolic compound of the present invention, and examples of the curable resin include epoxy resins and maleimide resins.
  • Epoxy resins that can be used in the present curable resin composition are not particularly limited, but include, for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, phenol novolac type epoxy resins, naphthol novolac type epoxy resins, dicyclopentadiene type epoxy resins, phenol aralkyl type epoxy resins, naphthol type epoxy resins, naphthol aralkyl type epoxy resins, naphthalene type epoxy resins, glycidylamine type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, linear aliphatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane dimethanol type epoxy resins, trimethylol type epoxy resins, halogenated epoxy resins, triphen
  • the amounts of the phosphorus-containing phenolic compound and the epoxy resin are determined based on the phosphorus content of the resin composition.
  • the phosphorus content in the resin composition is preferably 0.5 to 5.0% by mass, and more preferably 1.0 to 4.0% by mass. If the phosphorus content is 0.5% by mass or less, flame retardancy is not exhibited, and if it is 5.0% by mass or more, the amount of phosphorus-containing phenolic compound is high, resulting in an excess of hydroxyl groups relative to epoxy groups, which is not preferred as it results in insufficient crosslinking and a brittle cured product.
  • an epoxy resin when used as a curable resin, it may contain a curing agent other than the phosphorus-containing phenolic compound of the present invention.
  • the amount of hardener other than the phosphorus-containing phenolic compound of the present invention is preferably such that the phosphorus content of the resin composition of the present invention is 0.5 to 5.0 mass %, and the molar ratio (Nh/Ne) of the total number of moles (Nh) of reaction points between the phosphorus-containing phenolic compound and the epoxy groups of the other hardener to the number of moles (Ne) of the epoxy groups is 0.7 to 1.3, preferably 0.9 to 1.1. Molar ratios outside this range are not preferred because they result in insufficient crosslinking and a brittle cured product.
  • the resin composition of the present invention may also contain a curable resin other than an epoxy resin.
  • curable resins other than an epoxy resin include vinyl ester resins, polyvinylbenzyl resins, unsaturated polyester resins, curable vinyl resins, radical polymerizable resins such as maleimide resins, and cyanate resins.
  • the curable resin composition of the present invention may contain a curing accelerator as necessary.
  • the curing accelerator used here include phosphorus-based compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts.
  • the amount of the curing accelerator added is preferably 0.1 to 10.0 parts by mass per 100 parts by mass of the total of the phosphorus-containing phenolic compound, the curable resin, and other curing agents.
  • the resin composition of the present invention can contain other components, such as thermosetting resins, thermoplastic resins, organic fillers, inorganic fillers, organic solvents, thickeners, defoamers, adhesion promoters, colorants, and additives, as appropriate.
  • thermoplastic resins include polystyrene, polyphenylene ether resin, polyetherimide resin, polyethersulfone resin, PPS resin, polycyclopentadiene resin, polycycloolefin resin, etc., known thermoplastic elastomers such as styrene-ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, etc., and rubbers such as polybutadiene and polyisoprene.
  • Preferred examples include polyphenylene ether resin (unmodified) and hydrogenated styrene-butadiene copolymer.
  • a filler can be blended into the curable resin composition of the present invention.
  • fillers include those added to enhance 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.
  • the heat resistance, dimensional stability, flame retardancy, etc. can be further improved.
  • Specific examples include 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.
  • metal hydroxides such as aluminum hydroxide and magnesium hydroxide are used, they act as flame retardant assistants, and flame retardancy can be ensured even with a low phosphorus content.
  • metal hydroxides such as aluminum hydroxide and magnesium hydroxide are used, they act as flame retardant assistants, and flame retardancy can be ensured even with a low phosphorus content.
  • silica, mica, and talc are preferred, and spherical silica is more preferred.
  • one of these may be used alone, or two or more may be used in combination.
  • the filler may be used as is, or may be surface-treated with a silane coupling agent such as a vinyl silane type, methacryloxy silane type, acryloxy silane type, or styryl silane type, or an epoxy silane type, amino silane type, or cationic silane type.
  • a silane coupling agent such as a vinyl silane type, methacryloxy silane type, acryloxy silane type, or styryl silane type, or an epoxy silane type, amino silane type, or cationic silane type.
  • the amount of filler is preferably 10 to 200 parts by mass, and more preferably 30 to 150 parts by mass, per 100 parts by mass of the total solids excluding the filler (including organic components such as monomers and flame retardants, but excluding solvents).
  • the curable resin composition of the present invention may further contain additives other than those mentioned above.
  • additives include defoamers such as silicone-based defoamers and acrylic acid ester-based defoamers, heat stabilizers, antistatic agents, UV absorbers, dyes and pigments, lubricants, dispersants such as wetting dispersants, etc.
  • the cured product obtained by curing the curable resin composition of the present invention can be used as a molded product, laminate, cast product, adhesive, coating, or film.
  • a cured product of a semiconductor encapsulation material is a cast product or molded product, and a method for obtaining a cured product for such applications is to cast the curable resin composition or mold it using a transfer molding machine or injection molding machine, and then heat it at 80 to 230°C for 0.5 to 10 hours to obtain a cured product.
  • the curable resin composition of the present invention can also be used as a prepreg.
  • the composition can be prepared in a varnish form to be used as a resin varnish for the purpose of impregnating a substrate (fibrous substrate) for forming a prepreg or for the purpose of using the composition as a circuit board material for forming a circuit board.
  • This resin varnish is suitable for circuit boards and can be used as a varnish for circuit board materials. Specific applications of the circuit board materials referred to here include printed wiring boards, printed circuit boards, flexible printed wiring boards, build-up wiring boards, etc.
  • the above resin varnish is prepared, for example, as follows. First, each component that can be dissolved in an organic solvent, such as the phosphorus-containing phenol compound of the present invention and the epoxy resin component, is put into an organic solvent and dissolved. At this time, heating may be performed as necessary. Then, as necessary, a component that is not dissolved in an organic solvent, such as an inorganic filler, is added, and dispersed using a ball mill, a bead mill, a planetary mixer, a roll mill, or the like, to prepare a varnish-like curable resin composition.
  • the organic solvent used here is not particularly limited as long as it dissolves the resin component used in the epoxy resin composition of the present invention and 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, and the like can be used alone or in combination of two or more of them.
  • the amount of organic solvent used is preferably 5 to 900% by mass, more preferably 10 to 700% by mass, and particularly preferably 20 to 500% by mass, relative to 100% by mass of the curable resin composition of the present invention.
  • Suitable materials are used as the substrates used to create prepregs, and examples of such substrates include glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, and paper, which may be used alone or in combination of two or more. If necessary, coupling agents may be used with these substrates to improve adhesion at the interface between the resin and the substrate. Common coupling agents include silane coupling agents, titanate coupling agents, aluminum-based coupling agents, and zircoaluminate coupling agents.
  • the prepreg of the present invention can be obtained by impregnating a substrate with the resin varnish and then drying it. Impregnation is performed by dipping, coating, etc. Impregnation can be repeated multiple times as necessary, and in this case, it is also possible to repeat impregnation using multiple solutions with different compositions and concentrations to adjust to the final desired resin composition and resin amount.
  • the substrate can be heated and dried at 100 to 180°C for 1 to 30 minutes to obtain a prepreg.
  • the amount of resin in the prepreg is preferably 30 to 80% by mass.
  • the curable resin composition of the present invention can also be used as a laminate.
  • a laminate is formed using prepregs, one or more prepregs are laminated, metal foil is placed on one or both sides to form a laminate, and the laminate is heated and pressed to laminate and integrate it.
  • the metal foil can be a single metal foil, an alloy metal foil, or a composite metal foil such as copper, aluminum, brass, or nickel.
  • the conditions for heating and pressing the laminate can be appropriately adjusted to the conditions under which the curable resin composition is cured, but if the pressure is too low, air bubbles may remain inside the obtained laminate and the electrical properties may deteriorate, so it is preferable to pressurize under conditions that satisfy the moldability.
  • the temperature can be set to 180 to 230°C, the pressure to 49.0 to 490.3 N/cm2 (5 to 50 kgf/cm2), and the heating and pressing time to 40 to 240 minutes.
  • a multilayer board can be produced by using the single-layer laminate obtained in this way as an inner layer material.
  • a circuit is first formed on the laminate using an additive or subtractive method, and the surface of the formed circuit is then treated with an acid solution for blackening to obtain an inner layer material.
  • An insulating layer is formed on one or both circuit-forming surfaces of this inner layer material using a resin sheet, metal foil with resin, or prepreg, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board.
  • a method for producing a build-up film from the curable composition of the present invention includes, for example, applying the above-mentioned resin varnish onto a support film and drying it 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.
  • the drying step is preferably carried out so that the organic solvent content in the build-up film resin composition layer is 10% by mass or less, and preferably 5% by mass or less. Drying conditions vary depending on the type of organic solvent in the varnish and the amount of organic solvent, but drying can be carried out at 50 to 160°C for about 3 to 20 minutes.
  • the thickness of the build-up film formed on the support is usually equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of a circuit board is usually in the range of 5 to 70 ⁇ m, it is preferable that the thickness of the resin composition layer is 10 to 100 ⁇ m.
  • the build-up film of the present invention is protected by a protective film, since this can prevent the adhesion of dirt and the like to the surface and prevent scratches.
  • the above-mentioned support film and protective film may be made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate; polyimide; and even release paper and metal foils such as copper foil and aluminum foil.
  • the support film and protective film may be subjected to a mud treatment, corona treatment, or release treatment.
  • the thickness of the support film is not particularly limited, but is usually in the range of 10 to 150 ⁇ m, and preferably in the range of 25 to 50 ⁇ m.
  • the thickness of the protective film is preferably 1 to 40 ⁇ m.
  • the support film described above is peeled off after laminating it onto the circuit board, or after forming an insulating layer by heat curing. Peeling off the support film after the adhesive film has been heat cured can prevent curing inhibition caused by oxygen during the curing process, and can also prevent the adhesion of dirt, etc. When peeling off after curing, the support film is usually subjected to a release treatment beforehand.
  • Molecular weight and molecular weight distribution of polymer The molecular weight and molecular weight distribution of the phosphorus-containing phenol compound were measured using GPC (Tosoh Corporation, HLC-8120GPC) with tetrahydrofuran as a solvent, a flow rate of 1.0 ml/min, a column temperature of 38° C., and a calibration curve based on monodisperse polystyrene.
  • Phosphorus content Sulfuric acid, hydrochloric acid, and perchloric acid were added to the sample, which was then heated and wet-ashed to convert all phosphorus atoms into orthophosphate. Metavanadate and molybdate were reacted in the sulfuric acid acid solution, and the absorbance at 420 nm of the resulting phosphorus vanadate molybdate complex was measured. The phosphorus atom content was expressed in mass% based on a calibration curve previously prepared using potassium dihydrogen phosphate.
  • Glass transition temperature Measured from the baseline shift using a differential scanning calorimeter manufactured by Hitachi High-Tech Science Corporation at a heating rate of 10° C./min.
  • Dielectric constant and dielectric loss tangent The dielectric constant (Dk) and dielectric loss tangent (Df) at a frequency of 1 GHz were determined by a capacitance method in an environment of 25° C. and humidity of 60% using a material analyzer (manufactured by AGILENT Technologies) in accordance with the IPC-TM-6502.5.5.9 standard.
  • Flame retardancy Evaluated by the vertical method using five test pieces in accordance with UL 94. The evaluation was recorded as V-0, V-1, or V-2.
  • Water absorption In accordance with JIS K 7209, a cured sample was immersed in water at 23° C. and the saturated water content was determined.
  • Rate of change in dielectric properties after water absorption The rate of change was calculated from the measured value (A1) of the cured sample before the water absorption test and the measured value (A2) after water absorption according to the following formula.
  • Dielectric property change rate (%) (A2 - A1) / A1 x 100
  • Synthesis Example 1 Synthesis of di-2,6-xylyl phosphorochloridate (DXPC) Into a 2 L four-neck flask equipped with a stirrer, a thermometer, and a hydrochloric acid recovery device (a condenser connected to a water scrubber), 767 g (5 mol) of phosphorus oxychloride (structural formula below), 2,6-dimethylphenol (structural formula below) 1200 g (9.8 mol), 140 g of xylene as a solvent and 6.2 g (0.065 mol) of magnesium chloride as a catalyst were charged.
  • DXPC di-2,6-xylyl phosphorochloridate
  • the resulting mixed solution was gradually heated to a temperature of 160°C over about 3 hours while stirring to react, and the generated hydrogen chloride gas was collected with a water scrubber. Thereafter, the pressure in the flask was gradually reduced to 20 kPa at the same temperature, and xylene, unreacted phosphorus oxychloride and 2,6-dimethylphenol, and by-product hydrogen chloride were removed to obtain 1700 g of a reaction product mainly composed of di-2,6-xylyl phosphorochloridate (DXPC: structural formula below). The chlorine content of the reaction mixture was 10.9% by mass.
  • DXPC di-2,6-xylyl phosphorochloridate
  • Example 1 Synthesis of Phosphorus-Containing Phenol (Compound A) Into a 200 mL four-neck flask equipped with a stirrer, a thermometer, and a hydrochloric acid recovery device (a condenser connected to a water scrubber), 51.6 g of mesitylene, 12.6 g (0.1 mol) of phloroglucinol (structural formula below), 21.8 g (0.06 mol) of di-2,6-xylyl phosphorochloridate obtained in Synthesis Example 1 and 0.4 g (0.004 mol) of anhydrous magnesium chloride as a catalyst were charged.
  • a hydrochloric acid recovery device a condenser connected to a water scrubber
  • the compound contained 68 mol % of a compound in which one hydroxyl group of phloroglucinol had reacted with di-2,6-xylyl phosphorochloridate (monosubstitution, structural formula below), 10 mol % of a compound in which two hydroxyl groups had reacted (disubstitution, structural formula below), 2 mol % of a compound in which three hydroxyl groups had reacted (trisubstitution, structural formula below), and 20 mol % of phloroglucinol.
  • Example 2 Synthesis of phosphorus-containing phenol (compound B) 110.9 g of mesitylene, 12.6 g (0.1 mol) of phloroglucinol, 54.5 g (0.15 mol) of di-2,6-xylyl phosphorochloridate, and 0.8 g (0.008 mol) of anhydrous magnesium chloride as a catalyst were charged into a 200 mL four-neck flask equipped with a stirrer, a thermometer, and a hydrochloric acid recovery device (a condenser connected to a water scrubber). The resulting mixed solution was gradually heated to 155°C while stirring, and after reaching 155°C, the mixture was reacted for 18 hours and the generated hydrogen chloride was collected.
  • compound B 110.9 g of mesitylene, 12.6 g (0.1 mol) of phloroglucinol, 54.5 g (0.15 mol) of di-2,6-xylyl phosphorochloridate, and 0.8 g
  • Compound B had a hydroxyl equivalent of 412 g/eq and a phosphorus content of 8.4% by mass.
  • the compound contained 39.5 mol % of a compound in which one hydroxyl group of phloroglucinol had reacted with di-2,6-xylyl phosphorochloridate (monosubstitution product), 34.0 mol % of a compound in which two hydroxyl groups had reacted (disubstitution product), 25.0 mol % of a compound in which three hydroxyl groups had reacted (trisubstitution product), and 1.5 mol % of phloroglucinol.
  • the resulting mixed solution was gradually heated to 155°C while stirring, and after reaching 155°C, the mixture was reacted for 18 hours and the generated hydrogen chloride was collected. After cooling to 60°C, 60 g of ethyl acetate was added, and the mixture was subjected to acid washing, neutralization, and two water washings, and the solvent was removed to obtain 51.2 g of compound C.
  • Compound C had a hydroxyl equivalent of 587 g/eq and a phosphorus content of 9.0% by mass.
  • the compound contained 25 mol % of a compound in which one hydroxyl group of phloroglucinol had reacted with di-2,6-xylyl phosphorochloridate (mono-substitution product), 35 mol % of a compound in which two hydroxyl groups had reacted (di-substitution product), and 40 mol % of a compound in which three hydroxyl groups had reacted (tri-substitution product).
  • the mixed solution in the four-neck flask was heated to a temperature of 20° C. while stirring, and while maintaining the same temperature (20° C.), mono 2,6-dimethylphenyl phosphorodichloridate in the dropping funnel was dropped over 2 hours. After the dropwise addition was completed, the mixture was heated to 65° C. and stirred for 5 hours to obtain a reaction product.
  • the obtained reaction product was washed with dilute hydrochloric acid and water, heated to a temperature of 150° C., reduced pressure to 2 kPa to distill off water, toluene, and low boiling points, and cooled to room temperature to obtain 330 g of a black-brown solid (compound D) having the following structure.
  • a varnish was prepared by mixing the various components in the ratios shown in Table 1, and was then applied to a PET film and dried in an oven at 130°C for 5 minutes to prepare a film of the resin composition. The film was then pulverized to obtain a powder of the resin composition. The powder was then sandwiched between a stainless steel mirror plate and a spacer, molded in a vacuum oven at 190°C for 90 minutes, and cured at 200°C for 5 hours to obtain a cured sample. The glass transition temperature and dielectric properties were evaluated using the cured sample.
  • a varnish was prepared by mixing the various components in the ratios shown in Table 1. This resin varnish was impregnated into a glass cloth (manufactured by Nitto Boseki Co., Ltd.; 7628 type; product number H258), which was then dried by heating at 130° C. for 5 minutes to obtain a prepreg. Eight sheets of the obtained prepreg were laminated with copper foil (3EC-III, thickness 35 ⁇ m, manufactured by Mitsui Mining & Smelting Co., Ltd.) on top and bottom, and vacuum pressed at 2 MPa under temperature conditions of 130°C x 15 minutes + 190°C x 80 minutes to obtain a laminated board with a thickness of 1.6 mm. The copper foil was etched and cut to obtain a flame retardant test piece. The flame retardant test piece was used to evaluate the flame retardancy.
  • ESN-475V Naphthalene type epoxy resin (epoxy equivalent: 325 g/eq) manufactured by Nippon Steel Chemical & Material Co., Ltd.
  • SN-485 Naphthol resin (hydroxyl equivalent: 210 g/eq) manufactured by Nippon Steel Chemical & Material Co., Ltd.
  • TPP Triphenyl phosphate (phosphorus content 9.5% by mass) manufactured by Daihachi Chemical Industry Co., Ltd.
  • PX-200 Aromatic condensed phosphate ester (phosphorus content 9.02% by mass) manufactured by Daihachi Chemical Industry Co., Ltd.
  • LC-950PM60 DOPO-BPA manufactured by Shin A Co., Ltd. (hydroxyl equivalent: 570 g/eq, phosphorus content: 10.9% by mass, solid content: 60% by mass)
  • 2E4MZ 2-ethyl-4-methylimidazole manufactured by Shikoku Kasei Co., Ltd.
  • the phosphorus-containing phenol compound of the present invention is useful for imparting flame retardancy to plastic materials, for example, thermosetting resins such as epoxy resins, used in electric and electronic products, office automation equipment, communication equipment, building materials, etc., and is particularly useful as a flame-retardant material for reducing transmission loss at higher frequencies associated with increased information processing volume in electronic devices.

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Abstract

L'invention concerne un composé phénolique contenant du phosphore, un produit durci de celui-ci présente une excellente ininflammabilité, une excellente résistance à la chaleur et de très bonnes propriétés diélectriques, un faible taux d'absorption d'humidité et un faible changement des propriétés diélectriques après absorption d'humidité.　L'invention concerne un composé phénolique contenant du phosphore représenté par la formule générale (1). Dans la formule générale (1), Ar est un groupe cyclique aromatique en C6-30 éventuellement substitué, R1 sont chacun indépendamment hydrogène ou un substituant représenté par la formule générale (2), et au moins un R1 contient un substituant représenté par la formule générale (2), m est un nombre entier de 3 à 6.
PCT/JP2023/034269 2022-09-30 2023-09-21 Composé phénolique contenant du phosphore, composition de résine durcissable contenant ledit composé phénolique contenant du phosphore, produit durci et procédé de production dudit composé phénolique contenant du phosphore WO2024070886A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090073474A (ko) * 2007-12-31 2009-07-03 제일모직주식회사 새로운 인계 난연제, 그 제조방법 및 이를 함유하는 난연열가소성 수지 조성물
KR20210037872A (ko) * 2019-09-30 2021-04-07 신일화학공업(주) 투명성, 난연성, 열적 및 기계적 물성이 우수한 폴리카보네이트 수지 조성물, 이를 이용한 폴리카보네이트 난연 시트 제조 방법
WO2021256351A1 (fr) * 2020-06-15 2021-12-23 日鉄ケミカル＆マテリアル株式会社 Composé phénolique contenant du phosphore, composition de résine durcissable le contenant et objet durci ainsi obtenu

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090073474A (ko) * 2007-12-31 2009-07-03 제일모직주식회사 새로운 인계 난연제, 그 제조방법 및 이를 함유하는 난연열가소성 수지 조성물
KR20210037872A (ko) * 2019-09-30 2021-04-07 신일화학공업(주) 투명성, 난연성, 열적 및 기계적 물성이 우수한 폴리카보네이트 수지 조성물, 이를 이용한 폴리카보네이트 난연 시트 제조 방법
WO2021256351A1 (fr) * 2020-06-15 2021-12-23 日鉄ケミカル＆マテリアル株式会社 Composé phénolique contenant du phosphore, composition de résine durcissable le contenant et objet durci ainsi obtenu

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* Cited by examiner, † Cited by third party
Title
HAI VOTHI; SOEKMIN HALM; CONGTRANH NGUYEN; IMHYUCK BAE; JINHWAN KIM: "Thermal stabilities and flame retardancies of phloroglucinol‐based organo phosphates when applied to polycarbonate", FIRE AND MATERIALS, NEW YORK, NY, US, vol. 38, no. 1, 24 July 2012 (2012-07-24), US , pages 36 - 45, XP071613339, ISSN: 0308-0501, DOI: 10.1002/fam.2158 *
RAPHAËL MÉNARD: "Synthesis of biobased phosphate flame retardants", PURE & APPLIED CHEMISTRY, PERGAMON PRESS, OXFORD, GB, vol. 86, no. 11, 1 November 2014 (2014-11-01), GB , pages 1637 - 1650, XP093156691, ISSN: 0033-4545, DOI: 10.1515/pac-2014-0703 *

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