Phosphorus compounds, methods of synthesis and uses thereof

Abstract

The present invention provides: a novel phosphorus compound; methods of synthesizing the compounds; a flame retardant containing the compound; and a resin composition containing the compound and a resin component. Also provided are: a prepreg containing the resin composition; a metal foil with a resin; a thermosetting resin film; a metal clad laminate; a printed wiring board; and a binder. The present invention relates, for example, to a phosphorus compound represented by chemical formula (I): # imgabs0 # (wherein R1 represents a C1-10 alkyl group, R2 represents a C1-10 alkyl group, and R3 may be the same or different and each represents a hydrogen atom or a C1-10 alkyl group).

Description

Technical Field

[0001] The present invention relates to a novel phosphorus compound having three p-vinylphenyl groups, a synthesis method of the compound and application of the compound. Background Art

[0002] In recent years, electronic devices have continued to shrink in size while improving their performance. This has led to the formation of multiple build-up layers in multilayer printed circuit boards, driving the need for miniaturization and high-density wiring. In high-frequency applications, in particular, to reduce signal transmission loss, insulating materials (resins) with low dielectric constants are required. In addition to electrical performance, these resins are also required to exhibit flame retardancy after curing, leading to ongoing research into various flame retardants.

[0003] As a conventional flame retardant, a phosphorus compound represented by Chemical Formula (V) is known (for example, Patent Document (PTL) 1). This phosphorus compound has a reactive group (vinyl group) and a phosphorus atom in its molecule.

[0004]

[0005] Although the cured product of the resin composition containing this phosphorus compound exhibits excellent flame retardancy, electrical properties, and heat resistance, its electrical properties still have room for improvement. In addition, this phosphorus compound also has the problem of poor moisture absorption resistance and hydrolysis resistance.

[0006] Reference List

[0007] Patent Literature

[0008] PTL 1: CN109762115A. Summary of the Invention

[0009] Technical issues

[0010] An object of the present invention is to provide a novel phosphorus compound, a method for synthesizing the compound, a flame retardant containing the compound, and a resin composition containing the compound and a resin component.

[0011] Another object of the present invention 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 containing the resin composition.

[0012] Technical solutions to the problem

[0013] The inventors of the present invention have conducted repeated and intensive studies to solve the above-mentioned problems. As a result, they found that the intended purpose can be achieved by using a phosphorus compound obtained by reacting a certain p-vinylphenol compound with phosphorus oxychloride, thereby completing the present invention.

[0014] Specifically, the first invention relates to a phosphorus compound represented by chemical formula (I):

[0015]

[0016] Among them, each R 1 Indicates C 1-10 Alkyl, each R 2 Indicates C 1-10 Alkyl, each R 3 Same or different, represents hydrogen atoms or C 1-10 alkyl.

[0017] The second invention relates to a method for synthesizing the phosphorus compound according to the first invention, which comprises reacting a p-vinylphenol compound represented by chemical formula (II) with phosphorus oxychloride represented by chemical formula (III):

[0018]

[0019] Among them, R 1 、R 2 and each R 3 As mentioned above,

[0020]

[0021] The third invention relates to a flame retardant comprising the phosphorus compound according to the first invention.

[0022] The fourth invention relates to a resin composition comprising the phosphorus compound according to the first invention; and a resin component.

[0023] The fifth invention relates to a prepreg comprising the resin composition according to the fourth invention; and a base material.

[0024] The sixth invention relates to a metal foil with resin, comprising: a resin layer containing the resin composition according to the fourth invention or a semi-cured product of the resin composition; and a metal foil.

[0025] The seventh invention relates to a thermosetting resin film formed from the resin composition according to the fourth invention.

[0026] The eighth invention relates to a metal-clad laminate comprising: an insulating layer containing a cured product of the resin composition according to the fourth invention; and a metal foil.

[0027] The ninth invention relates to a printed wiring board comprising: an insulating layer containing a cured product of the resin composition according to the fourth invention or a cured product of the thermosetting resin film according to the seventh invention; and a circuit.

[0028] The tenth invention relates to an adhesive comprising the resin composition according to the fourth invention as a component.

[0029] Beneficial effects of the present invention

[0030] The phosphorus compound of the present invention contains three reactive groups (vinyl groups) and phosphorus in its molecule and is expected to be used as a flame retardant for various resins.

[0031] Phosphorus content is high in the phosphorus compound molecule of the present invention, and has the p-vinylphenyl that has alkyl respectively on two ortho positions.Therefore, when this phosphorus compound is used as the raw material of resin (resin material), compared with using conventional phosphorus compound, this phosphorus compound is expected to provide the cured product with excellent flame retardancy, electrical characteristic (for example, low dielectric tangent), thermotolerance, moisture absorption resistance and hydrolysis resistance.Therefore, resin combination of the present invention can be suitable as materials such as printed wiring boards.

[0032] Furthermore, the adhesive of the present invention is expected to have excellent adhesion, flame retardancy, electrical properties (eg, low dielectric tangent), heat resistance, moisture absorption resistance, hydrolysis resistance, and flame retardancy. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is the infrared spectrum of the light yellow liquid obtained in Example 1. DETAILED DESCRIPTION

[0034] 1. Phosphorus compounds

[0035] The present invention relates to a phosphorus compound represented by chemical formula (I) (hereinafter sometimes also referred to as "the phosphorus compound of the present invention").

[0036] Examples of the phosphorus compound of the present invention include phosphorus compounds represented by chemical formulas (I-1) to (I-4):

[0037]

[0038] Other examples of the phosphorus compound of the present invention include tris(2,6-diisopropyl-4-vinylphenyl)phosphate (I-5), tris(2,6-di-tert-butyl-4-vinylphenyl)phosphate (I-6), and the like.

[0039] R 1 、R 2 and R 3 C shown 1-10 The alkyl group can be a straight or branched C 1-10 Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, heptyl, octyl, nonyl, decyl, and the like.

[0040] In the phosphorus compound of the present invention, preferred substituents are as follows.

[0041] Each R 1 Same, preferably C 1-5 Alkyl, more preferably C 1-4 The alkyl group is more preferably a methyl group or a butyl group.

[0042] Each R 2 Same, preferably C 1-5 Alkyl, more preferably C 1-4 The alkyl group is more preferably a methyl group or a butyl group.

[0043] Each R 3 The same, preferably hydrogen.

[0044] 2. Synthesis of Phosphorus Compounds

[0045] The phosphorus compound of the present invention can be synthesized by reacting a p-vinylphenol compound represented by chemical formula (II) with phosphorus oxychloride represented by chemical formula (III) (see reaction scheme (A)):

[0046]

[0047] Each R 1 , each R 2 and each R 3 As mentioned above.

[0048] Examples of the p-vinylphenol compound represented by the chemical formula (II) include p-vinylphenol compounds represented by chemical formulas (II-1) to (II-6):

[0049]

[0050] The p-vinylphenol compounds used can be purchased commercial reagents or synthesized according to the methods described in, for example, Royal Society Open Science (2022), 9(4), 220014, Tetrahedron Letters (2005), 46(40), 6893-6896, Current Organic Synthesis (2019), 16(1), 130-135, Organic Letters (2012), 14(18), 4722-4725, Synthesis (2017), 49(23), 5217-5223, etc.

[0051] The phosphorus oxychloride used may be a commercially available reagent.

[0052] In the present reaction, preferably, the amount of the p-vinylphenol compound used (feed amount) is appropriately selected within the range of 3 to 6 times the molar amount of phosphorus oxychloride used (feed amount).

[0053] In carrying out this reaction, a base (a) may be used to accelerate the reaction, and a reaction solvent (b) may be optionally used as needed.

[0054] Examples of the base (a) include trimethylamine, triethylamine, N,N-diisopropylethylamine, diazabicyclononene, diazabicycloundecene, pyridine, 4-dimethylaminopyridine, imidazole, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium hydrogencarbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, cesium hydrogencarbonate, trilithium phosphate, trisodium phosphate, tripotassium phosphate, tricesium phosphate, dilithium hydrogenphosphate, disodium hydrogenphosphate, dipotassium hydrogenphosphate, dicesium hydrogenphosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, cesium dihydrogen phosphate, lithium acetate, sodium acetate, potassium acetate, cesium acetate, sodium alkoxide, potassium alkoxide, potassium tert-butoxide, etc. These may be used alone or in combination of two or more.

[0055] Preferably, the amount of the base (a) used (charging amount) is appropriately selected within the range of 0 to 40 times the molar amount (charging amount) of the phosphorus oxychloride used.

[0056] Any reaction solvent (b) can be used as long as it does not interfere with the reaction. Examples include: tetrahydrofuran, dioxane, ethyl acetate, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, water and other solvents. These can be used in combination as needed and used in appropriate amounts.

[0057] In this reaction, the reaction temperature is preferably set in the range of -10 to 150° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 1 to 100 hours.

[0058] After the reaction is completed, the phosphorus compound as the target product can be extracted from the obtained reaction solution (reaction mixture) by methods such as distilling the reaction solvent to concentrate the reaction solution, solvent extraction, and crystallization.

[0059] Furthermore, the phosphorus compound can be purified, if necessary, by washing with water or the like, treating with activated carbon, silica gel chromatography, recrystallization, or the like.

[0060] 3. Flame retardant and resin composition

[0061] The flame retardant and resin composition of the present invention both contain the phosphorus compound of the present invention. The phosphorus compound of the present invention has a high flame retardant effect and is therefore suitable for use as a flame retardant for resins. The cured product (molded article) of the resin composition containing the phosphorus compound of the present invention exhibits excellent flame retardancy.

[0062] The resin composition of the present invention may contain, in addition to the phosphorus compound and the resin component of the present invention, one or more other flame retardants, polymerizable components, polymerization initiators, reactive diluents, fluororesins, inorganic fillers, and additives as needed. In the present invention, the term "resin composition" refers to the mixture before curing.

[0063] Resin component

[0064] Any resin component (including pre-cured resin and semi-cured resin) can be used in the resin composition of the present invention as long as it is a material generally used as a resin molding material.

[0065] Examples of the resin component include polyethylene resin, chlorinated polyethylene resin, polyvinyl chloride resin, polypropylene resin, polyisoprene resin, high-impact polystyrene resin, acrylonitrile-styrene resin (AS resin), acrylonitrile-butadiene-styrene resin (ABS resin), methyl methacrylate-butadiene-styrene resin (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin), acrylonitrile-acrylic rubber-styrene resin (AAS resin), polymethyl (meth)acrylate resin, polyester resin (polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate, etc.), unsaturated polyester resin, polyesterimide resin, polyketone resin, polycarbonate resin, polyamide resin, polyimide resin, polyamideimide resin, polycarbodiimide resin, polyetherimide resin, polyetherketone resin, polyetheretherketone resin (PEEK resin), polyethersulfone resin, polysulfide ethersulfone resin, polysulfone resin, polyphenylene sulfide resin (polyphenylene sulfide resin), polyether nitrile resin, polyarylate resin, polybenzimidazole resin, benzoxazine resin, liquid crystal polymer resin, silicone resin, epoxy resin, polyurethane resin, phenolic resin, melamine resin, urea resin, diallyl phthalate resin, etc. These can be used alone or in combination of two or more.

[0066] In the resin composition of the present invention, the amount of the phosphorus compound of the present invention is not limited. Relative to 100 parts by weight of the resin component, the amount of the phosphorus compound of the present invention is preferably 1 to 200 parts by weight, more preferably 1 to 160 parts by weight, and even more preferably 2 to 150 parts by weight.

[0067] Other flame retardants

[0068] The resin composition of the present invention may contain one or more different flame retardants (other flame retardants) as flame retardants in addition to the phosphorus compound of the present invention, as long as the resin composition of the present invention can exert its effect.

[0069] Examples of other flame retardants include phosphate compounds, phosphazene compounds, phosphite compounds, phosphine compounds, melamine phosphate, phosphoramide compounds, phosphoramide ester compounds, phosphinate compounds and salts thereof, ammonium phosphate, ammonium polyphosphate, melam, melam polyphosphate, melem, melem polyphosphate, red phosphorus, melamine, melamine pyrophosphate, melamine cyanurate, succinoguanamine, phosphonic acid ester, phosphinic acid ester, phosphine oxide, ethylenebispentabromobenzene, ethylenebistetrabromophthalimide, and the like.

[0070] Examples of the phosphate compound include triphenyl phosphate, tricresyl phosphate, ditolyl diphenyl phosphate, cresyl diphenyl phosphate, 1,3-phenylenebis(di-2,6-ditolyl phosphate), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), condensed phosphate compounds (e.g., aromatic condensed phosphate compounds), cyclic phosphate compounds, and the like.

[0071] Examples of the phosphazene compound include cyclic or linear phosphazene compounds. Cyclic phosphazene compounds, also known as cyclophosphazenes, are compounds having a cyclic structure with a double bond between a phosphorus atom and a nitrogen atom in the molecule.

[0072] Examples of the phosphite compound include trimethyl phosphite, triethyl phosphite, and the like.

[0073] Examples of the phosphine compound include tri-(4-methoxyphenyl)phosphine, triphenylphosphine and the like.

[0074] These may be used alone or in combination of two or more.

[0075] In the resin composition of the present invention, the amount of other flame retardants is not limited as long as it is within the range in which the resin composition of the present invention can exert its effect. The amount of other flame retardants is 0 to 100 parts by weight, preferably 1 to 80 parts by weight, and more preferably 10 to 40 parts by weight, relative to 100 parts by weight of the resin component.

[0076] polymerizable component

[0077] The resin composition of the present invention may contain 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.), and the like.

[0078] Examples of these polymerizable components include vinyl chloride, butadiene, isoprene, styrene, a high impact polystyrene precursor, an acrylonitrile-styrene resin (AS resin) precursor, an acrylonitrile-butadiene-styrene resin (ABS resin) precursor, a methyl methacrylate-butadiene-styrene resin (MBS resin) precursor, a methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin) precursor, an acrylonitrile-acrylic rubber-styrene resin (AAS resin) precursor, methyl (meth)acrylate, an epoxy acrylate resin precursor, an epoxidized oil acrylate resin precursor, a polyacrylate precursor, and the like. Urethane acrylate resin precursors, polyester acrylate resin precursors, polyether acrylate resin precursors, acrylic acrylate resin precursors, unsaturated polyester resin precursors, vinyl / acrylate resin precursors, vinyl ether resin precursors, polyene / thiol resin precursors, silicone acrylate resin precursors, polybutadiene acrylate resin precursors, polystyrene (ethyl) methacrylate resin precursors, polycarbonate acrylate resin precursors, alicyclic epoxy resin precursors, glycidyl ether epoxy resin precursors, photocurable or heat-curable polyimide resin precursors, silicone-containing resin precursors, epoxy resin precursors, etc. These can be used alone or in combination of two or more. The term "precursor" refers to a monomer or oligomer.

[0079] In the resin composition of the present invention, the amount of the polymerizable component is not limited. Relative to 100 parts by weight of the resin component, the amount of the polymerizable component is 0 to 200 parts by weight, preferably 0.5 to 100 parts by weight, and more preferably 1 to 50 parts by weight.

[0080] Polymerization initiator

[0081] The resin composition of the present invention may contain a polymerization initiator. The polymerization initiator can be appropriately selected according to the polymerization method of the resin composition of the present invention. Examples of the polymerization initiator include thermal polymerization initiators, photopolymerization initiators, free radical polymerization initiators, and the like.

[0082] Examples of thermal polymerization initiators include azo compounds such as 2,2-azobisisobutyronitrile (AIBN), 2,2-azobis(2-methylbutyronitrile), azobis-2,4-dimethylvaleronitrile, azobiscyclohexylnitrile, and azobiscyanovaleric acid; peroxides such as benzoyl peroxide, dicumyl peroxide, and diisopropyl peroxydicarbonate; acid generators such as aromatic sulfonates; and the like. These may be used alone or in combination of two or more.

[0083] Examples of the photopolymerization initiator include acetophenone-based photopolymerization initiators, benzophenone-based photopolymerization initiators, benzoin-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, sulfonium-based photopolymerization initiators, and iodonium-based photopolymerization initiators, etc. These may be used alone or in combination of two or more.

[0084] When one or more photopolymerization initiators are used, a sensitizer such as a tertiary amine may be used in combination with these photopolymerization initiators as needed.

[0085] Examples of free radical polymerization initiators include peroxides such as di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butyl peroxide)hexane, 2,5-dimethyl-2,5-di(tert-butyl peroxide)hexyne-3, α,α'-di(tert-butyl peroxy)diisopropylbenzene, and tert-butyl peroxybenzoate. These can be used alone or in combination of two or more.

[0086] In the resin composition of the present invention, the amount of the polymerization initiator is not limited. Relative to 100 parts by weight of the resin component, the amount of the polymerization initiator is 0.001 to 10 parts by weight, preferably 0.01 to 8 parts by weight, and more preferably 0.1 to 5 parts by weight.

[0087] Reactive diluent

[0088] The resin composition of the present invention may contain a reactive diluent as needed.

[0089] Examples of reactive diluents include aliphatic alkyl glycidyl ethers such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and allyl glycidyl ether; alkyl glycidyl esters such as glycidyl methacrylate and glycidyl esters of tertiary carboxylic acids; and aromatic alkyl glycidyl ethers such as styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, and nonylphenyl glycidyl ether. These may be used alone or in combination of two or more.

[0090] In the resin composition of the present invention, the amount of the reactive diluent is not limited. Relative to 100 parts by weight of the resin component, the amount of the reactive diluent is 0 to 100 parts by weight, preferably 0.1 to 50 parts by weight, and more preferably 0.1 to 20 parts by weight.

[0091] Fluororesin

[0092] The resin composition of the present invention may contain a fluororesin in order to improve the flame retardancy (particularly the anti-drip performance) of a cured product (molded article) of the resin composition.

[0093] Examples of fluororesins include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), poly(chlorotrifluoroethylene) (CTFE), polyvinylidene fluoride (PVdF), etc. These may be used alone or in combination of two or more.

[0094] In the resin composition of the present invention, the amount of the fluororesin is not limited and is 0 to 20 parts by weight, preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of the resin component.

[0095] Inorganic fillers

[0096] The resin composition of the present invention may contain an inorganic filler in order to improve the flame retardancy (particularly the anti-dripping property) and mechanical strength of the cured product (molded article) of the resin composition.

[0097] Examples of the inorganic filler include mica, natural mica, synthetic mica, kaolin, calcined kaolin, talc, calcined talc, wollastonite, silica, alumina, boron nitride, clay, calcined clay, titanium dioxide, barium sulfate, barium carbonate, calcium carbonate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, calcium silicate, titanium dioxide, zinc oxide, zinc borate, glass beads, glass microspheres, glass flakes, short glass fibers, fine glass powder, hollow glass, fibrous alkali metal titanates (potassium titanate fibers, sodium titanate fibers, etc.), fibrous borates (aluminum borate fibers, magnesium borate fibers, zinc borate fibers, etc.), zinc oxide fibers, titanium oxide fibers, magnesium oxide fibers, gypsum fibers, aluminum silicate fibers, calcium silicate fibers, silicon carbide fibers, titanium carbide fibers, silicon nitride fibers, titanium nitride fibers, carbon fibers, aluminum oxide fibers, alumina-silica fibers, zirconium oxide fibers, quartz fibers, sheet titanates, sheet titanium dioxide, and the like. These may be used alone or in combination of two or more.

[0098] In particular, in order to reduce the dielectric constant of the resin composition, it is preferred to use a low dielectric constant filler such as silica or boron nitride as the inorganic filler. Examples of silica include ground silica, fused silica, natural silica, calcined silica, synthetic silica, crystalline silica, amorphous silica, and the like.

[0099] The average particle size of the inorganic filler is preferably 5 μm or less. For example, when the resin composition is used for metal-clad laminates, the use of an inorganic filler having an average particle size of 5 μm or less (such as silica particles) can enhance its adhesion to metal foil.

[0100] In order to prevent or alleviate degradation of the resin component, the surface of the inorganic filler may be coated with a silane coupling agent.

[0101] In the resin composition of the present invention, the amount of the inorganic filler is not limited. From the perspective of taking both flame retardancy and mechanical properties into consideration, the amount of the inorganic filler is 0 to 800 parts by weight, preferably 1 to 600 parts by weight, and more preferably 10 to 400 parts by weight relative to 100 parts by weight of the resin component.

[0102] additive

[0103] The resin composition of the present invention may contain various additives depending on the application, the type of resin component, etc., within a range not impairing the desired physical properties.

[0104] Examples of additives include white carbon, aluminum nitride, zinc borate, zinc stannate, zinc molybdate, molybdenum oxide, silicon nitride, aerosil, wollastonite, nanocarbon (carbon nanotubes, graphene, fullerene, etc.), organic fibers (aramid fibers, polyparaphenylene benzobisoxazole fibers, etc.), silane coupling agents, waxes, fatty acids and their metal salts, release agents (amides, paraffin, etc.), chlorinated paraffins, silicone flame retardants, brominated flame retardants, flame retardant aids (antimony trioxide, etc.), ultraviolet absorbers (benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds, etc.), antioxidants (hindered phenol compounds, styrenated phenol compounds, organophosphorus peroxide decomposers, organosulfur peroxide decomposers, etc.), fluorescent brighteners (stilbene derivatives, etc.), light stabilizers (hindered amine compounds, etc.), photosensitizers, glossing agents, metal deactivators (benzotriazole compounds, etc.), opacifiers (rutile titanium dioxide, zinc oxide, chromium oxide, cerium oxide, etc.), quenchers (organic nickel, etc.), curing agents, curing accelerators, crosslinking agents, diluents, flow regulators, polymerization inhibitors, dyes, pigments, colorants, antifogging agents, mildew inhibitors, antibacterial agents, deodorants, plasticizers, antistatic agents, surfactants, defoamers, foaming agents, leveling agents, slip agents, lubricants, thixotropic agents, thickeners, nucleating agents, reinforcing agents, compatibilizers, conductive agents, anti-blocking agents, anti-tracking agents, phosphorescent agents, plasticizers, adhesives, glues, tackifiers, various stabilizers, etc. These may be used alone or in combination of two or more.

[0105] In the resin composition of the present invention, the amount of the additive is not limited. Relative to 100 parts by weight of the resin component, the amount of the additive is 0 to 50 parts by weight, preferably 1 to 20 parts by weight.

[0106] Resin combination of the present invention can be by resin component and phosphorus compound of the present invention and other fire retardants, polymerizable components, polymerization initiator, reactive diluent, fluororesin, inorganic filler and additive are mixed and / or kneaded by known method and manufacture.For example, resin combination can be by using forcing machine (single screw extruder, twin screw extruder etc.), kneader (Banbury mixer, pressure kneader, two-roll mill, three-roll mill etc.), the mixture of each component of liquid, powder, bead, flaky or granular is mixed and / or kneaded and manufacture.

[0107] 4. Thermal radical curable resin composition

[0108] The resin composition of the present invention (hereinafter referred to as the "thermally radical curable resin composition of the present invention") contains the phosphorus compound of the present invention and a thermally radical curable resin component. In addition to the phosphorus compound and thermally radical curable resin component of the present invention, the thermally radical curable resin composition of the present invention may also contain other resin components, other flame retardants, crosslinking agents, radical polymerization initiators, inorganic fillers, stress relievers, organic solvents, and additives as needed. In the present invention, the term "resin composition" refers to the mixture before curing.

[0109] Thermal radical curable resin component

[0110] Examples of the thermally radical curable resin component (including pre-cured resin and semi-cured resin) used in the thermally radical curable resin composition of the present invention include polyphenylene ether resin, bismaleimide resin, bismaleimide-triazine resin, multifunctional styrene compound, polystyrene resin, polybutadiene resin, benzocyclobutene resin, polytetrafluoroethylene resin, acrylic resin, etc.

[0111] Examples of the polyphenylene ether resin include compounds having a structure represented by formula (1):

[0112]

[0113] Among them, each R a Same or different, represents hydrogen, C 1-6 Alkyl or C 2-6 Alkenyl; n represents the number of repeating units, usually an integer of 1 or greater.

[0114] R a C 1-6 The alkyl group can be a straight or branched C 1-6 Alkyl. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, etc. Among them, methyl is preferred.

[0115] R a C 2-6 The alkenyl group can be a straight or branched C 2-6 Specific examples include vinyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, pentenyl, hexenyl, and the like.

[0116] Optimize each R a The same or different groups represent hydrogen or methyl.

[0117] Preferably, n is 1 to 400.

[0118] Examples of embodiments of the compound having the structure represented by formula (1) include a compound having the structure represented by formula (1-1), a compound having the structure represented by formula (1-2), and a compound having the structure represented by formula (1-3):

[0119]

[0120] Where n is as described above,

[0121]

[0122] Where n is as described above,

[0123]

[0124] where n is as described above.

[0125] The compound having the structure represented by formula (1) preferably has two or more structures represented by formula (1) in the molecule. In addition, the compound preferably has a crosslinking group (for example, a group having a carbon-carbon double bond, such as a (meth)acryloyl group, an allyl group, or a vinylbenzyl group). The crosslinking group is preferably present at one or both ends of the compound molecule.

[0126] A preferred embodiment of the compound having the structure represented by formula (1) is, for example, a compound represented by chemical formula (IV):

[0127]

[0128] Among them, each X a are the same or different, represent hydrogen or a group represented by formula (2), Y a represents -O- or a group represented by formula (3), R a As described above, each n is the same or different, and as described above:

[0129]

[0130] where R b 、R c and R d the same or different, each representing hydrogen or C 1-3 Alkyl, each Z is the same or different, represents C 1-10 Alkylene, -C(=O)-, -Ph-, -Ph-CH2- or -Ph-CH2CH2-,

[0131]

[0132] Among them, each R e Same or different, represents hydrogen, C 1-6 Alkyl, C 2-6Alkenyl, or aryl; W represents a single bond, C optionally substituted by phenyl 1-6 Alkylene, cycloalkylene, C optionally substituted by halogen 2-6 Alkenediyl, -C(=O)-, -S(O) m -(wherein m represents 0, 1 or 2) or -(alkylene)-(phenylene)-(alkylene)-.

[0133] R b 、R c and R d C 1-3 Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, and the like. b and R c Preferably, R is hydrogen. d Preferred are hydrogen or methyl.

[0134] C represented by Z 1-10 Examples of the alkylene group include methylene, methylmethylene, dimethylene, trimethylene, ethylmethylene, dimethylmethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene and the like.

[0135] Z is preferably -C(=O)-, -Ph-, -Ph-CH2- or -Ph-CH2CH2-.

[0136] R e C 1-6 The alkyl group can be a straight or branched C 1-6 Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, and the like.

[0137] R e C 2-6 The alkenyl group can be a straight or branched C 2-6 Specific examples include vinyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, pentenyl, hexenyl, and the like.

[0138] R e Examples of the aryl group represented include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, and the like.

[0139] R e Preferred are hydrogen or methyl.

[0140] W represents a C optionally substituted by a phenyl group 1-6 Examples of the alkylene group include methylene, methylmethylene, dimethylmethylene, phenylmethylene, phenylmethylmethylene, diphenylmethylene and the like.

[0141] Examples of the cycloalkylene group represented by W include cyclohexane-1,1-diyl and the like.

[0142] W represents C optionally substituted by halogen 2-6 Examples of the alkenediyl group include ethylene-1,1-diyl, 2,2-dichloroethylene-1,1-diyl, and the like.

[0143] Examples of -(alkylene)-(phenylene)-(alkylene)- represented by W include -(C 1-3 alkylene)-(phenylene)-(C 1-3 Alkylene)- etc. C 1-3 The alkylene group may be methylene, methylmethylene, dimethylene, trimethylene, ethylmethylene, dimethylmethylene, etc., preferably dimethylmethylene. The phenylene group may be 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene, preferably 1,4-phenylene.

[0144] W is preferably C 1-6 Alkylene, more preferably C 1-3 Alkylene (especially dimethylmethylene).

[0145] Y a Preferably, the group represented by formula (3) (wherein R e represents hydrogen or methyl, W represents C 1-3 alkylene).

[0146] Preferred examples of the compound represented by Chemical Formula (IV) include a compound represented by Chemical Formula (IV-1), a compound represented by Chemical Formula (IV-2), and a compound represented by Chemical Formula (IV-3):

[0147] where R a 、R d 、R e , W and n are as described above,

[0148]

[0149] Among them, R a 、R b 、R c 、R d 、R e , W and n as above, and

[0150] where R a 、R e , W and n are as described above.

[0151] These polyphenylene ether resins can be synthesized by or based on a known method described in, for example, US Pat. No. 4,059,568 or Journal of Organic Chemistry (1969), 34, 297-303.

[0152] Commercially available polyphenylene ether resins may also be used. Examples of commercially available products include SA9000-111 (product name) supplied by SABIC, OPE-2St (product name) and OPE-2EA (product name) supplied by Mitsubishi Gas Chemical Company, Inc., and the like.

[0153] These polyphenylene ether resins may be used alone or in combination of two or more.

[0154] The weight average molecular weight (Mw) of the polyphenylene ether resin is generally 1000 to 120000, preferably 1000 to 50000, and more preferably 1000 to 20000. The weight average molecular weight can be measured by gel permeation chromatography (GPC) using a polystyrene standard.

[0155] Bismaleimide resin refers to a compound containing two maleimide groups in the molecule, and refers to a bismaleimide compound before curing. Examples of bismaleimide resins include aliphatic bismaleimide compounds, aromatic bismaleimide compounds, and the like.

[0156] Examples of the aliphatic bismaleimide compound include N,N'-(2,2,4-trimethylhexamethylene)bismaleimide, N,N'-decamethylenebismaleimide, N,N'-octamethylenebismaleimide, N,N'-heptamethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-pentamethylenebismaleimide, N,N'-tetramethylenebismaleimide, N,N'-trimethylenebismaleimide, N,N'-ethylenebismaleimide, N,N'-(oxydimethylene)bismaleimide, 1,13-bismaleimido-4,7,10-trioxatridecane, 1,11-bismaleimido-3,6,9-trioxaundecane, and the like.

[0157] Examples of aromatic bismaleimide compounds include N,N'-(4-methyl-1,3-phenylene)bismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'-(1,4-phenylene)bismaleimide, N,N'-(1,2-phenylene)bismaleimide, N,N'-(1,5-naphthylene)bismaleimide, N,N'-(4-chloro-1,3-phenylene)bismaleimide, N,N'-(methylenebis-para- bismaleimide, N,N'-(4,4'-biphenylene)bismaleimide, N,N'-(sulfonylbis-p-phenylene)bismaleimide, N,N'-(oxybis-p-phenylene)bismaleimide, N,N'-(3,3'-dimethyl-4,4'-biphenylene)bismaleimide, N,N'-(benzylidenebis-p-phenylene)bismaleimide, N,N'-[methylenebis(3-chloro-4-phenylene)]bismaleimide, N,N'-[methylenebis(3-methyl-4-phenylene)]bismaleimide, N,N'-[methylenebis(3-methoxy-4-phenylene)]bismaleimide, N,N'-(thiobis-p-phenylene)bismaleimide, N,N'-3,3'-benzophenonebismaleimide, N,N'-[methylenebis(3-methyl-5-ethyl-4-phenylene)]bismaleimide, N,N'-[tetramethylenebis(oxy-p-phenylene)]bismaleimide imide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, bis[4-(4-maleimidophenoxy)phenyl)]sulfone, 1,4-phenylenebis(4-maleimidophenoxy), bis[3-(4-maleimidophenoxy)phenyl]sulfone, bis[4-(3-maleimidophenoxy)phenyl]ketone, 1,3-phenylenebis(4-maleimidophenoxy), bis[4-(4-maleimidophenylthio)phenyl]ether, etc.

[0158] Commercially available bismaleimide resins can also be used. Examples of commercially available products include: BMI-689 (product name), BMI-1500 (product name), BMI-2500 (product name), and BMI-3000J (product name) provided by Designer Molecules Inc.; BMI-1000 (product name), BMI-2300 (product name), BMI-4000 (product name), and BMI-5100 (product name) provided by Daiwa Kasei Industry Co., Ltd.; MIR-3000-70MT (product name) and MIR-5000 (product name) provided by Nippon Kayaku Co., Ltd.; BMI (product name), BMI-70 (product name), and BMI-80 (product name) provided by KIChemical Industry Co., Ltd.; and the like.

[0159] These bismaleimide resins may be used alone or in combination of two or more.

[0160] Any bismaleimide-triazine resin can be used as long as it is prepolymerized from a maleimide compound and a cyanate ester compound as main components. Examples include: a resin formed by heating and melting 2,2-bis(4-cyanatophenyl)propane and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane and polymerizing them; and a resin formed by heating and melting a novolac cyanate resin and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane and polymerizing them, followed by dissolving them in methyl ethyl ketone.

[0161] Examples of the polyfunctional styrene compound include divinylphenylmethane, 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, the compound represented by Chemical Formula (VI), and divinylbenzene polymers (oligomers) having a vinyl group on the side chain:

[0162]

[0163] Among them, each Y b Same or different, means -(C 1-3Alkylene)-(divalent organic group having a cyclic structure)-(C 1-3 alkylene)-, p represents an integer of 1 to 10.

[0164] C 1-3 Examples of the alkylene group include methylene, methylmethylene, dimethylene, trimethylene, ethylmethylene, dimethylmethylene and the like.

[0165] Examples of the divalent organic group having a cyclic structure include a phenylene group, a xylylene group, a naphthylene group, a tolylene group, a biphenylene group, a group containing an indane structure, a group containing a cycloolefin structure, and the like.

[0166] Preferred examples of the compound represented by Chemical Formula (VI) include the compound represented by Chemical Formula (VI-1), the compound represented by Chemical Formula (VI-2), and the like:

[0167]

[0168] wherein p represents an integer from 1 to 10,

[0169]

[0170] Here, p represents an integer from 1 to 10.

[0171] Examples of polystyrene resins include compounds having a structure represented by formula (4):

[0172]

[0173] Among them, R f 、R g and R h the same or different, each representing hydrogen or C 1-6 alkyl.

[0174] R f 、R g and R h C 1-6 The alkyl group can be a straight or branched C 1-6 Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, and the like.

[0175] Examples of embodiments of the compound of the structure represented by formula (4) include a compound having a structure represented by formula (4-1) and a compound having a structure represented by formula (4-2):

[0176]

[0177] Preferably, the compound having the structure represented by formula (4) has the structure represented by formula (5) in the molecule. The compound may be a polymer in which the structure represented by formula (4) and the structure represented by formula (5) are randomly bonded, or the compound may be a block copolymer or a random copolymer:

[0178]

[0179] Among them, R i 、R j and R k the same or different, each representing hydrogen or C 1-6 Alkyl, R l Represents an aryl group.

[0180] R i 、R j and R k C 1-6 The alkyl group can be a straight or branched C 1-6 Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, and the like.

[0181] R l The aryl group represented by may be an unsubstituted aryl group or an aryl group substituted with an alkyl group, etc. Specific examples include methylphenyl, ethylphenyl, propylphenyl, butylphenyl, tert-butylphenyl, vinylphenyl, naphthyl, ethylnaphthyl, biphenyl, ethylbiphenyl, and the like.

[0182] Examples of embodiments of the structure represented by formula (5) include the structure represented by formula (5-1), the structure represented by formula (5-2), and the structure represented by formula (5-3):

[0183]

[0184] The compound having the structure represented by formula (4) has the structure represented by formula (6) in the molecule. The compound may be a polymer in which the structure represented by formula (4) and the structure represented by formula (6) are randomly bonded, or the compound may be a block copolymer or a random copolymer. Alternatively, the compound may be a polymer in which the structure represented by formula (4), the structure represented by formula (5) and the structure represented by formula (6) are randomly bonded, or the compound may be a block copolymer or a random copolymer:

[0185]

[0186] where R m Represents hydrogen, C 1-18 Alkyl, C 5-8 cycloalkyl, aryl or benzyl.

[0187] R m C 1-18The alkyl group can be a straight or branched C 1-18 Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and the like.

[0188] R m C 5-8 Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.

[0189] R m The aryl group represented by may be unsubstituted or substituted. Specific examples include phenyl, 4-hydroxyphenyl, 4-acetylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-chlorophenyl, 4-bromophenyl, and the like.

[0190] A preferred embodiment of the compound having the structure represented by formula (4) may be a compound having a structural unit represented by formula (4-1) and at least one of a structural unit represented by formula (5-1) and a structural unit represented by formula (5-2) in the molecule. The compound may be a block copolymer or a random copolymer.

[0191] Preferably, the molar content of the structural unit represented by formula (4-1) is 1 to 92 mol%, the molar content of the structural unit represented by formula (5-1) is 0 to 54 mol%, and the molar content of the structural unit represented by formula (5-2) is 0 to 89 mol%.

[0192] The average number of the structural units represented by formula (4-1) is preferably 1 to 350. The average number of the structural units represented by formula (5-1) is preferably 0 to 160. The average number of the structural units represented by formula (5-2) is preferably 0 to 270.

[0193] Commercially available polystyrene resins may also be used. Examples of commercially available products include ODV-XET (X03) (product name), ODV-XET (X04) (product name), and ODV-XET (X05) (product name) provided by NIPPON STEEL Chemical & Material Co., Ltd.

[0194] These polystyrene resins may be used alone or in combination of two or more.

[0195] The weight average molecular weight (Mw) of the polystyrene resin is preferably 1500 to 40000, more preferably 1500 to 35000. The weight average molecular weight can be measured by gel permeation chromatography (GPC) using a styrene standard.

[0196] Examples of polybutadiene resins include compounds having at least one of the following structures: a polybutadiene structure represented by formula (7), a polybutadiene structure represented by formula (8), and a polybutadiene structure represented by formula (9). These polybutadiene structures include not only structures formed by polymerization of butadiene but also structures formed by hydrogenation of polybutadiene structures. In the compound, at least one polybutadiene structure may be present in the main chain or in a side chain:

[0197]

[0198] Where m represents the number of repeating units, usually an integer of 1 or greater,

[0199]

[0200] wherein m represents the number of repeating units, usually an integer of 1 or greater, and

[0201]

[0202] Wherein m represents the number of repeating units, which is usually an integer of 1 or greater.

[0203] A compound having at least one of the polybutadiene structures represented by formula (7), the polybutadiene structure represented by formula (8), and the polybutadiene structure represented by formula (9) may contain the structure represented by formula (6) in its molecule. The compound may be a polymer in which at least one of the polybutadiene structures represented by formula (7), the polybutadiene structure represented by formula (8), and the polybutadiene structure represented by formula (9) is randomly bonded to the structure represented by formula (6), or the compound may be a block copolymer or a random copolymer.

[0204] Other examples of the polybutadiene resin include butadiene homopolymer, epoxy-modified polybutadiene, butadiene-styrene random copolymer, maleic acid-modified polybutadiene, and the like.

[0205] Commercially available polybutadiene resins can also be used. Examples of commercially available products include: Ricon 130 (product name), Ricon 131 (product name), Ricon 142 (product name), Ricon 150 (product name), Ricon 152 (product name), Ricon 153 (product name), Ricon 156 (product name), and Ricon 157 (product name) supplied by Cray Valley; B-1000 (product name), B-2000 (product name), and B-3000 (product name) (butadiene homopolymers) supplied by Nippon Soda Co., Ltd.; Ricon 100 (product name) and Ricon 181 (product name) (butadiene-styrene-random copolymers) supplied by Cray Valley; Ricon 130MA8 (product name), Ricon 130MA13 (product name), Ricon 130MA20 (product name), and Ricon 130MA17 (product name) supplied by Cray Valley. 156MA17 (product name) (maleic acid-modified polybutadiene); etc.

[0206] These polybutadiene resins may be used alone or in combination of two or more.

[0207] The number average molecular weight (Mn) of the polybutadiene resin is preferably 500 to 10000, more preferably 1000 to 6000. The number average molecular weight can be measured by gel permeation chromatography (GPC) using a polystyrene standard.

[0208] Any benzocyclobutene resin can be used as long as two or more benzocyclobutene groups are bonded directly or through an organic group.

[0209] In the thermal radical curable resin composition of the present invention, the above-mentioned thermal radical curable resin components may be used alone or in combination of two or more.

[0210] Other resin components

[0211] The thermally radical curable resin composition of the present invention may contain, in addition to the thermally radical curable resin component, one or more resin components other than the thermally radical curable resin component (other resin components) as needed. Examples of such other resin components include the above-mentioned resin components and styrene block copolymers.

[0212] Examples of styrenic block copolymers include styrene-butadiene block copolymers, styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene block copolymers, styrene-ethylene / butylene-styrene block copolymers (SEBS), styrene-(ethylene-ethylene / propylene)-styrene block copolymers (SEEPS), and styrene-ethylene / propylene-styrene block copolymers (SEPS). These copolymers can be used alone or in combination of two or more.

[0213] Available styrene block copolymers may be commercially available products. Examples of commercially available products include Tufprene (trade name), Asaprene T (trade name) and Tuftec (trade name) provided by Asahi Kasei Corporation; Elastomer AR (trade name) provided by Aronkasei Co., Ltd.; Kraton G (trade name) and Califlex (trade name) provided by Kraton Polymer Japan Co., Ltd.; JSR-TR (trade name), TSR-SIS (trade name) and Dynaron (trade name) provided by JSR; Denka STR (trade name) provided by Denka Company Limited; Quintac (trade name) provided by Zeon Corporation; Esporex SB series (trade name) provided by Sumitomo Chemical Co., Ltd.; Kuraray Co., Ltd. Co., Ltd.; Sumiflex (trade name) from Sumitomo Bakelite Co., Ltd.; and Leostomer (trade name) and Actimer (trade name) from Riken Technos Corporation. These styrenic block copolymers can be used alone or in combination of two or more.

[0214] In the thermal radical curable resin composition of the present invention, the amount of other resin components is not limited. Relative to 100 parts by weight of the thermal radical curable resin component, the amount of other resin components is 0 to 1000 parts by weight, preferably 1 to 800 parts by weight, and more preferably 10 to 700 parts by weight.

[0215] flame retardants

[0216] In addition to the phosphorus compound of the present invention, the thermally radical curable resin composition of the present invention may further contain one or more other flame retardants described in the above section "3. Flame retardant and resin composition" as needed.

[0217] In the thermal radical curable resin composition of the present invention, the amount of the phosphorus compound of the present invention is not limited. The amount of the phosphorus compound of the present invention is 1 to 200 parts by weight, preferably 1 to 160 parts by weight, and more preferably 2 to 150 parts by weight, relative to 100 parts by weight of the resin component (the total amount of the thermal radical curable resin component and other resin components).

[0218] In the thermal free radical curable resin composition of the present invention, the amount of other flame retardants is not limited. Relative to 100 parts by weight of the resin component (the total amount of the thermal free radical curable resin component and other resin components), the amount of other flame retardants is 0 to 100 parts by weight, preferably 1 to 80 parts by weight, and more preferably 10 to 40 parts by weight.

[0219] crosslinking agent

[0220] The thermal radical curable resin composition of the present invention may contain a crosslinking agent as long as the effects of the resin composition of the present invention can be exhibited.

[0221] Examples of cross-linking agents include mono(C 6-20 The present invention also includes the following: monobenzyldiaryl isocyanurate, tris(4-vinylbenzyl)isocyanurate, tris(4-vinylbenzyloxy)triazine, triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl trimellitate, and the above-mentioned multifunctional styrene compounds. These compounds can be used alone or in combination of two or more.

[0222] In the thermally radical curable resin composition of the present invention, the amount of the crosslinking agent is not limited. The amount of the crosslinking agent is 0 to 200 parts by weight, preferably 5 to 150 parts by weight, and more preferably 10 to 100 parts by weight, relative to 100 parts by weight of the resin component (the total amount of the thermally radical curable resin component and other resin components).

[0223] The thermal radical curable resin composition of the present invention may further contain other components as needed. Examples of these other components include the above-mentioned radical polymerization initiator, the above-mentioned inorganic filler, the stress reliever, the organic solvent, and the above-mentioned additives.

[0224] Free radical polymerization initiator

[0225] Examples of usable radical polymerization initiators include the radical polymerization initiators described in the above section "3. Flame retardant and resin composition".

[0226] In the thermal radical curable resin composition of the present invention, the amount of the radical polymerization initiator is not limited. The amount of the radical polymerization initiator is 0.001 to 10 parts by weight, preferably 0.01 to 8 parts by weight, and more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the resin component (the total amount of the thermal radical curable resin component and other resin components).

[0227] Inorganic fillers

[0228] Examples of usable inorganic fillers include the inorganic fillers described in the above section "3. Flame retardant and resin composition".

[0229] In the thermal free radical curable resin composition of the present invention, the amount of the inorganic filler is not limited. Relative to 100 parts by weight of the resin component (the total amount of the thermal free radical curable resin component and other resin components), the amount of the inorganic filler is 0 to 800 parts by weight, preferably 1 to 600 parts by weight, and more preferably 10 to 400 parts by weight.

[0230] stress relievers

[0231] The stress reliever used is not limited. Examples include silicone resin particles. The average particle size of the stress reliever is preferably 10 μm or less. Using a stress reliever having such an average particle size can improve the adhesion of the thermally radical curable resin composition of the present invention to metal foil when applied to a metal-clad laminate.

[0232] The amount of the stress reliever in the thermally radical curable resin composition of the present invention is not limited. The amount of the stress reliever is 0 to 100 parts by weight, preferably 0 to 50 parts by weight, relative to 100 parts by weight of the resin component (the total amount of the thermally radical curable resin component and other resin components).

[0233] organic solvents

[0234] Any organic solvent that can dissolve or disperse the thermal free radical curing resin component can be used. Examples include: ketone solvents, such as methyl ethyl ketone (MEK); ether solvents, such as dibutyl ether; ester solvents, such as ethyl acetate; amide solvents, such as dimethylformamide; aromatic hydrocarbon solvents, such as benzene, toluene and xylene; and chlorinated hydrocarbon solvents, such as trichloroethylene. These solvents can be used alone or in combination of two or more. The thermal free radical curing resin composition of the present invention containing an organic solvent can be used to make a prepreg by impregnating a substrate with the resin composition in the form of a resin varnish, as described below.

[0235] The amount of organic solvent in the thermally radical curable resin composition of the present invention can be adjusted depending on whether the substrate is impregnated with the resin varnish, coated with the resin varnish, or both. The amount of organic solvent is 30 to 1000 parts by weight, preferably 100 to 500 parts by weight, per 100 parts by weight of the resin component (the total amount of the thermally radical curable resin component and other resin components).

[0236] additive

[0237] Examples of the additives include the additives described in the above section "3. Flame retardant and resin composition".

[0238] In the thermal free radical curable resin composition of the present invention, the amount of the additive is not limited. Relative to 100 parts by weight of the resin component (the total amount of the thermal free radical curable resin component and other resin components), the amount of the additive is 0 to 50 parts by weight, preferably 1 to 20 parts by weight.

[0239] The thermal free radical curable resin composition of the present invention can be prepared by mixing and / or kneading a thermal free radical curable resin component and the phosphorus compound of the present invention, and optionally other resin components, other flame retardants, crosslinking agents, free radical polymerization initiators, inorganic fillers, stress relievers, organic solvents and additives using known methods. For example, the thermal free radical curable resin composition of the present invention can be prepared by mixing and / or kneading a mixture of the components in liquid, powder, beaded, flaky or granular form using an extruder (e.g., a single-screw extruder, a twin-screw extruder), a kneader (e.g., a Banbury mixer, a pressure kneader, a two-roll mill, a three-roll mill), or the like.

[0240] 5. Application of the resin composition of the present invention

[0241] The resin composition described in the above section 3 and the thermally free radical curable resin composition described in the above section 4 (hereinafter collectively referred to as "the resin composition of the present invention") can be used for applications such as prepregs, metal foils with resins, thermosetting resin films, metal-clad laminates, printed wiring boards, resin boards, semiconductor devices, adhesives, etc.

[0242] Prepreg

[0243] The prepreg of the present invention is as follows.

[0244] When using resin combination of the present invention to prepare the prepreg for RCC etc., resin combination of the present invention can be prepared into varnish shape and as resin varnish.This resin varnish can for example be prepared as follows.First, the component soluble in organic solvent (component contained in resin combination of the present invention) is added in organic solvent and dissolves.At this moment, if desired, can heat.Then, add the optional component (component contained in resin combination of the present invention) that is insoluble in organic solvent, for example inorganic filler, and use ball mill, bead mill, planetary mixer, roller mill etc. that gained mixture is dispersed, until reaching predetermined dispersed state, thereby can prepare varnish shape resin combination of the present invention.

[0245] The prepreg of the present invention comprises the resin composition of the present invention or a semi-cured product of the resin composition of the present invention, and a substrate. The semi-cured product refers to the resin composition of the present invention in a partially cured state (B-stage resin composition).

[0246] The prepreg of the present invention may be a prepreg comprising the semi-cured resin composition of the present invention (B-stage resin composition) and a substrate, or a prepreg comprising the resin composition of the present invention before curing (A-stage resin composition) and a substrate.

[0247] Examples of substrates for prepregs include glass cloth, aramid cloth, polyester cloth, LCP (liquid crystal polymer) nonwoven fabric, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper and linter paper. Examples of materials for glass cloth include common E glass, as well as D glass, S glass, NE glass, quartz glass, L glass, etc. If glass cloth is used, a laminate with excellent mechanical strength can be obtained. Glass cloth is preferably flattened glass cloth. The flattening process can be carried out by, for example, continuously pressurizing the glass cloth with a suitable pressure using a pressure roller to suppress and flatten the yarn. The thickness of the substrate is, for example, 0.02 to 0.3 mm.

[0248] The proportion of the substrate in the prepreg is 20 to 80% by weight, preferably 25 to 70% by weight, of the entire prepreg.

[0249] The example of prepreg manufacturing method comprises that resin combination of the present invention is prepared into varnish shape, is then coated on substrate or is impregnated in the method for substrate.The example of the method for impregnation and / or coating comprises the method for impregnating substrate (dip coating method), the coating method using roller coater, die coater, rod coater etc. and the spraying method using sprayer etc..Impregnation and / or coating can be carried out repeatedly as required.Coating or impregnation can also be carried out repeatedly by using a variety of resin combinations with different resin component concentrations as required.After impregnation or coating, can be dried or heated.

[0250] The substrate impregnated and coated with the resin composition of the present invention is heated at 80 to 180° C. for 1 to 10 minutes to obtain a prepreg in a semi-cured state (B-stage resin composition).

[0251] Table 1 shows an example of a preferred formulation (excluding an organic solvent) of the resin composition of the present invention for use as a prepreg. The amount of each component is based on 100 parts by weight of the total amount of component (A).

[0252] Table 1

[0253]

[0254]

[0255] Note: The total amount of component (A) is 100 parts by weight.

[0256] Using such prepregs, metal-clad laminates and printed wiring boards having excellent electrical properties (eg, dielectric properties), heat resistance, flame retardancy, adhesive strength, and chemical resistance can be manufactured.

[0257] Metal foil with resin

[0258] The resin-coated metal foil of the present invention is as follows.

[0259] The resin-coated metal foil of the present invention comprises: a resin layer containing the resin composition of the present invention or a semi-cured product of the resin composition of the present invention; and a metal foil.

[0260] The resin-coated metal foil of the present invention has a metal foil on the surface of a resin layer containing the resin composition of the present invention or a semi-cured product of the resin composition of the present invention. In addition, the resin-coated metal foil of the present invention may have another layer between the resin layer and the metal foil.

[0261] As described above, the resin layer may be a semi-cured product of the resin composition of the present invention (B-stage resin composition), or may be a resin composition of the present invention before curing (A-stage resin composition). The resin layer may or may not contain a substrate. The substrate may be the same as the substrate of the prepreg.

[0262] The metal foil may be, for example, a copper foil or an aluminum foil. The copper foil may have a thickness of, for example, about 12 to 70 μm.

[0263] The method for producing the resin-coated metal foil of the present invention includes, for example, coating the resin composition of the present invention, prepared in a varnish-like state as described above, onto a metal foil. The coating method is not limited, as long as it is a method capable of coating the resin composition of the present invention onto a metal foil. Examples include coating methods using a roll coater, die coater, rod coater, etc., as well as spray coating methods using a sprayer, etc. After coating, the coating may be dried and heated.

[0264] The metal foil coated with the resin composition of the present invention is heated at 80 to 180° C. for 1 to 10 minutes to obtain a semi-cured metal foil with resin (B-stage resin composition).

[0265] Examples of preferred formulations (excluding organic solvents) for the resin composition of the present invention used as a metal foil with a resin containing a substrate are the same as the examples of preferred formulations for the resin composition of the present invention used as a prepreg (see Table 1 above). Table 2 shows examples of preferred formulations (excluding organic solvents) for the resin composition of the present invention used as a metal foil with a resin containing no substrate. The amounts of each component are expressed based on 100 parts by weight of the total amount of component (A).

[0266] Table 2

[0267]

[0268] Note: The total amount of component (A) is 100 parts by weight.

[0269] Using this resin-coated metal foil, metal-clad laminates and printed wiring boards having excellent electrical properties (such as dielectric properties), heat resistance, flame retardancy, adhesive strength, and chemical resistance can be manufactured.

[0270] Thermosetting resin film

[0271] The thermosetting resin film of the present invention is as follows.

[0272] The thermosetting resin film of the present invention can be produced by molding the resin composition of the present invention into a desired shape. For example, the thermosetting resin film of the present invention can be produced by coating the resin composition of the present invention on a support and drying it.

[0273] The support is not particularly limited. Examples include metal foils such as copper foil or aluminum foil, and organic films such as polyester resin, polyethylene resin, or polyethylene terephthalate resin (PET) films. The support can be subjected to a demolding treatment using a silicone compound or the like. The resin composition of the present invention can be used in various shapes, and the shape is not particularly limited.

[0274] The method for coating the resin composition of the present invention on the support is not limited. From the perspective of thin filmization and film thickness control, for example, gravure printing, slot die coating, and doctor blade method are preferred. The slot die coating method can be used to manufacture an uncured film (thermosetting resin film of the present invention) of the resin composition having a thickness of 5 to 300 μm after curing.

[0275] Drying conditions can be appropriately set depending on the type and amount of the organic solvent used in the resin composition of the present invention, the coating thickness, and other factors. For example, drying conditions can be 50 to 120°C for 1 to 60 minutes. The thermosetting resin film of the present invention thus obtained has excellent storage stability. The thermosetting resin film can be peeled from the support at any desired time.

[0276] The thermosetting resin film of the present invention can be cured at, for example, 150 to 230°C for 30 to 180 minutes. The thermosetting resin film of the present invention can be cured after being sandwiched between substrates having circuits formed thereon using, for example, copper foil, or after being appropriately laminated with thermosetting resin films having circuits formed thereon using, for example, copper foil. The thermosetting resin film can also be used as a cover film to protect the circuits on the substrate. The curing conditions used in this case are similar.

[0277] Furthermore, the thermosetting resin film of the present invention can be suitably used as a flexible copper clad laminate (FCCL) of a flexible printed wiring board (FPC), a copper clad laminate (CCL) of a multilayer board, or a build-up material.

[0278] Table 3 shows an example of a preferred formulation (excluding organic solvent) of the resin composition of the present invention for use as a thermosetting resin film. The amounts of each component are based on 100 parts by weight of component (A). When an organic solvent is added, it is preferably added in an amount to achieve a viscosity within the range of 200 to 3000 mPa·s.

[0279] Table 3

[0280]

[0281]

[0282] Note: The total amount of component (A) is 100 parts by weight.

[0283] Metal-clad laminate

[0284] The metal-clad laminate of the present invention is as follows.

[0285] The metal-clad laminate of the present invention comprises an insulating layer comprising a cured product of the resin composition of the present invention and a metal foil. The metal-clad laminate comprises the metal foil on the surface of the insulating layer. The metal-clad laminate may further comprise another layer between the insulating layer and the metal foil.

[0286] The insulating layer may or may not contain a base material. The base material may be the same as that of the prepreg. The same metal foil as that coated with the resin may be used as the metal foil.

[0287] A method for manufacturing a metal-clad laminate may, for example, be a method using the above-mentioned prepreg. A method for manufacturing a metal-clad laminate using a prepreg may, for example, include stacking at least one prepreg, then stacking a metal foil (e.g., copper foil) on both or one side of the prepreg, and then heating and press-molding these stacked layers to form an integrated laminate. This method can produce a laminate with metal foil clad on one or both sides of the laminate.

[0288] The heating and pressing conditions can be appropriately set according to the thickness of the metal-clad laminate to be manufactured and the formulation of the resin composition used in the prepreg. For example, the conditions can be a temperature of 170 to 220°C, a pressure of 1.5 to 5.0 MPa, and a time of 60 to 150 minutes.

[0289] Metal-clad laminates can also be produced without using prepregs. Examples of such methods include a method comprising applying the varnish-like resin composition of the present invention to a metal foil to form a layer containing the resin composition of the present invention on the metal foil, followed by heating and pressurizing; and a method comprising curing a thermosetting resin film using the metal foil as a support.

[0290] An example of a preferred formulation (excluding an organic solvent) of the resin composition of the present invention for use as a metal-clad laminate including a substrate is the same as the formulation of the resin composition for use as a prepreg (see Table 1 above). An example of a preferred formulation (excluding an organic solvent) of the resin composition of the present invention for use as a metal-clad laminate not including a substrate is the same as the formulation of the resin composition for use as a resin-coated metal foil not including a substrate (see Table 2 above).

[0291] Using this metal-clad laminate, a printed wiring board having excellent electrical properties (such as dielectric properties), heat resistance, flame retardancy, adhesive strength, and chemical resistance can be manufactured.

[0292] printed circuit boards

[0293] The printed wiring board of the present invention is as follows.

[0294] The printed wiring board of the present invention includes an insulating layer and wiring, wherein the insulating layer comprises a cured product of the resin composition of the present invention or a cured product of the thermosetting film of the present invention. The printed wiring board of the present invention has wiring on the surface of the insulating layer. In addition, the printed wiring board of the present invention may have one or more other layers between the insulating layer and the wiring.

[0295] The insulating layer may or may not contain a substrate. The substrate may be the same material as the prepreg.

[0296] The printed wiring board of the present invention has an insulating layer comprising a cured product of the resin composition of the present invention or a cured product of the thermosetting resin film of the present invention, and therefore has excellent electrical properties (eg, dielectric properties) and high flame retardancy.

[0297] The circuit is not particularly limited as long as it can be provided on a printed wiring board. For example, the circuit can be formed by partially removing a metal foil stacked on an insulating layer. Examples of the circuit include circuits formed by a subtractive method, an additive method, a semi-additive method, chemical mechanical polishing (CMP), a trench method, an inkjet method, a scraper method, a transfer method, and the like.

[0298] A method for manufacturing a printed wiring board, for example, uses the metal-clad laminate described above. The method for manufacturing a printed wiring board using a metal-clad laminate involves, for example, etching or otherwise processing the metal foil on the surface of the metal-clad laminate to form a circuit. This method produces a printed wiring board having a conductor pattern formed as a circuit on the surface of the metal-clad laminate.

[0299] An example of a preferred formulation (excluding an organic solvent) of the resin composition of the present invention for a printed wiring board containing a substrate in the insulating layer is the same as the formulation of the resin composition used as a prepreg (see Table 1 above). An example of a preferred formulation (excluding an organic solvent) of the resin composition of the present invention for a printed wiring board containing no substrate in the insulating layer is the same as the formulation of the resin composition used as a copper foil with a resin containing no substrate (see Table 2 above).

[0300] The resulting printed wiring board has excellent electrical properties (such as dielectric properties), heat resistance, flame retardancy, and chemical resistance, and can effectively suppress circuit peeling. In addition, the printed wiring board is easy to install even in a packaged form with a semiconductor chip bonded thereto, has stable quality, and has excellent signal speed and impedance.

[0301] Resin board

[0302] The resin composition of the present invention can be used as a resin plate produced by curing the resin composition to form a plate. For example, a resin plate can be obtained by coating the varnish-like resin composition of the present invention to form a plate, drying it, and then curing the dried coating. Examples of resin plates include unclad plates obtained by removing the metal foil of a metal-clad laminate.

[0303] semiconductor devices

[0304] The following describes the case where the resin composition of the present invention is used for a semiconductor device.

[0305] A semiconductor device can be manufactured by using the resin composition of the present invention or the thermosetting resin film of the present invention and curing the composition or the film. Based on the cured product of the resin composition of the present invention or the cured product of the thermosetting resin film of the present invention, the semiconductor device has excellent electrical properties (such as dielectric properties) and high flame retardancy, and is therefore suitable for high-frequency applications.

[0306] A semiconductor device is any device that utilizes the properties of a semiconductor to function. Examples of semiconductor devices include electronic components, semiconductor circuits, modules containing these components and circuits, and electronic devices.

[0307] Adhesives

[0308] The adhesive of the present invention is as follows.

[0309] The adhesive of the present invention contains the resin composition of the present invention as a component. The adhesive of the present invention can be used as an adhesive between two materials selected from metals, inorganic materials, and resin materials. The adhesive of the present invention is particularly preferably used as an adhesive between a metal and one material selected from metals, inorganic materials, and resin materials.

[0310] Examples of metals include copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof. Of these metals, copper is preferred. Forms of the metals include plates, foils, and films of these metals.

[0311] Examples of inorganic materials include silicon, ceramics, carbon used as fillers, inorganic salts, and glass. Specific examples include silicon compounds such as silicon, silicon carbide, silicon dioxide, glass, diatomaceous earth, calcium silicate, talc, glass beads, sericite activated clay, bentonite, aluminosilicate, and mica; oxides such as aluminum oxide, zinc oxide, iron oxide, magnesium oxide, tin oxide, and titanium oxide; hydroxides such as magnesium hydroxide, aluminum hydroxide, and basic magnesium carbonate; carbonates such as calcium carbonate, zinc carbonate, hydrotalcite, and magnesium carbonate; sulfates such as barium sulfate and gypsum; titanates such as barium titanate; nitrides such as aluminum nitride and silicon nitride; graphites such as flake graphite (natural graphite), expandable graphite, and expandable graphite (synthetic graphite); activated carbon; carbon fibers; and carbon black.

[0312] Among these inorganic materials, silicon, ceramics (aluminum oxide, silicon carbide, aluminum nitride, silicon nitride, barium titanate, etc.), glass, and inorganic salts are preferred.

[0313] Examples of resin materials include nylon, acrylic resins, epoxy resins, olefin resins, benzoxazine resins, polybenzoxazole resins, siloxane resins, polyamide resins, polyimide resins, bismaleimide resins, maleimide resins, cyanate resins, polyphenylene oxide resins, polyphenylene oxide resins, fluorine-containing resins, polyether resins, polyetherimide resins, polyetheretherketone resins, polyester resins, siloxane resins, liquid crystal resins, etc. These materials can be used in combination by mixing or modification, etc.

[0314] Among these resin materials, acrylate resins, epoxy resins, olefin resins, benzoxazine resins, polybenzoxazole resins, bismaleimide resins, polyphenylene ether resins, fluorine-containing resins, polyether resins, liquid crystal resins, siloxane resins, and polyimide resins are preferred.

[0315] As a method for bonding materials using an adhesive, known methods can be used. Specific examples include: (1) a method comprising applying an adhesive to a surface of a material selected from metal, inorganic material, and resin material, pressing another material onto part or all of the applied adhesive, and then bonding the materials (by curing the adhesive); and (2) a method comprising forming a semi-cured adhesive into a sheet, adhering the sheet to the surface of one material selected from metal, inorganic material, and resin material, and then pressing another material onto part or all of the other side of the adhesive to bond the materials (by curing the adhesive).

[0316] The adhesive can be cured using known methods. Examples include a method involving heating and pressurizing using a hot press, and a method involving drying the applied adhesive before heat treatment. Heating and pressurizing conditions include, for example, a temperature of 50 to 300°C (particularly 80 to 250°C), a pressure of 0.1 to 50 MPa (particularly 0.5 to 10 MPa), and a duration of approximately 1 minute to 10 hours (particularly 30 minutes to 5 hours).

[0317] As described above, since the adhesive of the present invention can bond two materials, especially two different materials, the adhesive of the present invention is suitable for electronic devices such as various electric or electronic components, semiconductor wafers, printed wiring boards, and flexible metal clad laminates.

[0318] Examples of preferred formulations (excluding the organic solvent) of the resin composition of the present invention for use as an adhesive are the same as the formulations of the above-mentioned thermosetting resin films (see Table 3 above).

[0319] In this specification, the terms “comprising” or “having” also encompass the concepts of “consisting essentially of” and “consisting of.

[0320] Example

[0321] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

[0322] The main raw materials used in the embodiment are as follows:

[0323] Main raw materials

[0324] -2,6-dimethyl-4-vinylphenol (see Chemical Formula (II-1)); (Synthesized according to the method described in Royal Society Open Science (2022), 9(4), 220014)

[0325] -Phosphorus oxychloride (see Chemical Formula (III); provided by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0326] -Dichloromethane (provided by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0327] -Potassium tert-butoxide (provided by Tokyo Chemical Industry Co., Ltd.)

[0328] The main raw materials used in the evaluation tests are as follows:

[0329] Main raw materials

[0330] (i) Thermal radical curable resin component

[0331] -Methacrylate-modified polyphenylene ether (SABIC, polyphenylene ether resin, product name "SA9000-111", molecular weight: 2300)

[0332] (ii) Other resin components

[0333] - Styrene-butadiene-styrene block copolymer (product name: Tufprene A, provided by Asahi Kasei Corporation, styrene-based block copolymer, styrene / butadiene weight ratio = 40 / 60)

[0334] (iii) Flame retardants

[0335] -Tris(2,6-dimethyl-4-vinylphenyl)phosphate (see Chemical Formula (I-1), Example 1; hereinafter referred to as "flame retardant 1")

[0336] -Tris(4-vinylphenyl)phosphate (see chemical formula (V); synthesized according to the method described in CN109762115A; hereinafter referred to as "flame retardant 2")

[0337] - Triallyl isocyanurate (see chemical formula (VII), supplied by Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as "flame retardant 3").

[0338]

[0339] (iv) Radical polymerization initiator

[0340] -α,α'-di(tert-butylperoxy)diisopropylbenzene (Nippon Oil & Fats, product name "Perbutyl P")

[0341] (v) Organic solvents

[0342] -Toluene (provided by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0343] The evaluation tests (flame retardancy evaluation method, glass transition temperature measurement method, dielectric properties measurement method, and moisture absorption resistance evaluation) used in the examples and comparative examples are as follows:

[0344] (1) Flame retardancy evaluation

[0345] Each resin composition was applied to a 25 μm-thick polyimide film using a bar coater to a dried film thickness of 50 ± 5 μm. Toluene was then evaporated until constant weight was achieved. The resulting product was then heat-treated at 150°C for 30 minutes and at 190°C for 1 hour to obtain a film for evaluation. The flame retardancy of the resulting film was evaluated according to the UL94V™ vertical flame test method, a standard of the US UL standard.

[0346] (2) Measurement of glass transition temperature (Tg)

[0347] Each resin composition was poured into a mold set to 1 mm thick using a 1 mm thick silicone spacer. The mold was then placed in a forced air drying oven heated to 80°C to evaporate the toluene to a constant weight. The resulting mixture was then heated at 120°C for 30 minutes, 150°C for 30 minutes, and 190°C for 1 hour to obtain a 1 mm thick plate-shaped cured product.

[0348] A test piece measuring 20 mm in length, 5 mm in width, and 1 mm in thickness was cut from each of the resulting cured products and mounted on the solid torsion fixture of a dynamic mechanical analyzer (DMA) (Rheosol-G5000, supplied by UBM). Dynamic viscoelasticity was measured over a temperature range of 50 to 300°C at a heating rate of 5°C / min, a frequency of 1 Hz, and a strain of 0.08%. The glass transition temperature (unit: °C) was defined as the peak temperature of the loss modulus.

[0349] The higher the glass transition temperature of the test piece, the better the heat resistance of the cured product.

[0350] Materials having a glass transition temperature of 230°C or higher were rated as "A", materials having a glass transition temperature of 150°C or higher and lower than 230°C were rated as "B", and materials lower than 150°C were rated as "C".

[0351] (3) Dielectric properties measurement (relative dielectric constant: Dk, dielectric tangent: Df)

[0352] Each resin composition was poured into a mold set to 1 mm thick using a 1 mm thick silicone spacer. The mold was then placed in a forced air drying oven heated to 80°C to evaporate the toluene to a constant weight. The resulting composition was then heated at 120°C for 30 minutes, 150°C for 30 minutes, and 190°C for 1 hour to obtain a 1 mm thick plate-shaped cured product.

[0353] A test sample 50 mm long, 2 mm wide, and 1 mm thick was cut from each of the cured products thus obtained and dried at 200°C for 3 hours. The dielectric properties (relative dielectric constant Dk and dielectric tangent Df) before humidification were measured at a measurement frequency (10 GHz) using a network analyzer (E8361A; supplied by Agilent Technologies) using a cavity resonance method.

[0354] The smaller the relative dielectric constant (Dk) and dielectric tangent (Df) of the test sample, the better the dielectric properties of the cured product.

[0355] (4) Hygroscopicity resistance evaluation

[0356] A cured product was prepared in the same manner as in (3). After the cured product was allowed to stand for 24 hours under humidified conditions (25°C / 50% RH), the dielectric tangent (Df) after humidification was measured under the same conditions as in (3). The change (%) in dielectric tangent (Df) before and after humidification was calculated as follows:

[0357] Change rate (%) = (dielectric tangent Df after humidification - dielectric tangent Df before humidification) ÷ dielectric tangent Df before humidification × 100

[0358] The smaller the change rate (%), the better the moisture absorption resistance of the cured product.

[0359] Example 1

[0360] Synthesis of Tris(2,6-Dimethyl-4-vinylphenyl) Phosphate

[0361] 133.38 g (900.0 mmol) of 2,6-dimethyl-4-vinylphenol and 1000 mL of dichloromethane were placed in a 2000 mL reactor and cooled to -10°C with stirring. Subsequently, 96.50 g (860.0 mmol) of potassium tert-butoxide were added while maintaining the temperature between -10 and 0°C. The temperature was then raised to 5°C and stirring continued for 1 hour. Subsequently, 30.67 g (200.0 mmol) of phosphorus oxychloride were added dropwise while maintaining the temperature between -10 and 0°C. After the addition was complete, the temperature was raised to 5°C and the mixture was stirred for 3 hours. The temperature was then raised to 25°C and the mixture was stirred for 14 hours. The reaction mixture was then washed with water and the organic layer was concentrated. The resulting concentrate was purified by column chromatography (toluene / hexane = 2 / 1 (volume ratio)) to obtain 63.21 g of a light yellow liquid (yield: 64.7%).

[0362] The light yellow liquid 1 The H-NMR spectral data are as follows:

[0363] · 1 H-NMR (CDCl3) δ: 7.07 (s, 6H), 6.60 (dd, 3H), 5.66 (d, 3H), 5.19 (d, 3H), 2.31 (s, 18H).

[0364] The infrared spectrum data of the light yellow liquid is as follows Figure 1 shown.

[0365] Based on these spectral data, the obtained light yellow liquid was identified as the compound represented by chemical formula (I-1).

[0366] Example 2

[0367] A thermal radical-curable resin composition was prepared by mixing 4.88 parts by weight of SA9000-111 as a thermal radical-curable resin component, 1.52 parts by weight of Tufprene A as another resin component, 3.60 parts by weight of the phosphorus compound obtained in Example 1 as a flame retardant, 0.12 parts by weight of Perbutyl P as a radical polymerization initiator, and 10.12 parts by weight of toluene as an organic solvent.

[0368] The resin composition was subjected to evaluation tests (flame retardancy evaluation, glass transition temperature measurement, dielectric property measurement, and moisture absorption resistance evaluation). Table 4 shows the obtained test results.

[0369] Comparative Examples 1 to 3

[0370] A resin composition having the formulation shown in Table 4 was prepared in the same manner as in Example 2. The resin composition was subjected to evaluation tests. Table 4 shows the obtained test results.

[0371] Table 4

[0372]

[0373]

[0374] From Table 4, it can be confirmed that, compared with the case where no flame retardant is used (Comparative Example 1) or a conventional flame retardant is used (Comparative Examples 2 and 3), when the phosphorus compound of the present invention is used as a flame retardant (Example 2), the cured product has high flame retardancy, high glass transition temperature (Tg), low relative dielectric constant Dk, and low dielectric tangent Df. In addition, it is also confirmed that the rate of change after humidification of Example 2 is significantly lower than that of Comparative Examples 2 and 3. Therefore, the resin composition containing the flame retardant of the present invention is believed to provide a cured product with excellent flame retardancy, heat resistance, electrical properties, and moisture absorption resistance.

[0375] Industrial Applicability

[0376] The resin composition containing the phosphorus compound of the present invention can provide a cured product having excellent flame retardancy, heat resistance, electrical properties and moisture absorption resistance, and is therefore suitable for use as a material for printed wiring boards, adhesives, and the like.

Claims

1. A phosphorus compound represented by chemical formula (I): in, Each R 1 Indicates C 1-10 Alkyl, each R 2 Indicates C 1-10 Alkyl, each R 3 Same or different, represents hydrogen atoms or C 1-10 alkyl.

2. A method for synthesizing the phosphorus compound according to claim 1, comprising: The p-vinylphenol compound represented by chemical formula (II) is reacted with phosphorus oxychloride represented by chemical formula (III): Among them, R 1 、R 2 and each R 3 As mentioned above, A flame retardant comprising the phosphorus compound according to claim 1 .

4. A resin composition comprising: The phosphorus compound according to claim 1; as well as Resin component.

5. A prepreg comprising: The resin composition according to claim 4; as well as substrate.

6. A metal foil with resin, comprising: a resin layer comprising the resin composition according to claim 4 or a semi-cured product of the resin composition; as well as Metal foil. 7 . A thermosetting resin film formed from the resin composition according to claim 4 .

8. A metal-clad laminate comprising: an insulating layer comprising a cured product of the resin composition according to claim 4; as well as Metal foil.

9. A printed circuit board comprising: an insulating layer comprising a cured product of the resin composition according to claim 4 or a cured product of the thermosetting resin film according to claim 7; as well as line.

10. An adhesive comprising the resin composition according to claim 4 as a component.

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