WO2023007982A1 - Composé de phosphore ayant un cycle isocyanurate, son procédé de synthèse et utilisation dudit composé de phosphore ayant un cycle isocyanurate - Google Patents

Composé de phosphore ayant un cycle isocyanurate, son procédé de synthèse et utilisation dudit composé de phosphore ayant un cycle isocyanurate Download PDF

Info

Publication number
WO2023007982A1
WO2023007982A1 PCT/JP2022/024453 JP2022024453W WO2023007982A1 WO 2023007982 A1 WO2023007982 A1 WO 2023007982A1 JP 2022024453 W JP2022024453 W JP 2022024453W WO 2023007982 A1 WO2023007982 A1 WO 2023007982A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
phosphorus compound
resin composition
carbon atoms
same
Prior art date
Application number
PCT/JP2022/024453
Other languages
English (en)
Japanese (ja)
Inventor
隆志 柏原
僚祐 塩入
和徳 青木
岳 熊野
Original Assignee
四国化成工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2021134480A external-priority patent/JP2023020775A/ja
Application filed by 四国化成工業株式会社 filed Critical 四国化成工業株式会社
Publication of WO2023007982A1 publication Critical patent/WO2023007982A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • 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
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C08K5/5455—Silicon-containing compounds containing nitrogen containing at least one group
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C09J171/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • C09K21/10—Organic materials containing nitrogen
    • 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
    • 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 a novel phosphorus compound having an isocyanurate ring, a method for synthesizing the phosphorus compound having the isocyanurate ring, and utilization of the phosphorus compound having the isocyanurate ring.
  • Flame retardants used in resin materials include inorganic flame retardants and organic flame retardants.
  • Inorganic flame retardants have excellent dielectric properties, but because they exhibit water absorption and hydrolyzability, they tend to cause deterioration over time of cured products. had a problem.
  • phosphorus compounds, which are organic flame retardants have plasticity, there is a problem that increasing the amount of addition to enhance flame retardancy impairs the mechanical strength of the cured product.
  • Patent Document 1 proposes (2,5-dimethacryloxyphenyl)diphenylphosphine oxide and analogues thereof as flame retardants.
  • resin compositions using these compounds still have room for improvement in terms of low thermal expansion, heat resistance, mechanical strength and electrical properties.
  • An object of the present invention is to provide a novel phosphorus compound having an isocyanurate ring, a method for synthesizing the phosphorus compound, a flame retardant containing the phosphorus compound, and a resin composition containing the phosphorus compound and a resin component. and A further object is to provide a prepreg, a resin-coated metal foil, a thermosetting resin film, a metal-clad laminate, a printed wiring board, and an adhesive using the resin composition.
  • the present inventors have made intensive studies to solve the above problems, and as a result, a phosphorus compound having an isocyanurate ring obtained by reacting a certain phosphorus compound with a certain isocyanurate compound , recognized that the intended purpose could be achieved, and completed the present invention. That is, the first invention is a phosphorus compound having an isocyanurate ring represented by the chemical formula (I).
  • R 1 represents an alkyl group having 1 to 20 carbon atoms, an aryl group, or a benzyl group
  • R 2 represents a group represented by formula (1).
  • R 1 and R 2 are linked may form a ring
  • R 3 is the same or different and represents an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms
  • R 4 is the same or different and is hydrogen represents an atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a benzyl group, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms
  • Y is the same or different and each has 1 to 20 carbon atoms. 20 alkylene group).
  • the second invention is a phosphorus compound having an isocyanurate ring represented by the chemical formula (I-1).
  • the third invention is a phosphorus compound having an isocyanurate ring represented by chemical formula (I-2).
  • a fourth invention is a method for synthesizing a phosphorus compound having an isocyanurate ring according to the first invention, comprising a step of reacting a phosphorus compound represented by the chemical formula (II) with an isocyanurate compound represented by the chemical formula (III). is.
  • R 1 is the same as defined above, and R 8 represents -YX. Alternatively, R 1 and R 8 may be linked to form a ring.
  • Y is the same as defined above.
  • X is the same or different and represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a mesyloxy group (OMs), a tosyloxy group (OTs), or a trifluoromethanesulfonyloxy group (OTf).
  • a fifth invention is a flame retardant containing the phosphorus compound having an isocyanurate ring according to any one of the first to third inventions.
  • a sixth invention is a resin composition containing the phosphorus compound having an isocyanurate ring according to any one of the first to third inventions and a resin component.
  • a seventh invention is the resin composition of the sixth invention, wherein the resin component is a polyphenylene ether resin.
  • An eighth invention is a prepreg comprising the resin composition of the sixth invention or the seventh invention and a substrate.
  • a ninth invention is a resin-coated metal foil comprising a resin layer containing the resin composition of the sixth or seventh invention or a semi-cured product of the resin composition, and a metal foil.
  • a tenth invention is a thermosetting resin film formed from the resin composition of the sixth invention or the seventh invention.
  • An eleventh invention is a metal-clad laminate comprising an insulating layer containing a cured product of the resin composition of the sixth invention or the seventh invention, and a metal foil.
  • a twelfth invention is a printed wiring board comprising an insulating layer containing a cured product of the resin composition of the sixth or seventh invention, or a cured product of the thermosetting resin film of the tenth invention, and wiring. is.
  • a thirteenth invention is an adhesive containing the resin composition of the sixth invention or the seventh invention as a component.
  • the phosphorus compound having an isocyanurate ring of the present invention is a novel phosphorus compound having an isocyanurate ring. Such phosphorus compounds are expected to be used as flame retardants for resins. Then, the phosphorus compound having an isocyanurate ring of the present invention has an isocyanurate ring and an unsaturated bond group in the molecule, so when used as a resin raw material (resin material), a conventional phosphorus compound can be used. It is expected that a cured product having low thermal expansion, heat resistance, adhesiveness (adhesion), mechanical properties, electrical properties and flame retardancy will be obtained. Therefore, the resin composition of the present invention can be suitably used as a material for printed wiring boards and the like. Furthermore, the adhesive of the present invention is expected to be excellent in flame retardancy, low thermal expansion, heat resistance, adhesion, mechanical properties and electrical properties.
  • FIG. 1 is an IR spectrum chart of the white powder obtained in Example 1.
  • FIG. 4 is an IR spectrum chart of the white powder obtained in Example 2.
  • FIG. 1 is an IR spectrum chart of the white powder obtained in Example 1.
  • the present invention relates to a phosphorus compound having an isocyanurate ring represented by the above chemical formula (I) (hereinafter sometimes referred to as "the phosphorus compound of the present invention").
  • the phosphorus compound of the present invention includes a phosphorus compound represented by the chemical formula (I-1) and a phosphorus compound represented by the chemical formula (I-2).
  • R 1 represents an alkyl group having 1 to 20 carbon atoms , an aryl group or a benzyl group
  • R 4 is the same or different and represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a benzyl group, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms.
  • Y are the same or different and represent an alkylene group having 1 to 20 carbon atoms.
  • R 3 represents an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms
  • R 4 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a benzyl group
  • Y represents an alkylene group having 1 to 20 carbon atoms.
  • Examples of the phosphorus compound represented by the chemical formula (I-1) include phosphorus compounds represented by the chemical formulas (I-1-1) to (I-1-12). Further, examples of the phosphorus compound represented by the chemical formula (I-2) include phosphorus compounds represented by the chemical formulas (I-2-1) to (I-2-3).
  • Examples of the alkyl group having 1 to 20 carbon atoms represented by R 1 and R 4 include chain or branched alkyl groups having 1 to 20 carbon atoms, and specifically, methyl group, ethyl group, n -propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group , pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like.
  • Aryl groups represented by R 1 and R 4 include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5- xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,4,6-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6- trimethylphenyl group, 2,4,5-trimethylphenyl group, 2,3,5,6-tetramethylphenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group and the like.
  • R 1 and R 2 may be linked to form a ring as described above.
  • Examples of R 1 and R 2 linked to form a ring include phosphorus compounds represented by the chemical formula (I-2).
  • alkenyl group having 2 to 20 carbon atoms represented by R 3 and R 4 examples include chain or branched alkenyl groups having 2 to 20 carbon atoms, specifically vinyl group, allyl group, iso propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group , hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icosenyl group and the like.
  • the alkynyl group having 2 to 20 carbon atoms represented by R 3 and R 4 includes a chain or branched alkynyl group having 2 to 20 carbon atoms, and specifically, an ethynyl group and a 1-propynyl group.
  • 2-propynyl group 1-butynyl group, 2-butynyl group, 3-butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, undecynyl group, dodecynyl group, tridecynyl group, tetradecynyl group , pentadecynyl group, hexadecynyl group, heptadecynyl group, octadecynyl group, nonadecynyl group, icosinyl group and the like.
  • Examples of the alkylene group having 1 to 20 carbon atoms represented by Y include linear or branched alkylene groups having 1 to 20 carbon atoms, specifically, methylene group, methylmethylene group, dimethylene group, trimethylene group, ethylmethylene group, dimethylmethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group and the like.
  • R 1 is preferably an alkyl group having 1 to 5 carbon atoms, a phenyl group, a 2,6-xylyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group and a benzyl group.
  • R 3 and R 4 are the same as each other, and are preferably an alkenyl group having 2 to 4 carbon atoms or an alkynyl group having 2 to 4 carbon atoms.
  • Y is preferably a methylene group.
  • R 3 and R 4 are the same as each other, and are preferably an alkenyl group having 2 to 4 carbon atoms or an alkynyl group having 2 to 4 carbon atoms.
  • Y is preferably a methylene group.
  • the phosphorus compound of the present invention can be synthesized by reacting a phosphorus compound represented by the chemical formula (II) with an isocyanurate compound represented by the chemical formula (III).
  • the phosphorus compound represented by the chemical formula (II) includes the phosphorus compound represented by the chemical formula (II-1) and the phosphorus compound represented by the chemical formula (II-2).
  • R 1 and Y are the same as defined above.
  • X is the same or different, fluorine atom, chlorine atom, bromine atom, iodine atom, mesyloxy group (OMs), tosyloxy group (OTs) or trifluoromethane represents a sulfonyloxy group (OTf).
  • R 1 and R 8 may be linked to form a ring as described above.
  • Examples of R 1 and R 8 linked to form a ring include phosphorus compounds represented by the chemical formula (II-2).
  • Phosphorus compounds represented by chemical formula (II-1) include, for example, phosphorus compounds represented by chemical formulas (II-1-1) to (II-1-10). Further, examples of the phosphorus compound represented by the chemical formula (II-2) include phosphorus compounds represented by the chemical formulas (II-2-1) to (II-2-4).
  • phosphorus compounds can be used by purchasing commercially available reagents, for example, Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 44B(6), 1248-1251(2005), RSC Advances, 6( 57), 52485-52394 (2016), Youji Huaxue, 13(5), 527-532(1993), Agricultural and Biological Chemistry, 46(2), 411-418(1982), etc. Can be synthesized.
  • Examples of isocyanurate compounds represented by chemical formula (III) include isocyanurate compounds represented by chemical formulas (III-1) to (III-3).
  • isocyanurate compounds can be used by purchasing commercially available reagents, or can be synthesized, for example, according to the method described in JP-A-2016-216399.
  • Reaction scheme (A) shows an example of synthesizing a phosphorus compound represented by the chemical formula (I-1) by reacting a phosphorus compound represented by the chemical formula (II-1) with an isocyanurate compound represented by the chemical formula (III). shown in An example of synthesizing the phosphorus compound represented by the chemical formula (I-2) by reacting the phosphorus compound represented by the chemical formula (II-2) with the isocyanurate compound represented by the chemical formula (III) is shown in the reaction scheme ( B).
  • the amount (charged amount) of the isocyanurate compound represented by the chemical formula (III) is 2 to 2 to the amount (charged amount) of the phosphorus compound represented by the chemical formula (II-1) An appropriate ratio within the range of 4-fold molar is preferable.
  • the amount (charged amount) of the isocyanurate compound represented by the chemical formula (III) is 1 to An appropriate ratio within the range of 2-fold molar is preferable.
  • reaction schemes (A) and (B) it is preferable to use a base (a) for removing the acid by-produced as the reaction progresses. Moreover, if necessary, a reaction catalyst (b) and a reaction solvent (c) may be used as appropriate.
  • Examples of the base (a) include trimethylamine, triethylamine, N,N-diisopropylethylamine, diazabicyclononene, diazabicycloundecene, pyridine, imidazole, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide.
  • the amount (amount charged) of the base (a) is 2 to 5 times the amount (amount charged) of the phosphorus compound represented by the chemical formula (II-1). An appropriate ratio is preferable.
  • the amount (amount charged) of the base (a) used is 1 to 2.5 times the molar amount (amount charged) of the phosphorus compound represented by the chemical formula (II-2). An appropriate ratio within the range is preferable.
  • reaction catalyst (b) examples include alkali metal iodide salts such as lithium iodide, sodium iodide and potassium iodide. These may be used alone or in combination of two or more.
  • the amount (charged amount) of the reaction catalyst (b) used is 0.01 to 0.3 with respect to the used amount (charged amount) of the phosphorus compound represented by the chemical formula (II-1). It is preferable to use an appropriate ratio within the range of double moles.
  • the amount (charged amount) of the reaction catalyst (b) used is 0.01 to 0.3 with respect to the used amount (charged amount) of the phosphorus compound represented by the chemical formula (II-2). It is preferable to use an appropriate ratio within the range of double moles.
  • the reaction solvent (c) is not particularly limited as long as it does not inhibit the reaction. Solvents such as tetrahydrofuran, dioxane, ethyl acetate, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexamethylphosphoric acid triamide, water, etc., and if necessary, Suitable amounts thereof can be used in combination.
  • reaction temperature is preferably set in the range of 50 to 140°C.
  • the reaction time is appropriately set according to the set reaction temperature, but is preferably set within the range of 1 to 30 hours.
  • the target phosphorus compound of the present invention can be isolated from the obtained reaction solution (reaction mixture) by means of, for example, concentration of the reaction solution by distilling off the reaction solvent, solvent extraction, or the like. . Furthermore, if necessary, purification can be carried out using means such as washing with water, etc., treatment with activated carbon, silica gel chromatography, recrystallization, and the like.
  • the flame retardant and resin composition of the invention contain the phosphorus compound of the invention. Since the phosphorus compound of the present invention has a high flame retardant effect, it can be suitably used as a flame retardant for resins. By containing the phosphorus compound of the present invention in the resin composition, the cured product (molded product) of the resin composition exhibits excellent flame retardancy.
  • the resin composition of the present invention contains other flame retardants, polymerizable components, polymerization initiators, reactive diluents, fluororesins, inorganic fillers, It may contain additives.
  • the resin composition means the state of the mixture before curing.
  • the resin component (including pre-cured and semi-cured resins) used in the resin composition of the present invention is not particularly limited as long as it is commonly used as a material for resin moldings.
  • resin components include polybutadiene resins, polystyrene resins, impact-resistant polystyrene resins, polyimide resins, benzoxazine resins, and liquid crystal polymer resins. These may be used alone or in combination of two or more.
  • the amount of the phosphorus compound of the present invention in the resin composition of the present invention is not particularly limited, and is 0.1 to 200 parts by weight, preferably 0.5 to 100 parts by weight, and more than 100 parts by weight of the resin component. Preferably, it is 1 to 80 parts by weight.
  • the resin composition of the present invention may be used in combination with a flame retardant other than the phosphorus compound of the present invention (another flame retardant).
  • flame retardants include, for example, phosphate ester compounds, phosphazene compounds, phosphite ester compounds, phosphine compounds, phosphoramide compounds, phosphoramide ester compounds, melam, melam polyphosphate, melem, melem polyphosphate, melamine , melamine cyanurate, phosphonate, phosphinate, phosphine oxide and the like. These may be used alone or in combination of two or more.
  • the amount of the other flame retardant compounded in the resin composition of the present invention is not particularly limited, and is 0 to 200 parts by weight, preferably 0.5 to 100 parts by weight, more preferably 0.5 to 100 parts by weight, with respect to 100 parts by weight of the resin component. 1 to 50 parts by weight.
  • the resin composition of the present invention may contain a polymerizable component (polymerizable monomer and/or oligomer).
  • a polymerizable component polymerizable monomer and/or oligomer.
  • examples of the polymerizable component include vinyl compounds, vinylidene compounds, diene compounds, acrylic compounds, cyclic compounds (epoxy compounds, lactone compounds, lactam compounds, cyclic ether compounds, etc.).
  • These polymerizable components include, for example, butadiene, isoprene, and styrene. These may be used alone or in combination of two or more.
  • the amount of the polymerizable component in the resin composition of the present invention is not particularly limited. ⁇ 50 parts by weight.
  • the resin composition of the present invention may contain a polymerization initiator.
  • the polymerization initiator can be appropriately selected depending on the method of polymerizing the resin composition of the present invention.
  • examples of polymerization initiators include thermal polymerization initiators, photopolymerization initiators, radical polymerization initiators, and the like.
  • radical polymerization initiators include di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butyl peroxide)hexane, 2,5-dimethyl-2,5-di(t -butylperoxide)hexyne-3, ⁇ , ⁇ '-di(t-butylperoxy)diisopropylbenzene, t-butylperoxybenzoate and other peroxides. These may be used alone or in combination of two or more.
  • the amount of the polymerization initiator compounded in the resin composition of the present invention is not particularly limited, and is 0 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0 parts by weight with respect to 100 parts by weight of the resin component. .1 to 3 parts by weight.
  • the resin composition of the present invention may optionally contain a reactive diluent.
  • the amount of the reactive diluent compounded in the resin composition of the present invention is not particularly limited, and is 0 to 100 parts by weight, preferably 0.1 to 50 parts by weight, more preferably 0.1 to 50 parts by weight, with respect to 100 parts by weight of the resin component. 0.1 to 20 parts by weight.
  • the resin composition of the present invention may contain a fluororesin for the purpose of improving the flame retardancy (especially anti-dripping performance) of the cured product (formed body).
  • the blending amount of the fluororesin in the resin composition of the present invention is not particularly limited, and is 0 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the resin component.
  • the resin composition of the present invention may contain an inorganic filler for the purpose of improving flame retardancy (especially anti-dripping performance) and mechanical strength of the cured product (formed product).
  • inorganic fillers include silica, alumina, and boron nitride. These may be used alone or in combination of two or more.
  • a silane coupling agent may be used to coat the surface of the inorganic filler.
  • the blending amount of the inorganic filler in the resin composition of the present invention is not particularly limited.
  • the amount of the inorganic filler to be blended is 0 to 200 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the resin component from the viewpoint of the balance between improvement in flame retardancy and improvement in mechanical properties.
  • the resin composition of the present invention may contain various additives in accordance with its use, the type of resin component, etc., as long as the desired physical properties are not impaired.
  • additives include silane coupling agents, antioxidants (hindered phenol compounds, styrenated phenol compounds, organic phosphorus peroxide decomposers, organic sulfur peroxide decomposers, etc.), light stabilizers ( hindered amine compounds, etc.), curing agents, curing accelerators, cross-linking agents, diluents, fluidity modifiers, polymerization inhibitors, plasticizers, thixotropic agents, thickeners, compatibilizers, adhesives, adhesives, adhesives A property-imparting agent, various stabilizers, and the like can be mentioned. These may be used alone or in combination of two or more.
  • the amount of the additive compounded in the resin composition of the present invention is not particularly limited, and is 0 to 50 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the resin component.
  • the resin composition of the present invention contains the flame retardant of the present invention and optionally other flame retardants, polymerizable components, polymerization initiators, reactive diluents, fluororesins, inorganic fillers and additives in the resin component. It can be produced by mixing and/or kneading by known methods.
  • the resin composition of the present invention (hereinafter referred to as "the heat radically curable resin composition of the present invention") contains the phosphorus compound of the present invention and a heat radically curable resin component.
  • the thermoradical-curable resin composition of the present invention contains, in addition to the phosphorus compound and the thermoradical-curable resin component of the present invention, other resin components, other flame retardants, cross-linking agents, compatibilizers, It may contain radical polymerization initiators, inorganic fillers, stress relaxation agents, organic solvents, and additives.
  • the resin composition means the state of the mixture before curing.
  • thermoradical-curable resin component used in the thermoradical-curable resin composition of the present invention includes, for example, polyphenylene ether resins, bismaleimide resins, bismaleimide-triazine resins, poly Functional styrene compounds, benzocyclobutene resins, polytetrafluoroethylene resins, acrylic resins and the like are included.
  • polyphenylene ether resins examples include compounds having a structure represented by formula (2).
  • R a is the same or different and represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms.
  • n represents the number of repeating units, usually 1 or more. represents an integer of
  • the alkyl group having 1 to 6 carbon atoms represented by R a includes a chain or branched alkyl group having 1 to 6 carbon atoms, and specifically, a methyl group, an ethyl group, and an n-propyl group. , isopropyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group and the like, of which methyl group is preferred.
  • Examples of the alkenyl group having 2 to 6 carbon atoms represented by R a include chain or branched alkenyl groups having 2 to 6 carbon atoms, and specific examples include vinyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, pentenyl group, hexenyl group and the like.
  • R a is the same or different and is preferably a hydrogen atom or a methyl group.
  • n is preferably 1-400.
  • a compound having a structure represented by formula (2-1), a compound having a structure represented by formula (2-2), a compound having a structure represented by formula (2- A compound having a structure represented by 3) and the like can be mentioned.
  • n is the same as described above.
  • n is the same as described above.
  • n is the same as described above.
  • the compound having the structure represented by formula (2) preferably has two or more structures represented by formula (2) in the molecule. Further, this compound preferably has a crosslinkable group (eg, a group having a carbon-carbon double bond such as (meth)acrylic group, allyl group, vinylbenzyl group, etc.). The crosslinkable groups are preferably present at the ends of the molecule of this compound.
  • a crosslinkable group eg, a group having a carbon-carbon double bond such as (meth)acrylic group, allyl group, vinylbenzyl group, etc.
  • a preferred embodiment of the compound having the structure represented by formula (2) is, for example, the compound represented by chemical formula (IV).
  • X a is the same or different and represents a hydrogen atom or a group represented by formula (3).
  • Y a represents —O— or a group represented by formula (4).
  • R a is It is the same as above, and n is the same or different and is the same as above.
  • alkyl groups having 1 to 3 carbon atoms represented by R b , R c and R d include methyl group, ethyl group, n-propyl group and isopropyl group.
  • R b and R c are preferably hydrogen atoms, and R d is preferably a hydrogen atom or a methyl group.
  • the alkylene group having 1 to 10 carbon atoms represented by Z includes methylene group, methylmethylene group, dimethylene group, trimethylene group, ethylmethylene group, dimethylmethylene group, tetramethylene group, pentamethylene group, hexamethylene group, hepta methylene group, octamethylene group, nonamethylene group, decamethylene group and the like.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R e include chain or branched alkyl groups having 1 to 6 carbon atoms, and specifically, methyl group, ethyl group and n-propyl group. , isopropyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group and the like.
  • Examples of the alkenyl group having 2 to 6 carbon atoms represented by R e include linear or branched alkenyl groups having 2 to 6 carbon atoms, and specifically, vinyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, pentenyl group, hexenyl group and the like.
  • Examples of the aryl group represented by R e include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group and the like.
  • R e is preferably a hydrogen atom or a methyl group.
  • the alkylene group having 1 to 6 carbon atoms which may be substituted with a phenyl group represented by W includes, for example, a methylene group, a methylmethylene group, a dimethylmethylene group, a phenylmethylene group, a phenylmethylmethylene group and a diphenylmethylene group. etc.
  • Examples of the cycloalkylene group represented by W include cyclohexane-1,1-diyl group and the like.
  • Examples of the alkenediyl group having 2 to 6 carbon atoms which may be substituted with a halogen atom represented by W include ethylene-1,1-diyl and 2,2-dichloroethylene-1,1-diyl. .
  • -(Alkylene)-(phenylene)-(alkylene)- represented by W includes, for example, -(alkylene having 1 to 3 carbon atoms)-(phenylene)-(alkylene having 1 to 3 carbon atoms)- and the like. mentioned.
  • the alkylene having 1 to 3 carbon atoms includes methylene group, methylmethylene group, dimethylene group, trimethylene group, ethylmethylene group, dimethylmethylene group and the like, preferably dimethylmethylene group.
  • the phenylene group includes 1,2-phenylene group, 1,3-phenylene group and 1,4-phenylene group, preferably 1,4-phenylene group.
  • W is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms (especially a dimethylmethylene group).
  • Y a is preferably a group represented by formula (4) (wherein R e represents a hydrogen atom or a methyl group, and W represents an alkylene group having 1 to 3 carbon atoms).
  • preferred examples include the compound represented by the chemical formula (IV-1), the compound represented by the chemical formula (IV-2), the compound represented by the chemical formula (IV-3), and the like. mentioned.
  • n is the same as described above.
  • polyphenylene ether resins can be synthesized according to or according to known methods, for example, US Pat. No. 4,059,568, The Journal of Organic Chemistry, 34, 297-303 (1969).
  • the weight average molecular weight (Mw) of the polyphenylene ether resin is usually 1,000 to 120,000, preferably 1,000 to 50,000, and more preferably 1,000 to 20,000.
  • a weight average molecular weight can be measured using a gel permeation chromatography (GPC) by styrene conversion.
  • a bismaleimide resin is a compound having two maleimide groups in the molecule, and means a bismaleimide compound before curing.
  • Examples of bismaleimide resins include aliphatic bismaleimide compounds and aromatic bismaleimide compounds. These may be used alone or in combination of two or more.
  • Polyfunctional styrene compounds include, for example, bisvinylphenylmethane, 1,2-bis(m-vinylphenyl)ethane, 1,2-bis(p-vinylphenyl)ethane, 1-(p-vinylphenyl)-2 -(m-vinylphenyl)ethane, 1,3-bis(m-vinylphenylethyl)benzene, 1,3-bis(p-vinylphenylethyl)benzene, 1-(p-vinylphenylethyl)-3-( m-vinylphenylethyl)benzene, 1,4-bis(m-vinylphenylethyl)benzene, 1,4-bis(p-vinylphenylethyl)benzene, 1,6-bis(vinylphenyl)hexane and side chains
  • divinylbenzene polymers oligomers having vinyl groups.
  • the benzocyclobutene resin is not particularly limited as long as two or more benzocyclobutene groups are bonded directly or via an organic group.
  • thermoradical-curable resin composition of the present invention the above-mentioned thermoradical-curable resin components may be used alone, or two or more of them may be used in combination.
  • thermoradical-curable resin composition of the present invention in addition to the thermoradical-curable resin component, if necessary, resin components other than the thermoradical-curable resin component (other resin components) may be used in combination.
  • resin components include, for example, the resin components described above (the resin components described in the section 3. Flame retardant and resin composition), styrene block copolymers, and the like.
  • styrene block copolymers examples include styrene-butadiene block copolymers, styrene-isoprene block copolymers, styrene-ethylene/butylene-styrene block copolymers (SEBS), styrene-(ethylene-ethylene/propylene )-styrene block copolymer (SEEPS), styrene-ethylene/propylene-styrene block copolymer (SEPS), and the like. These may be used alone or in combination of two or more.
  • SEBS styrene-butadiene block copolymers
  • SEEPS styrene-isoprene block copolymers
  • SEEPS styrene-ethylene/butylene-styrene block copolymers
  • SEEPS styrene-(ethylene-ethylene/propylene )-styrene block copolymer
  • the amount of the other resin components in the thermoradical-curable resin composition of the present invention is not particularly limited, and is 0 to 1000 parts by weight, preferably 50 to 800 parts by weight, based on 100 parts by weight of the thermoradical-curable resin component. parts, more preferably 100 to 700 parts by weight.
  • the heat radical curable resin composition of the present invention may optionally contain a flame retardant other than the phosphorus compound of the present invention (e.g., the above (3. Flame retardant and resin composition). ) may be used in combination with the flame retardants described in the section [Other flame retardants].
  • a flame retardant other than the phosphorus compound of the present invention e.g., the above (3. Flame retardant and resin composition).
  • the amount of the phosphorus compound of the present invention to be incorporated in the thermoradical-curable resin composition of the present invention is not particularly limited. 1 to 200 parts by weight, preferably 1 to 160 parts by weight, more preferably 2 to 100 parts by weight.
  • the amount of other flame retardants in the thermoradical-curable resin composition of the present invention is not particularly limited, and is , 0 to 100 parts by weight, preferably 1 to 80 parts by weight, more preferably 1 to 40 parts by weight.
  • thermoradical-curable resin composition of the present invention may contain a cross-linking agent as long as the effects of the resin composition can be exhibited.
  • cross-linking agents include mono(alkyl having 6 to 20 carbon atoms) diallyl isocyanurate, 1-benzyl-3,5-diallyl isocyanurate, 1-(4-vinylbenzyl)-3,5-diallyl isocyanurate, and the like.
  • the amount of the cross-linking agent in the thermoradical-curable resin composition of the present invention is not particularly limited, and is 0 to 200 parts per 100 parts by mass of the resin component (total of the thermoradical-curable resin component and other resin components). parts by weight, preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight.
  • thermoradical curable resin composition of the present invention may optionally contain other components such as a compatibilizer, a radical polymerization initiator (e.g., the [radical polymerization Initiator] section), inorganic filler (e.g., the inorganic filler described in the section [Inorganic filler] of (3. Flame retardant and resin composition) above), stress relaxation agents, organic solvents, additives (for example, the additives described in the section [Additives] in (3. Flame retardant and resin composition) described above) and the like.
  • a compatibilizer e.g., a radical polymerization initiator (e.g., the [radical polymerization Initiator] section), inorganic filler (e.g., the inorganic filler described in the section [Inorganic filler] of (3. Flame retardant and resin composition) above), stress relaxation agents, organic solvents, additives (for example, the additives described in the section [Additives] in (3. Flame retardant and resin composition) described above)
  • compatibilizers examples include 1,2-polybutadiene, 1,4-polybutadiene, malein-modified polybutadiene, acrylic-modified polybutadiene, and epoxy-modified polybutadiene. These may be used alone or in combination of two or more.
  • the content of the compatibilizer in the thermoradical-curable resin composition of the present invention is not particularly limited, and is 0 to 0 per 100 parts by mass of the resin component (total of the thermoradical-curable resin component and other resin components). 100 parts by weight, preferably 20 to 50 parts by weight.
  • the amount of the radical polymerization initiator to be blended in the thermoradical-curable resin composition of the present invention is not particularly limited. 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, more preferably 0.01 to 3 parts by weight.
  • the amount of the inorganic filler compounded in the thermoradical-curable resin composition of the present invention is not particularly limited, and is 0 to 0 per 100 parts by weight of the resin component (total of the thermoradical-curable resin component and other resin components). 500 parts by weight, preferably 1 to 200 parts by weight, more preferably 5 to 100 parts by weight.
  • Organic solvent is not particularly limited as long as it can dissolve or disperse the thermoradical curable resin component.
  • examples include ketone solvents such as methyl ethyl ketone (MEK); aromatic hydrocarbon solvents such as benzene, toluene and xylene. mentioned. These may be used alone or in combination of two or more.
  • the amount of the organic solvent in the thermoradical-curable resin composition of the present invention may be adjusted according to the operation of applying or impregnating/coating the resin varnish onto the base material. 30 to 1,000 parts by weight, preferably 100 to 500 parts by weight, per 100 parts by weight of the total resin components.
  • the amount of the additive compounded in the thermoradical-curable resin composition of the present invention is not particularly limited, and is 0 to 50 parts per 100 parts by weight of the resin component (total of the thermoradical-curable resin component and other resin components). parts by weight, preferably 1 to 20 parts by weight.
  • thermoradical-curable resin composition of the present invention comprises a thermoradical-curable resin component, the flame retardant of the present invention, and optionally other resin components, other flame retardants, cross-linking agents, compatibilizers, and radical polymerization. It can be produced by mixing and/or kneading an initiator, an inorganic filler, a stress relaxation agent, an organic solvent and additives by a known method.
  • the resin composition described above in (3. Flame retardant and resin composition) and the thermally radically curable resin composition described in (4. Thermally radically curable resin composition) (hereinafter, both are collectively referred to as " The resin composition of the present invention") can be suitably used for applications such as prepregs, resin-coated metal foils, thermosetting resin films, metal-clad laminates, printed wiring boards, resin boards, semiconductor devices, and adhesives. .
  • the main raw materials (excluding the phosphorus compound of the present invention) used in the evaluation test are as follows.
  • [Main raw material] (A) Flame retardant 1,3-phenylene bis(di-2,6-xylenyl phosphate) (manufactured by Daihachi Chemical Industry, trade name "PX-200", see chemical formula (V).)
  • (C) Other resin components Styrene-butadiene block copolymer (manufactured by Asahi Kasei Co., Ltd., styrene-based block copolymer, trade name “Tufprene A”, styrene/butadiene weight ratio 40/60)
  • Tg and CTE The resin composition was poured into an aluminum cup having a radius of 3.5 cm to which a release agent was applied so that the thickness after curing was 1.5 mm, and toluene was distilled off until the weight became constant. Then, a cured product for evaluation was produced by performing heat treatment under the conditions of 150° C. for 30 minutes and 200° C. for 1 hour. The cured product for evaluation was measured for glass transition temperature (Tg) and linear expansion coefficient (CTE) using a thermomechanical analyzer (TMA, manufactured by Hitachi High-Tech Science, "TMA7100”) (flow gas: nitrogen, rising Temperature condition: 5°C/min.).
  • Tg glass transition temperature
  • CTE linear expansion coefficient
  • the resin composition was applied onto a 10 ⁇ 10 cm polyimide film (thickness: 40 ⁇ m, manufactured by Toray DuPont, “Kapton LK”) so that the thickness after drying would be 15 ⁇ m, and toluene was distilled off until the weight became constant. .
  • a glass epoxy base material (FR-4 grade) is layered on the coated surface of the resin composition, and the test is performed by pressing at 150° C. for 30 minutes, 200° C. for 1 hour, and a heating and pressure condition of 0.5 MPa. A piece was made. The normal peel strength of this test piece was measured according to "JIS C6481".
  • Example 3 107.5 parts by weight of the phosphorus compound synthesized in Example 1 as a flame retardant, 22.4 parts by weight of methacrylic-modified polyphenylene ether as a thermoradical-curable resin component, and a styrene/butadiene block copolymer as other resin components. 138.8 parts by weight, 20.0 parts by weight of 1-dodecyl-3,5-diallyl isocyanurate as a cross-linking agent, and ⁇ , ⁇ '-di(t-butylperoxy)diisopropylbenzene as a radical polymerization initiator.
  • Example 4 Radical thermosetting resin compositions having the compositions shown in Table 1 were prepared in the same manner as in Example 3, and evaluation tests were performed on these resin compositions. The test results obtained were as follows. It was as shown in Table 1.
  • the phosphorus compound of the present invention (compounds of Examples 1 and 2) as a flame retardant, it is possible to give a cured product excellent in low thermal expansion, heat resistance, adhesiveness (adhesion) and flame retardancy. I understand.
  • the phosphorus compound of the present invention is expected to be used as a flame retardant for resins.
  • the resin composition containing the phosphorus compound of the present invention is expected to give a cured product excellent in low thermal expansion, heat resistance, adhesiveness (adhesion), mechanical properties, electrical properties and flame retardancy. Therefore, it is suitable for materials such as printed wiring boards and materials for adhesives.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

La présente invention concerne : un nouveau composé de phosphore ayant un cycle isocyanurate ; un procédé de synthèse dudit composé de phosphore ; un retardateur de flamme contenant ledit composé de phosphore ; et une composition de résine contenant ledit composé de phosphore et un composant de résine. De plus, l'invention concerne : un préimprégné utilisant ladite composition de résine ; une feuille métallique comprenant une résine ; un film de résine thermodurcissable ; un stratifié plaqué de métal ; une carte de circuit imprimé ; et un adhésif. La présente invention concerne : un composé de phosphore ayant un cycle isocyanurate et représenté par la formule chimique (I) ; un procédé de synthèse associé ; et son utilisation. (Dans la formule, R1 représente un groupe alkyle en C1-C20, un groupe aryle ou un groupe benzyle et R2 représente un groupe représenté par la formule (1). En variante, R1 et R2 peuvent être liés pour former un cycle. Chaque R3 représente de manière identique ou différente un groupe alcényle en C2-C20 ou un groupe alcynyle en C2-C20. Chaque R4 représente de manière identique ou différente un atome d'hydrogène, un groupe alkyle en C1-C20, un groupe aryle, un groupe benzyle, un groupe alcényle en C2-C20 ou un groupe alcynyle en C2-C20. Chaque Y représente de manière identique ou différente un groupe alkylène en C1-C20.) (Dans la formule, R3, R4 et Y sont les mêmes que ci-dessus.)
PCT/JP2022/024453 2021-07-30 2022-06-20 Composé de phosphore ayant un cycle isocyanurate, son procédé de synthèse et utilisation dudit composé de phosphore ayant un cycle isocyanurate WO2023007982A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2021-125891 2021-07-30
JP2021125891 2021-07-30
JP2021134480A JP2023020775A (ja) 2021-07-30 2021-08-20 イソシアヌレート環を有するリン化合物、その合成方法および該イソシアヌレート環を有するリン化合物の利用
JP2021-134480 2021-08-20

Publications (1)

Publication Number Publication Date
WO2023007982A1 true WO2023007982A1 (fr) 2023-02-02

Family

ID=85086590

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/024453 WO2023007982A1 (fr) 2021-07-30 2022-06-20 Composé de phosphore ayant un cycle isocyanurate, son procédé de synthèse et utilisation dudit composé de phosphore ayant un cycle isocyanurate

Country Status (2)

Country Link
TW (1) TW202311278A (fr)
WO (1) WO2023007982A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004108736A1 (fr) * 2003-06-09 2004-12-16 Daihachi Chemical Industry Co., Ltd. Compose d'organophosphore possedant une liaison phosphate-phosphonate, fibre de polyester et composition de resine de polyurethanne ignifuges contenant chacune ce compose
JP2017514890A (ja) * 2014-03-17 2017-06-08 エーエムペーアー・アイトゲネーシッシェ・マテリアルプリューフングス‐ウント・フォルシュングスアンシュタルト Ｄｏｐｏ系ハイブリッド難燃剤
CN111117205A (zh) * 2019-08-27 2020-05-08 张媛婷 一种二氧化硅气凝胶隔热密封材料

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004108736A1 (fr) * 2003-06-09 2004-12-16 Daihachi Chemical Industry Co., Ltd. Compose d'organophosphore possedant une liaison phosphate-phosphonate, fibre de polyester et composition de resine de polyurethanne ignifuges contenant chacune ce compose
JP2017514890A (ja) * 2014-03-17 2017-06-08 エーエムペーアー・アイトゲネーシッシェ・マテリアルプリューフングス‐ウント・フォルシュングスアンシュタルト Ｄｏｐｏ系ハイブリッド難燃剤
CN111117205A (zh) * 2019-08-27 2020-05-08 张媛婷 一种二氧化硅气凝胶隔热密封材料

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SCHARTEL BERNHARD, PERRET BIRGIT, DITTRICH BETTINA, CIESIELSKI MICHAEL, KRÄMER JOHANNES, MÜLLER PATRICK, ALTSTÄDT VOLKER, ZANG LIN: "Flame Retardancy of Polymers: The Role of Specific Reactions in the Condensed Phase : FR Polymers: Role of Condensed Phase", MACROMOLECULAR MATERIALS AND ENGINEERING., WILEY VCH VERLAG, WEINHEIM., DE, vol. 301, no. 1, 1 January 2016 (2016-01-01), DE , pages 9 - 35, XP093030669, ISSN: 1438-7492, DOI: 10.1002/mame.201500250 *

Also Published As

Publication number Publication date
TW202311278A (zh) 2023-03-16

Similar Documents

Publication Publication Date Title
US9399712B2 (en) Vinylbenzyl-etherified-DOPO compound resin composition and preparation and application thereof
JP6762933B2 (ja) アリルフェノキシシクロホスファゼン化合物及びその製造方法
JP5807186B2 (ja) ポリフェニレンエーテル樹脂組成物、樹脂ワニス、プリプレグ、金属張積層板、及びプリント配線板
US11124614B2 (en) Halogen-free low dielectric resin composition, and pre-preg, metal-clad laminate, and printed circuit board using the same
WO2001070904A1 (fr) Agent ignifugeant, composition de resine ignifugeante, objet moule et piece electronique
TW201444909A (zh) 低介電之無鹵素樹脂組成物及應用其之電路板
TW201518403A (zh) 低介電樹脂組合物，應用其的半固化膠片、銅箔基板及電路板
US20150351237A1 (en) Circuit materials with improved fire retardant system and articles formed therefrom
JP6589623B2 (ja) 熱硬化性樹脂組成物、プリプレグ、銅張積層板及びプリント配線板
JP6635415B2 (ja) 硬化性組成物、プリプレグ、組成物付き金属箔、金属張積層板、及び配線板
JP2020105352A (ja) 硬化性樹脂組成物、プリプレグ、金属張積層板、及びプリント配線板
TWI742643B (zh) 一種樹脂組合物以及使用其的預浸片及絕緣板
WO2017002319A1 (fr) Composition durcissable, préimprégné, feuille métallique avec composition, stratifié à revêtement métallique et tableau de connexions
WO2023007982A1 (fr) Composé de phosphore ayant un cycle isocyanurate, son procédé de synthèse et utilisation dudit composé de phosphore ayant un cycle isocyanurate
JP5013401B2 (ja) 反応性基含有環状ホスファゼン化合物からなる難燃剤およびその製造方法
JP2010106148A (ja) 難燃性樹脂組成物
JP2009161716A (ja) 難燃性樹脂組成物
JP2023020775A (ja) イソシアヌレート環を有するリン化合物、その合成方法および該イソシアヌレート環を有するリン化合物の利用
TW202309173A (zh) 樹脂組合物及其製品
WO2021166649A1 (fr) Composition de résine durcissable, prépeg, stratifié recouvert de métal, et carte de circuit imprimé
JP2018012791A (ja) 熱硬化性樹脂組成物、プリプレグ、積層板及びプリント配線板
JP2023020498A (ja) トリアジン環を有するリン化合物、その合成方法および該トリアジン環を有するリン化合物の利用
JP2023020499A (ja) トリアジン環を有するリン化合物、その合成方法および該トリアジン環を有するリン化合物の利用
JP5478850B2 (ja) 特定の製造方法により得られるリン含有フェノール化合物を用いたリン含有エポキシ樹脂、該樹脂を用いたリン含有エポキシ樹脂組成物および硬化物
JP2023119616A (ja) イソシアヌレート環を有するリン化合物、その合成方法および該イソシアヌレート環を有するリン化合物の利用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22849059

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE