Tris[(ethenylphenyl)methyl]benzene, method for synthesizing same, and use thereof

Abstract

The present invention provides a new tris[(ethenylphenyl)methyl]benzene, a method for synthesizing the same, a cross-linking agent containing said compound, and a resin composition containing said compound and a resin component. The present invention further provides a prepreg, a resin-attached metallic foil, a thermosetting resin film, a metal clad laminated board, a printed wiring board, and an adhesive agent, in all of which the resin composition is used. A tris[(ethenylphenyl)methyl]benzene according to the present invention is represented by chemical formula (I). Respective Rs in chemical formula (I) are identical or are different from each other, and each represent an alkyl group having 1-6 carbon atoms.

Description

Tris[(ethenylphenyl)methyl]benzenes, their synthesis method and use

[0001] The present invention relates to a polymerizable group (-C ６ H ４ -CH=CH ２ This invention relates to novel tris[(ethenylphenyl)methyl]benzenes having the formula (I), a method for synthesizing the same, and uses thereof.

[0002] In recent years, electronic devices have become smaller and more powerful, and in multilayer printed wiring boards, build-up layers have become more numerous, and finer and denser wiring is required. In particular, in high-frequency applications, insulating materials (resin materials) with excellent electrical properties (e.g., low dielectric loss tangent) are required to reduce transmission loss of electrical signals.

[0003] A compound represented by chemical formula (V) is known as a material with excellent electrical properties (see, for example, Patent Documents 1 and 2). This compound has a highly symmetrical molecular structure and a polymerizable group (-C ６ H ４ -CH=CH ２ ) As a result, a cured product of a resin composition containing this compound exhibits the properties of having a relatively low dielectric constant and a high glass transition temperature.

[0004]

[0005] International Publication No. 1988 / 05059 Japanese Patent Application Laid-Open No. 2003-26744

[0006] However, the compound represented by the above chemical formula (V) has a polar functional group (oxygen atom) in its molecular structure, so there is still room for improvement in its electrical properties. In addition, the compound has a high degree of crystallinity, which means that its compatibility (solubility) with various solvents and resin components is extremely low.

[0007] The present invention aims to provide novel tris[(ethenylphenyl)methyl]benzenes, a method for synthesizing the same, a crosslinking agent containing the compound, and a resin composition containing the compound and a resin component. It also aims to provide prepregs, resin-coated metal foils, thermosetting resin films, metal-clad laminates, printed wiring boards, and adhesives that use the resin compositions.

[0008] As a result of extensive research into solving the above problems, the present inventors have found that the desired object can be achieved by using certain tris[(ethenylphenyl)methyl]benzenes, and have thus completed the present invention.

[0009] That is, the first invention is a tris[(ethenylphenyl)methyl]benzene represented by the chemical formula (I).

[0010]

[0011] (In formula (I), R may be the same or different and represent an alkyl group having 1 to 6 carbon atoms.)

[0012] The second invention is a method for synthesizing the tris[(ethenylphenyl)methyl]benzenes of the first invention, which comprises reacting a compound represented by chemical formula (II) with a compound represented by chemical formula (III), and then reacting the resulting mixture with a base.

[0013]

[0014] (In formula (II), R is the same as above. X １ represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0015]

[0016] (In formula (III), X ２ represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0017] The third invention is a crosslinking agent containing the tris[(ethenylphenyl)methyl]benzene of the first invention. The fourth invention is a resin composition containing the tris[(ethenylphenyl)methyl]benzene of the first invention and a resin component. The fifth invention is a prepreg comprising the resin composition of the fourth invention and a substrate. The sixth invention is a resin-coated metal foil comprising a resin layer containing the resin composition of the fourth invention or a semi-cured product of the resin composition, and a metal foil. The seventh invention is a thermosetting resin film formed from the resin composition of the fourth invention. The eighth invention is a metal-clad laminate comprising an insulating layer containing a cured product of the resin composition of the fourth invention and a metal foil. The ninth invention is a printed wiring board comprising an insulating layer containing a cured product of the resin composition of the fourth invention or a cured product of the thermosetting resin film of the seventh invention, and wiring. The tenth invention is an adhesive comprising the resin composition of the fourth invention.

[0018] The tris[(ethenylphenyl)methyl]benzenes of the present invention have excellent compatibility (solubility) with various solvents and resin components, and also have a polymerizable group (-C ６ H ４ -CH=CH ２ ) and therefore is expected to be used as a crosslinking agent for resins. Furthermore, the tris[(ethenylphenyl)methyl]benzenes of the present invention have no polar functional groups in their molecular structure, are highly symmetric, and are highly compatible with various solvents and resin components. Therefore, when used as a crosslinking agent for resins, they are expected to give cured products with lower water absorption and excellent heat resistance and electrical properties (e.g., low dielectric tangent) compared to those obtained when conventional crosslinking agents are used. 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 have excellent adhesion, water absorption resistance, heat resistance, and electrical properties.

[0019] FIG. 1 shows the precursor obtained in the synthesis of crosslinker 1. １ 2 is a H-NMR spectrum chart of the crosslinking agent 1 obtained in the synthesis of crosslinking agent 1. １3 is an IR spectrum chart of Crosslinking Agent 1 obtained in the synthesis of Crosslinking Agent 1.

[0020] (1. Tris[(ethenylphenyl)methyl]benzenes) The present invention relates to tris[(ethenylphenyl)methyl]benzenes represented by chemical formula (I) (hereinafter, sometimes referred to as "compounds of the present invention").

[0021]

[0022] (In formula (I), R may be the same or different and represent an alkyl group having 1 to 6 carbon atoms.)

[0023] Examples of the alkyl group having 1 to 6 carbon atoms represented by R include linear or branched alkyl groups having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group.

[0024] In the compound of the present invention, preferred substituents are as follows: R are the same and are preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and even more preferably a methyl group.

[0025] Examples of the compound of the present invention include compounds represented by chemical formulas (I-1) to (I-8). In chemical formulas (I-5) to (I-8), "Et" represents an ethyl group.

[0026]

[0027] (2. Method for Synthesizing the Compound of the Present Invention) The compound of the present invention can be synthesized by reacting a compound represented by chemical formula (II) with a compound represented by chemical formula (III) (Step 1), and then reacting the resulting compound with a base (Step 2) (see Reaction Scheme (A)).

[0028]

[0029] (In formula (II), R may be the same or different and represent an alkyl group having 1 to 6 carbon atoms; X １represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. ２ represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0030] In formula (II), the alkyl group having 1 to 6 carbon atoms represented by R is the same as that exemplified in formula (I), and the preferred examples are also the same.

[0031] Examples of the compound represented by chemical formula (II) include compounds represented by the following chemical formulas (II-1) to (II-4).

[0032]

[0033] These compounds can be purchased as commercially available reagents or can be synthesized in accordance with the method described in, for example, Angewandte Chemie, International Edition (2018), 57 (18), 4981-4985.

[0034] Examples of the compound represented by the chemical formula (III) include (2-chloroethyl)benzene, (2-bromoethyl)benzene, and (2-iodoethyl)benzene.

[0035] These compounds can be purchased as commercially available reagents.

[0036] In the reaction of the first step, the amount of the compound represented by chemical formula (III) used (charge amount) is preferably an appropriate ratio in the range of 3 to 50 times the molar amount of the compound represented by chemical formula (II) used (charge amount).

[0037] In carrying out the first step, it is preferable to use an acid (i) to promote the reaction. If necessary, a reaction solvent (ii) may be used appropriately. Examples of the acid (i) include hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, carbonic acid, formic acid, acetic acid, benzoic acid, oxalic acid, citric acid, phosphoric acid, hexafluorophosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, boric acid, boron trifluoride, tetrafluoroboric acid, aluminum chloride, zinc chloride, titanium tetrachloride, tin tetrachloride, ferric chloride, ferric bromide, ethyl aluminum dichloride, and copper(II) bromide.

[0038] The amount of acid (i) used (charged amount) is preferably an appropriate ratio in the range of 0.01 to 3 times the amount of the compound represented by the chemical formula (II) used (charged amount).

[0039] The reaction solvent (ii) is not particularly limited as long as it does not inhibit the reaction, and examples thereof include solvents such as tetrahydrofuran, dioxane, ethyl acetate, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, and water, and these can be combined as necessary and used in appropriate amounts.

[0040] In the reaction of the first step, the reaction temperature is preferably set in the range of 20 to 160° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 1 to 80 hours.

[0041] After completion of the reaction in the first step, a precursor compound of the compound of the present invention (hereinafter referred to as the precursor compound of the present invention) can be isolated from the resulting reaction solution (reaction mixture) by, for example, concentrating the reaction solution by distilling off the reaction solvent or by solvent extraction. If necessary, the precursor compound can be purified by washing with water or the like, or by using activated carbon treatment, silica gel chromatography, recrystallization, or the like. The precursor compound of the present invention may be subjected to the above-described concentration, extraction, purification, or the like before being subjected to the second step, or the reaction solution obtained after completion of the reaction in the first step may be subjected to the second step as is.

[0042] Examples of the base used in the second step include trimethylamine, triethylamine, tributylamine, N,N-diisopropylethylamine, N-methylmorpholine, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), pyridine, 4-(N,N-dimethylamino)pyridine, picoline, N,N-dimethylaniline, N,N-diethylaniline, imidazole, lithium hydride, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate Examples of the alkoxide include lithium, potassium carbonate, cesium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, trilithium phosphate, trisodium phosphate, tripotassium phosphate, tricesium phosphate, dilithium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, cesium dihydrogen phosphate, lithium acetate, sodium acetate, potassium acetate, cesium acetate, lithium alkoxides (lithium methoxide, etc.), sodium alkoxides (sodium methoxide, sodium ethoxide, etc.), potassium alkoxides (potassium t-butoxide, etc.), etc. These may be used alone or in combination of two or more.

[0043] The amount of base used (charged amount) is preferably an appropriate ratio in the range of 3 to 20 times the amount of the precursor compound of the present invention used (charged amount).

[0044] In carrying out the second step, a reaction solvent (ii) may be used as needed. As the reaction solvent (ii), the same solvents as those exemplified in the first step can be used.

[0045] In the reaction of the second step, the reaction temperature is preferably set in the range of −10 to 100° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 1 to 80 hours.

[0046] After completion of the reaction in the second step, the target compound of the present invention can be isolated from the resulting reaction solution (reaction mixture) by, for example, concentrating the reaction solution by distilling off the reaction solvent, solvent extraction, etc. If necessary, the compound can be further purified by washing with water or the like, treatment with activated carbon, silica gel chromatography, recrystallization, etc.

[0047] In this synthesis method, four or more polymerizable groups (-C ６ H ４ -CH=CH ２ ) can be obtained (see reaction scheme (B)).

[0048]

[0049]

[0050] (In the formula, R, １ and X ２ is the same as above.)

[0051] Four or more polymerizable groups (-C ６ H ４ -CH=CH ２ ) include, for example, compounds represented by chemical formulas (A1) to (A11). These compounds may be contained in the crosslinking agent and resin composition of the present invention.

[0052]

[0053]

[0054] (3. Crosslinking Agent and Resin Composition) The crosslinking agent of the present invention contains the compound of the present invention. The compound of the present invention has excellent compatibility (solubility) with various solvents and resin components, and has a polymerizable group (-C ６ H ４ -CH=CH ２ ) and therefore can be suitably used as a crosslinking agent for resins. From the viewpoint of compatibility (solubility) with various solvents and resin components, ６ H ４ -CH=CH ２ ) is preferably a mixture of compounds having different bonding positions (for example, a mixture of compounds represented by chemical formulas (I-1) to (I-4)).

[0055] Furthermore, the resin composition of the present invention contains the compound of the present invention and a resin component. By including the compound of the present invention in the resin composition, the cured product (molded product) of the resin composition exhibits low water absorption and excellent heat resistance and electrical properties (for example, low dielectric tangent). In the present invention, the term "resin composition" refers to the state of the mixture before curing. The content of the compound of the present invention in the resin composition of the present invention is not particularly limited, and is preferably 0.1 to 200 parts by weight, more preferably 0.5 to 100 parts by weight, and even more preferably 1 to 80 parts by weight, per 100 parts by weight of the resin component.

[0056] [Resin Component] The resin component (including uncured and semi-cured resins) used in the resin composition of the present invention is not particularly limited as long as it is a material that is commonly used as a material for a resin molded article. Examples of the resin component include polyethylene resin, chlorinated polyethylene resin, polyvinyl chloride resin, polypropylene resin, polyisoprene resin, impact-resistant 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 polystyrene resin (ABS resin), polyvinyl chloride resin, ... Examples of suitable resins include polyester resins, polyesterimide resins, polyketone resins, polycarbonate resins, polyamide resins, polyimide precursors, polyimide resins, polyamideimide resins, polycarbodiimide resins, polyetherimide resins, polyetherketone resins, polyetheretherketone resins (PEEK resins), polyethersulfone resins, polythioethersulfone resins, polysulfone resins, polyphenylene sulfide resins, polyethernitrile resins, polyarylate resins, polybenzimidazole resins, benzoxazine resins, liquid crystal polymer resins, silicone resins, epoxy resins, polyurethane resins, phenolic resins, melamine resins, urea resins, and diallyl phthalate resins. These may be used alone or in combination of two or more.

[0057] The polyimide precursor may be, for example, a polyamide having a structural unit represented by the following chemical formula (B1): The polyimide precursor having a structural unit represented by the following formula (B1) is suitable when the resin composition is used as a photosensitive resin composition.

[0058]

[0059] (In formula (B1), X １１ is a tetravalent organic group having 6 to 40 carbon atoms, and Y １１is a divalent organic group having 6 to 40 carbon atoms, and n １ is an integer from 2 to 150, and R １ and R ２ are the same or different and are a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a group represented by the following chemical formula (B2): １ and R ２ At least one of the above is a group represented by the following chemical formula (B2):

[0060]

[0061] (In formula (B2), R ３ , R ４ and R ５ are the same or different and are a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms, m １ is an integer from 2 to 10.

[0062] R １ and R ２ Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by the formula (I) include a linear or branched alkyl group having 1 to 10 carbon atoms and a linear or branched alkynyl group having 2 to 10 carbon atoms. Examples of the linear or branched alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of the linear or branched alkynyl group having 2 to 10 carbon atoms include a vinyl group, an allyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and a decenyl group.

[0063] R ３ ~R ５ Examples of the monovalent hydrocarbon group having 1 to 3 carbon atoms represented by the formula (I) include a linear or branched alkyl group having 1 to 3 carbon atoms and a linear or branched alkynyl group having 2 to 3 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a vinyl group, an allyl group, and an isopropenyl group.

[0064] R of the structural unit represented by the above chemical formula (B1) contained in the polyimide precursor １ and R ２ The proportion of the group represented by the above chemical formula (B2) to all of the above is preferably 50 to 100 mol % from the viewpoint of high resolution, and more preferably 75 to 100 mol % from the viewpoint of high chemical resistance and sensitivity.

[0065] n in the above chemical formula (B1) １ is preferably an integer of 3 to 100, more preferably an integer of 5 to 70, from the viewpoint of the photosensitive properties and mechanical properties of the photosensitive resin composition.

[0066] In the above chemical formula (B1), X １１ The tetravalent organic group represented by the formula (I) is preferably an organic group having 6 to 40 carbon atoms, more preferably -COOR, in order to achieve both heat resistance and photosensitive properties. １ group and -COOR ２ The X group and the —CONH— group are in the ortho position relative to each other, or an alicyclic aliphatic group. １１ Specific examples of the tetravalent organic group represented by the formula (a) include organic groups containing an aromatic ring and having 6 to 40 carbon atoms, such as groups having structures represented by the following general formulas (a-1) to (a-19), but are not limited thereto.

[0067]

[0068] (In formulas (a-1) to (a-19), R6 represents a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms or a fluorine-containing alkyl group having 1 to 10 carbon atoms; d represents an integer of 0 to 2; e represents an integer of 0 to 3; and f represents an integer of 0 to 4.)

[0069] The monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R6 is the same as that exemplified in formula (B1).

[0070] Also, X １１ The structure of X having the structure represented by the above formula (a-1) to formula (a-19) may be one type or a combination of two or more types. １１ The group is particularly preferred in that it has both heat resistance and photosensitive properties.

[0071] X１１ As the structure represented by the formula (a-20), the structure represented by the following formula (a-20) is particularly preferred from the viewpoint of low dielectric tangent.

[0072]

[0073] (In formula (a-20), Ry may be the same or different and represent a monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain a halogen atom; a １ represents an integer of 0 to 4, and D １ are each independently an oxygen atom or a sulfur atom, and D ２ is a single bond or at least one group represented by the following formula:

[0074]

[0075] Among the above formula (a-20), the structure represented by the following formula (a-20-1) or formula (a-20-2) is particularly preferred.

[0076]

[0077] Also, X １１ As the structure represented by the formula (a-21), a structure represented by the following formula (a-21) is preferred from the viewpoint of the thermal weight loss rate.

[0078]

[0079] In the above chemical formula (B1), Y １１ The divalent organic group represented by the formula (b-1) is preferably an aromatic group having 6 to 40 carbon atoms, in order to achieve both heat resistance and photosensitive properties. Examples of the divalent organic group include, but are not limited to, structures represented by the following formulas (b-1) to (b-23):

[0080]

[0081]

[0082] (In formulas (b-1) to (b-23), R6, e, and f are the same as defined above.)

[0083] Also, Y １１ The structure of Y having the structure represented by the above formula (b-1) to formula (b-23) may be one type or a combination of two or more types. １１The group is particularly preferred in that it has both heat resistance and photosensitive properties.

[0084] Y １１ As the group, from the viewpoint of reducing the dielectric loss tangent, a structure represented by the following formula (b-24) is particularly preferred.

[0085]

[0086] (In formula (b-24), Rz's are the same or different and represent monovalent hydrocarbon groups having 1 to 10 carbon atoms which may contain a halogen atom; a ２ is an integer from 0 to 4, and E １ are each independently an oxygen atom or a sulfur atom, E ２ is a single bond or at least one group represented by the following formula:

[0087]

[0088] Among the above formula (b-24), the structures represented by the following formulas (b-24-1) to (b-24-3) are particularly preferred from the viewpoints of low dielectric tangent, low dielectric constant, and lithographic properties.

[0089]

[0090] R in the above general formula (B2) ３ is preferably a hydrogen atom or a methyl group, and R ４ and R ５ is preferably a hydrogen atom from the viewpoint of photosensitive properties. １ is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less, from the viewpoint of photosensitivity characteristics.

[0091] The resin composition of the present invention may contain, in addition to the compound of the present invention and the resin component, a flame retardant, a polymerizable component, a polymerization initiator, a reactive diluent, a fluororesin, an inorganic filler, and / or an additive, as necessary.

[0092] [Flame Retardant] The resin composition of the present invention may contain a flame retardant. Examples of the flame retardant include phosphate ester compounds, phosphazene compounds, phosphite ester compounds, phosphine compounds, melamine phosphate, phosphate amide compounds, phosphate amide ester compounds, phosphinate compounds and salts thereof, ammonium phosphate, ammonium polyphosphate, melam, melam polyphosphate, melem, melem polyphosphate, red phosphorus, melon, melamine, melamine pyrophosphate, melamine cyanurate, succinoguanamine, phosphonate esters, phosphinate esters, phosphine oxide, ethylenebispentabromobenzene, and ethylenebistetrabromophthalimide. Examples of phosphate ester compounds include condensed phosphate ester compounds such as triphenyl phosphate, tricresyl phosphate, xylenyl diphenyl phosphate, cresyl diphenyl phosphate, 1,3-phenylenebis(di-2,6-xylenyl phosphate), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), and aromatic condensed phosphate ester compounds, as well as cyclic phosphate ester compounds. Examples of phosphazene compounds include cyclic or chain phosphazene compounds. Cyclic phosphazene compounds, also known as cyclophosphazenes, are compounds with a cyclic structure containing phosphorus and nitrogen as constituent elements and a double bond in the molecule. Examples of phosphite ester compounds include trimethyl phosphite and triethyl phosphite. Examples of phosphine compounds include tris-(4-methoxyphenyl)phosphine and triphenylphosphine. These compounds may be used alone or in combination of two or more.

[0093] The content of the flame retardant in the resin composition of the present invention is not particularly limited, and is preferably 0 to 200 parts by weight, more preferably 0.5 to 100 parts by weight, and even more preferably 1 to 50 parts by weight, per 100 parts by weight of the resin component.

[0094] [Polymerizable Component] 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, and cyclic compounds (epoxy compounds, lactone compounds, lactam compounds, cyclic ether compounds, etc.). Examples of these polymerizable components include vinyl chloride, butadiene, isoprene, styrene, high-impact polystyrene precursors, acrylonitrile-styrene resin (AS resin) precursors, acrylonitrile-butadiene-styrene resin (ABS resin) precursors, methyl methacrylate-butadiene-styrene resin (MBS resin) precursors, methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin) precursors, acrylonitrile-acrylic rubber-styrene resin (AAS resin) precursors, methyl (meth)acrylate, epoxy acrylate resin precursors, epoxidized oil acrylate resin precursors, and urethane acrylate resins. precursor, polyester acrylate resin precursor, polyether acrylate resin precursor, acrylic acrylate resin precursor, unsaturated polyester resin precursor, vinyl / acrylate resin precursor, vinyl ether resin precursor, polyene / thiol resin precursor, silicon acrylate resin precursor, polybutadiene acrylate resin precursor, polystyryl(ethyl)methacrylate resin precursor, polycarbonate acrylate resin precursor, alicyclic epoxy resin precursor, glycidyl ether epoxy resin precursor, and photocurable or thermosetting polyimide resin precursor, silicon-containing resin precursor, epoxy resin precursor, etc. These may be used alone or in combination of two or more.

[0095] The content of the polymerizable component in the resin composition of the present invention is not particularly limited, and is preferably 0 to 200 parts by weight, more preferably 0.5 to 100 parts by weight, and even more preferably 1 to 50 parts by weight, per 100 parts by weight of the resin component.

[0096] [Polymerization Initiator] The resin composition of the present invention may contain a polymerization initiator. The polymerization initiator can be appropriately selected depending on the method for polymerizing the resin composition of the present invention. Examples of the polymerization initiator include a thermal polymerization initiator, a photopolymerization initiator, and a radical polymerization initiator. Examples of the thermal polymerization initiator 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; and acid generators such as aromatic sulfonates. These may be used alone or in combination of two or more.

[0097] Examples of photopolymerization initiators 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. These may be used alone or in combination of two or more. When a photopolymerization initiator is used, a sensitizer such as a tertiary amine may be used in combination, if necessary.

[0098] Examples of the radical polymerization initiator include peroxides such as di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxide)hexane, 2,5-dimethyl-2,5-di(t-butylperoxide)hexyne-3, α,α'-di(t-butylperoxy)diisopropylbenzene, and t-butyl peroxybenzoate. These may be used alone or in combination of two or more.

[0099] The content of the polymerization initiator in the resin composition of the present invention is not particularly limited, and is preferably 0 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and even more preferably 0.1 to 3 parts by weight, per 100 parts by weight of the resin component.

[0100] [Reactive Diluent] The resin composition of the present invention may contain a reactive diluent as needed. 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 tertiary carboxylic acid glycidyl esters; and aromatic alkyl glycidyl ethers such as styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-s-butylphenyl glycidyl ether, and nonylphenyl glycidyl ether. These may be used alone or in combination of two or more.

[0101] The content of the reactive diluent in the resin composition of the present invention is not particularly limited, and is preferably 0 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, and even more preferably 0.1 to 20 parts by weight, per 100 parts by weight of the resin component.

[0102] [Fluororesin] The resin composition of the present invention may contain a fluororesin for the purpose of improving the flame retardancy (particularly drip prevention performance) of the cured product (formed product). Examples of fluororesins include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), poly(trifluorochloroethylene) (CTFE), and polyfluorovinylidene (PVdF). These may be used alone or in combination of two or more.

[0103] The content of the fluororesin in the resin composition of the present invention is not particularly limited, and is preferably 0 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the resin component.

[0104] [Inorganic Filler] The resin composition of the present invention may contain an inorganic filler for the purpose of improving the flame retardancy (particularly drip prevention performance) and mechanical strength of the cured product (formed product). Examples of inorganic fillers include mica, natural mica, synthetic mica, kaolin, calcined kaolin, talc, calcined talc, wollastonite, silica, alumina, boron nitride, clay, calcined clay, titania, barium sulfate, barium carbonate, calcium carbonate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, calcium silicate, titanium oxide, zinc oxide, zinc borate, glass beads, glass balloons, glass flakes, short glass fibers, glass fine powder, hollow glass, and fibrous aluminum titanate. Examples of suitable inorganic fillers include potassium metal salts (such as potassium titanate fibers and sodium titanate fibers), fibrous borates (such as aluminum borate fibers, magnesium borate fibers, and zinc borate fibers), 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, alumina fibers, alumina-silica fibers, zirconia fibers, quartz fibers, flaky titanates, and flaky titanium dioxide. These may be used alone or in combination of two or more. In particular, to reduce the dielectric constant of the resin composition, it is preferable to use a low-dielectric-constant filler such as silica or boron nitride as an inorganic filler. Examples of silica include pulverized silica, fused silica, natural silica, fired silica, synthetic silica, crystalline silica, and amorphous silica.

[0105] The inorganic filler preferably has an average particle size of 5 μm or less. For example, by using an inorganic filler such as silica particles having an average particle size of 5 μm or less, adhesion to metal foil is improved when the resin composition is used in a metal-clad laminate or the like.

[0106] Furthermore, in order to prevent deterioration of the resin component, the surface of the inorganic filler may be coated with a silane coupling agent.

[0107] The content of the inorganic filler in the resin composition of the present invention is not particularly limited. In order to balance the improvement of flame retardancy and the improvement of mechanical properties, the content of the inorganic filler is preferably 0 to 200 parts by weight, more preferably 5 to 100 parts by weight, per 100 parts by weight of the resin component.

[0108] [Additives] The resin composition of the present invention may contain various additives depending on the intended use, the type of resin component, etc., within the range that does not impair the intended physical properties. Examples of additives include white carbon, aluminum nitride, zinc borate, zinc stannate, zinc molybdate, molybdenum oxide, silicon nitride, aerosil, wollastonite, nanocarbons (nanocarbon tubes, graphene, fullerene, etc.), organic fibers (aramid fibers, polyparaphenylene benzobisoxazole fibers, etc.), silane coupling agents, waxes, fatty acids and metal salts thereof, release agents (acid amides, paraffin, etc.), chlorinated paraffin, silicone-based flame retardants, bromine-based flame retardants, flame retardant assistants (antimony trioxide, etc.), ultraviolet absorbers (benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds, etc.), antioxidants (hindered phenol compounds, styrenated phenol compounds), and the like. Examples of the additives include organic peroxide decomposers, organic phosphorus peroxide decomposers, organic sulfur peroxide decomposers, etc.), fluorescent brighteners (stilbene derivatives, etc.), light stabilizers (hindered amine compounds, etc.), photosensitizers, gloss agents, metal deactivators (benzotriazole compounds, etc.), light-shielding agents (rutile titanium oxide, zinc oxide, chromium oxide, cerium oxide, etc.), quenchers (organic nickel, etc.), curing agents, curing accelerators, crosslinking agents, diluents, flowability modifiers, polymerization inhibitors, dyes, pigments, colorants, antifogging agents, antifungal agents, antibacterial agents, deodorizers, plasticizers, antistatic agents, surfactants, defoaming agents, foaming agents, leveling agents, lubricants, lubricants, thixotropy-imparting agents, thickeners, nucleating agents, reinforcing agents, compatibilizers, conductive agents, antiblocking agents, anti-tracking agents, luminous agents, plasticizers, adhesives, pressure-sensitive adhesives, tackifiers, and various stabilizers. These may be used alone or in combination of two or more.

[0109] The content of the additive in the resin composition of the present invention is not particularly limited, but is preferably 0 to 50 parts by weight, more preferably 1 to 20 parts by weight, per 100 parts by weight of the resin component.

[0110] The resin composition of the present invention can be produced by mixing and / or kneading the resin component, the compound of the present invention, and, if necessary, a flame retardant, a polymerizable component, a polymerization initiator, a reactive diluent, a fluororesin, an inorganic filler, and additives by a known method. For example, the resin composition can be produced by mixing and / or kneading a mixture of liquid, powder, bead, flake, or pellet-like components using an extruder (such as a single-screw extruder or a twin-screw extruder), a kneader (such as a Banbury mixer, a pressure kneader, a two-roll mill, or a three-roll mill), or the like.

[0111] (4. Thermally Radical Curable Resin Composition) The resin composition of the present invention may be a thermally radically curable resin composition that is cured using thermal energy (hereinafter referred to as the "thermally radically curable resin composition of the present invention"). The thermally radically curable resin composition of the present invention contains the compound of the present invention and a thermally radically curable resin component. Furthermore, the thermally radically curable resin composition of the present invention may contain, in addition to the compound of the present invention and the thermally radically curable resin component, other resin components, other crosslinking agents, flame retardants, radical polymerization initiators, inorganic fillers, stress relaxation agents, organic solvents, and additives as necessary.

[0112] [Thermal Radical Curable Resin Component] Examples of the thermal radical curable resin component (including resins in uncured and semi-cured states) used in the thermal radical curable resin composition of the present invention include polyphenylene ether resins, bismaleimide resins, bismaleimide-triazine resins, polyfunctional styrene compounds, polystyrene resins, polybutadiene resins, benzocyclobutene resins, polytetrafluoroethylene resins, and acrylic resins.

[0113] The polyphenylene ether resin may be, for example, a compound having a structure represented by formula (1).

[0114]

[0115] (In formula (1), R ａ are the same or different and represent 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 and is usually an integer of 1 or more.

[0116] R ａ Examples of the alkyl group having 1 to 6 carbon atoms represented by R include linear or branched alkyl groups having 1 to 6 carbon atoms, and specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, and n-hexyl groups, with methyl being preferred. ａ Examples of the alkenyl group having 2 to 6 carbon atoms represented by R include linear or branched alkenyl groups having 2 to 6 carbon atoms, and specific examples thereof include vinyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, pentenyl, and hexenyl groups. ａ are the same or different and are preferably a hydrogen atom or a methyl group. n is preferably an integer of 1 to 400.

[0117] Examples of the compound having the structure represented by formula (1) include a compound having a structure represented by formula (1-1), a compound having a structure represented by formula (1-2), and a compound having a structure represented by formula (1-3).

[0118]

[0119] (In formula (1-1), n ​​is the same as defined above.)

[0120]

[0121] (In formula (1-2), n is the same as defined above.)

[0122]

[0123] (In formula (1-3), n is the same as defined above.)

[0124] The compound having the structure represented by formula (1) preferably has two or more structures represented by formula (1) in the molecule. Furthermore, this compound preferably has a crosslinkable group (for example, a group having a carbon-carbon double bond such as a (meth)acrylic group, an allyl group, or a vinylbenzyl group). The crosslinkable group is preferably present at the terminal of the molecule of this compound.

[0125] A preferred embodiment of the compound having the structure represented by formula (1) is, for example, a compound represented by chemical formula (IV).

[0126]

[0127] (In formula (IV), X ａ are the same or different and represent a hydrogen atom or a group represented by formula (2). ａ represents —O— or a group represented by formula (3). ａ is the same as above. n may be the same or different and is the same as above.

[0128]

[0129] (In formula (2), R ｂ , R ｃ and R ｄ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Z is an alkylene group having 1 to 10 carbon atoms, -C(=O)-, -Ph-, -Ph-CH ２ -or-Ph-CH ２ CH ２ -, where "Ph" represents a phenylene group.

[0130]

[0131] (In formula (3), R ｅ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group. W is a single bond, an alkylene group having 1 to 6 carbon atoms which may be substituted with a phenyl group, a cycloalkylene group, an alkenediyl group having 2 to 6 carbon atoms which may be substituted with a halogen atom, -C(=O)-, -S(O) ｍ -(m represents 0, 1, or 2), or -(alkylene)-(phenylene)-(alkylene)-.

[0132] R ｂ , R ｃ and R ｄ Examples of the alkyl group having 1 to 3 carbon atoms represented by R include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. ｂ and R ｃis preferably a hydrogen atom, and R ｄ is preferably a hydrogen atom or a methyl group.

[0133] Examples of the alkylene group having 1 to 10 carbon atoms represented by Z include a methylene group, a methylmethylene group, a dimethylene group, a trimethylene group, an ethylmethylene group, a dimethylmethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, and a decamethylene group. Z is -C(=O)-, -Ph-, -Ph-CH ２ -or-Ph-CH ２ CH ２ - is preferred.

[0134] R ｅ Examples of the alkyl group having 1 to 6 carbon atoms represented by R include linear or branched alkyl groups having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group. ｅ Examples of the alkenyl group having 2 to 6 carbon atoms represented by R include linear or branched alkenyl groups having 2 to 6 carbon atoms, and specific examples thereof include vinyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, pentenyl, and hexenyl groups. ｅ Examples of the aryl group represented by R include a phenyl group, a 2-tolyl group, a 3-tolyl group, and a 4-tolyl group. ｅ is preferably a hydrogen atom or a methyl group.

[0135] Examples of alkylene groups having 1 to 6 carbon atoms and optionally substituted with a phenyl group, represented by W, include a methylene group, a methylmethylene group, a dimethylmethylene group, a phenylmethylene group, a phenylmethylmethylene group, and a diphenylmethylene group. Examples of cycloalkylene groups represented by W include a cyclohexane-1,1-diyl group. Examples of alkenediyl groups having 2 to 6 carbon atoms and optionally substituted with a halogen atom, represented by W, include ethylene-1,1-diyl and 2,2-dichloroethylene-1,1-diyl. Examples of -(alkylene)-(phenylene)-(alkylene)- represented by W include -(alkylene having 1 to 3 carbon atoms)-(phenylene)-(alkylene having 1 to 3 carbon atoms)-. Examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, a methylmethylene group, a dimethylene group, a trimethylene group, an ethylmethylene group, and a dimethylmethylene group, and preferably a dimethylmethylene group. Examples of the phenylene group include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group, and preferably a 1,4-phenylene group. W is preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms (particularly a dimethylmethylene group).

[0136] Y ａ is preferably a group represented by formula (3), and in formula (3), R ｅ More preferably, is a hydrogen atom or a methyl group, and W is an alkylene group having 1 to 3 carbon atoms.

[0137] 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).

[0138]

[0139] (In formula (IV-1), R ａ , R ｄ , R ｅ , W and n are the same as above.)

[0140]

[0141] (In formula (IV-2), R ａ , R ｂ , R ｃ , R ｄ , R ｅ , W and n are the same as above, and Ph represents a phenylene group.

[0142]

[0143] (In formula (IV-3), R ａ , R ｅ , W and n are the same as above.)

[0144] These polyphenylene ether resins can be synthesized according to or in accordance with known methods, for example, those described in US Pat. No. 4,059,568 and The Journal of Organic Chemistry (1969), 34, 297-303.

[0145] Furthermore, commercially available polyphenylene ether resins can also be used as the polyphenylene ether resin. Examples of commercially available products include "SA9000-111 (trade name)" manufactured by SABIC Corporation, and "OPE-2St (trade name)" and "OPE-2EA (trade name)" manufactured by Mitsubishi Gas Chemical Company, Inc. These polyphenylene ether resins may be used alone or in combination of two or more.

[0146] 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. The weight average molecular weight can be measured using gel permeation chromatography (GPC) in styrene equivalent terms.

[0147] The bismaleimide resin is a compound having two maleimide groups in the molecule, and refers to a bismaleimide compound before curing. Examples of the bismaleimide resin include an aliphatic bismaleimide compound and an aromatic bismaleimide compound.

[0148] 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-bismaleimide-4,7,10-trioxatridecane, and 1,11-bismaleimide-3,6,9-trioxaundecane.

[0149] 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, and N,N'-(methylenedi-p-phenylene)bismaleimide. bismaleimide, N,N'-(4,4'-biphenylene)bismaleimide, N,N'-(sulfonyldi-p-phenylene)bismaleimide, N,N'-(oxydi-p-phenylene)bismaleimide, N,N'-(3,3'-dimethyl-4,4'-biphenylene)bismaleimide, N,N'-(benzylidene di-p-phenylene)bismaleimide, N,N'-[methylenebis(3-chloro-4-phenylene)]bismaleimide, N,N'-[methylene N,N'-[methylenebis(3-methyl-4-phenylene)]bismaleimide, N,N'-[methylenebis(3-methoxy-4-phenylene)]bismaleimide, N,N'-(thiodi-p-phenylene)bismaleimide, N,N'-3,3'-benzophenone bismaleimide, N,N'-[methylenebis(3-methyl-5-ethyl-4-phenylene)]bismaleimide, N,N'-[tetramethylenebis(oxy-p-phenylene)]bismaleimide, 2,2-bis[4 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, and the like.

[0150] Commercially available bismaleimide resins can also be used. Examples of commercially available bismaleimide resins include "BMI-689 (trade name)," "BMI-1500 (trade name)," "BMI-2500 (trade name)," and "BMI-3000J (trade name)" manufactured by Designer Molecules Inc.; "BMI-1000 (trade name)," "BMI-2300 (trade name)," "BMI-4000 (trade name)," and "BMI-5100 (trade name)" manufactured by Daiwa Kasei Kogyo Co., Ltd.; "MIR-3000-70MT (trade name)" and "MIR-5000 (trade name)" manufactured by Nippon Kayaku Co., Ltd.; and "BMI (trade name)," "BMI-70 (trade name)," and "BMI-80 (trade name)" manufactured by K.I. Kasei Co., Ltd. These bismaleimide resins may be used alone or in combination of two or more.

[0151] The bismaleimide-triazine resin is not particularly limited as long as it is a prepolymer containing a maleimide compound and a cyanate ester compound as main components. Examples include a resin obtained by heating and melting 2,2-bis(4-cyanatophenyl)propane and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane to polymerize, and a resin obtained by heating and melting a novolac-type cyanate ester resin and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane to polymerize, followed by dissolving the resulting resin in methyl ethyl ketone.

[0152] Examples of polyfunctional styrene compounds include 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, compounds represented by chemical formula (VII), and divinylbenzene polymers (oligomers) having vinyl groups on the side chains.

[0153]

[0154] (In formula (VII), Y ｂ are the same or different and represent -(alkylene having 1 to 3 carbon atoms)-(divalent organic group having a cyclic structure)-(alkylene having 1 to 3 carbon atoms)-, and p represents an integer of 1 to 10.

[0155] Examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, a methylmethylene group, a dimethylene group, a trimethylene group, an ethylmethylene group, a dimethylmethylene group, etc. 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, and a group containing a cycloolefin structure.

[0156] Among the compounds represented by chemical formula (VII), preferred examples include compounds represented by chemical formula (VII-1) and compounds represented by chemical formula (VII-2).

[0157]

[0158] (In formula (VII-1), p represents an integer of 1 to 10.)

[0159]

[0160] (In formula (VII-2), p represents an integer of 1 to 10.)

[0161] An example of the polystyrene resin is a compound having a structure represented by formula (4).

[0162]

[0163] (In formula (4), R ｆ , R ｇ and R ｈ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0164] R ｆ , R ｇ and R ｈExamples of the alkyl group having 1 to 6 carbon atoms represented by the formula (I) include linear or branched alkyl groups having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group.

[0165] Examples of the structure represented by formula (4) include a structure represented by formula (4-1) and a structure represented by formula (4-2).

[0166]

[0167]

[0168] The compound having the structure represented by formula (4) preferably has a structure represented by formula (5) in the molecule. This compound may be a polymer in which the structure represented by formula (4) and the structure represented by formula (5) are randomly bonded, or may be a block copolymer or a random copolymer.

[0169]

[0170] (In formula (5), R ｉ , R ｊ and R ｋ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ｌ represents an aryl group.

[0171] R ｉ , R ｊ and R ｋ Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula (I) include linear or branched alkyl groups having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group.

[0172] R ｌExamples of the aryl group represented by the formula (I) include unsubstituted or substituted aryl groups with an alkyl group or the like, and specific examples thereof include a methylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a t-butylphenyl group, a vinylphenyl group, a naphthyl group, an ethylnaphthyl group, a biphenylyl group, and an ethylbiphenylyl group.

[0173] Examples of the structure represented by formula (5) include a structure represented by formula (5-1), a structure represented by formula (5-2), and a structure represented by formula (5-3).

[0174]

[0175]

[0176]

[0177] A compound having a structure represented by formula (4) may have a structure represented by formula (6) in the molecule. This compound may be a polymer in which the structure represented by formula (4) and the structure represented by formula (6) are randomly bonded, or may be a block copolymer, or may be a random copolymer. Furthermore, this 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 may be a block copolymer, or may be a random copolymer.

[0178]

[0179] (In formula (6), R ｍ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group, or a benzyl group.

[0180] R ｍExamples of the alkyl group having 1 to 18 carbon atoms represented by the formula (I) include linear or branched alkyl groups having 1 to 18 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group.

[0181] R ｍ Examples of the cycloalkyl group having 5 to 8 carbon atoms represented by the formula (I) include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

[0182] R ｍ Examples of the aryl group represented by the formula (I) include unsubstituted or substituted aryl groups, and specific examples thereof include a phenyl group, a 4-hydroxyphenyl group, a 4-acetylphenyl group, a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-chlorophenyl group, and a 4-bromophenyl group.

[0183] A preferred embodiment of the compound having the structure represented by formula (4) is a compound containing a structural unit represented by formula (4-1) in the molecule and further containing at least one of a structural unit represented by formula (5-1) and a structural unit represented by formula (5-2). This compound may be a block copolymer or a random copolymer. The molar contents of the structural unit represented by formula (4-1), the structural unit represented by formula (5-1), and the structural unit represented by formula (5-2) are preferably 1 to 92 mol%, 0 to 54 mol%, and 0 to 89 mol%, respectively. The average number of structural units represented by formula (4-1) is preferably 1 to 350, the average number of structural units represented by formula (5-1) is preferably 0 to 160, and the average number of structural units represented by formula (5-2) is preferably 0 to 270.

[0184] As the polystyrene resin, commercially available polystyrene resins can also be used. Examples of commercially available products include "ODV-XET (X03) (trade name)," "ODV-XET (X04) (trade name)," and "ODV-XET (X05) (trade name)," manufactured by Nippon Steel Chemical & Material Co., Ltd. These polystyrene resins may be used alone or in combination of two or more.

[0185] The weight average molecular weight (Mw) of the polystyrene resin is preferably 1500 to 40000, and more preferably 1500 to 35000. The weight average molecular weight can be measured using gel permeation chromatography (GPC) in terms of styrene.

[0186] Examples of polybutadiene resins include compounds having at least one of the polybutadiene structures represented by formula (7), (8), and (9). These polybutadiene structures include not only structures formed by polymerizing butadiene, but also structures formed by hydrogenating a polybutadiene structure. In these compounds, the polybutadiene structure may be contained in the main chain or in a side chain.

[0187]

[0188] (In formula (7), m represents the number of repeating units and is usually an integer of 1 or more.)

[0189]

[0190] (In formula (8), m represents the number of repeating units and is usually an integer of 1 or more.)

[0191]

[0192] (In formula (9), m represents the number of repeating units and is usually an integer of 1 or more.)

[0193] A compound having at least one of the polybutadiene structures represented by formula (7), (8), and (9) may have the structure represented by formula (6) in its molecule. This compound may be a polymer, a block copolymer, or a random copolymer in which at least one of the polybutadiene structures represented by formula (7), (8), and (9) and the structure represented by formula (6) are randomly bonded.

[0194] Other polybutadiene resins include, for example, butadiene homopolymer, epoxy-modified polybutadiene, butadiene-styrene-random copolymer, and maleic acid-modified polybutadiene.

[0195] As the polybutadiene resin, commercially available polybutadiene resins can also be used. Commercially available products include, for example, "Ricon 130 (trade name)", "Ricon 131 (trade name)", "Ricon 142 (trade name)", "Ricon 150 (trade name)", "Ricon 152 (trade name)", "Ricon 153 (trade name)", "Ricon 156 (trade name)", and "Ricon 157 (trade name)" manufactured by Cray Valley Corporation; "B-1000 (trade name)", "B-2000 (trade name)", and "B-3000 (trade name)" (butadiene homopolymers) manufactured by Nippon Soda Co., Ltd.; "Ricon 100 (trade name)" and "Ricon 181 (trade name)" (butadiene-styrene-random copolymers) manufactured by Cray Valley Corporation; and "Ricon 130MA8 (trade name)", "Ricon 130MA13 (trade name)", "Ricon 130MA20 (trade name)", and "Ricon 156MA17 (trade name)" (maleic acid modified polybutadiene), etc. These polybutadiene resins may be used alone or in combination of two or more.

[0196] The number average molecular weight (Mn) of the polybutadiene resin is preferably 500 to 10,000, and more preferably 1,000 to 6,000. The number average molecular weight can be measured using gel permeation chromatography (GPC) in terms of styrene.

[0197] The benzocyclobutene resin is not particularly limited as long as it has two or more benzocyclobutene groups bonded directly or via an organic group.

[0198] In the thermally radically curable resin composition of the present invention, the above-mentioned thermally radically curable resin components may be used alone or in combination of two or more.

[0199] [Other Resin Components] In addition to the thermoradical curable resin component, the thermoradical curable resin composition of the present invention may contain, if necessary, a resin component (other resin component) other than the thermoradical curable resin component. Examples of the other resin component include the above-mentioned resin component, a styrene-based block copolymer, etc.

[0200] Examples of styrene 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), styrene-ethylene / propylene-styrene block copolymers (SEPS), etc. These may be used alone or in combination of two or more.

[0201] Commercially available styrene-based block copolymers can be used. Examples of commercially available products include "Tufprene (trade name)," "Asaprene T (trade name)," and "Tuftec (trade name)" manufactured by Asahi Kasei Corporation, "Elastomer AR (trade name)" manufactured by Aron Kasei Co., Ltd., "Kraton G (trade name)" and "Califlex (trade name)" manufactured by Kraton Polymer Japan, "JSR-TR (trade name)," "TSR-SIS (trade name)," and "Dynaron (trade name)" manufactured by JSR Corporation, "Denka STR (trade name)" manufactured by Denka Co., Ltd., "Quintac (trade name)" manufactured by Nippon Zeon Co., Ltd., "Esporex SB Series (trade name)" manufactured by Sumitomo Chemical Co., Ltd., "Septon (trade name)" and "Hybra (trade name)" manufactured by Kuraray Co., Ltd., "Sumiflex (trade name)" manufactured by Sumitomo Bakelite Co., Ltd., and "Leostomer (trade name)" and "Actimer (trade name)" manufactured by Riken Technos Corporation. These styrene-based block copolymers may be used alone or in combination of two or more types.

[0202] The content of the other resin components in the thermal radical curable resin composition of the present invention is not particularly limited, and is preferably 0 to 1,000 parts by weight, more preferably 50 to 800 parts by weight, and even more preferably 100 to 700 parts by weight, relative to 100 parts by weight of the thermal radical curable resin component.

[0203] [Crosslinking Agent] In the thermoradical curable resin composition of the present invention, in addition to the compound of the present invention as a crosslinking agent, a crosslinking agent other than the compound of the present invention (other crosslinking agent) may be used in combination as needed.

[0204] The content of the compound of the present invention in the thermally radically curable resin composition of the present invention is not particularly limited, and is preferably 1 to 200 parts by weight, more preferably 1 to 150 parts by weight, and even more preferably 2 to 120 parts by weight, relative to 100 parts by weight of the resin components (the total of the thermally radically curable resin component and other resin components).

[0205] [Other Crosslinking Agents] Examples of other crosslinking agents include monobenzyl diallyl isocyanurates such as mono(alkyl having 6 to 20 carbon atoms)diallyl isocyanurate, 1-benzyl-3,5-diallyl isocyanurate, and 1-(4-vinylbenzyl)-3,5-diallyl isocyanurate, tris(4-vinylbenzyl)isocyanurate, tris(4-vinylbenzyloxy)triazine, triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl trimellitate, and the aforementioned polyfunctional styrene compounds. These may be used alone or in combination of two or more.

[0206] The content of the other crosslinking agent in the thermally radically curable resin composition of the present invention is not particularly limited, and is preferably 0 to 200 parts by weight, more preferably 5 to 150 parts by weight, and even more preferably 10 to 100 parts by weight, relative to 100 parts by weight of the resin component (the total of the thermally radically curable resin component and the other resin component).

[0207] The thermally radically curable resin composition of the present invention may further contain other components, as necessary, such as the above-mentioned flame retardant, the above-mentioned radical polymerization initiator, the above-mentioned inorganic filler, the stress relaxation agent, the organic solvent, and the above-mentioned additives.

[0208] [Flame retardant] The flame retardants described in the above section 3. Crosslinking agent and resin composition can be used as the flame retardant. The content of the flame retardant in the thermally curable resin composition of the present invention is not particularly limited, and is preferably 0 to 130 parts by weight, more preferably 1 to 80 parts by weight, and even more preferably 1 to 40 parts by weight, per 100 parts by weight of the resin components (total of the thermally curable resin component and other resin components).

[0209] [Radical Polymerization Initiator] The radical polymerization initiator may be any of those described in the section 3. Crosslinking Agent and Resin Composition. The content of the radical polymerization initiator in the thermally radically curable resin composition of the present invention is not particularly limited, and is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 5 parts by weight, and even more preferably 0.01 to 3 parts by weight, per 100 parts by weight of the resin components (the total of the thermally radically curable resin component and other resin components).

[0210] [Inorganic Filler] The inorganic filler may be any of those described in the section 3. Crosslinking Agent and Resin Composition. The content of the inorganic filler in the thermally curable resin composition of the present invention is not particularly limited, and is preferably 0 to 500 parts by weight, more preferably 1 to 200 parts by weight, and even more preferably 5 to 100 parts by weight, per 100 parts by weight of the resin components (the total of the thermally curable resin component and other resin components).

[0211] [Stress Relaxant] The stress relaxation agent is not particularly limited, and examples thereof include silicone resin particles. The average particle diameter of the stress relaxation agent is preferably 10 μm or less. By using a stress relaxation agent having such an average particle diameter, adhesion to metal foil is improved when the thermo-radical curable resin composition of the present invention is used in a metal-clad laminate or the like.

[0212] The content of the stress relaxation agent in the thermally radically curable resin composition of the present invention is not particularly limited, and is preferably 0 to 100 parts by weight, more preferably 0 to 50 parts by weight, per 100 parts by weight of the resin components (the total of the thermally radically curable resin component and other resin components).

[0213] [Organic Solvent] The organic solvent is not particularly limited as long as it can dissolve or disperse the thermally curable resin component, and examples thereof 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 may be used alone or in combination of two or more. The thermally curable resin composition of the present invention containing an organic solvent can be used to produce a prepreg by impregnating a substrate as a resin varnish, as described below.

[0214] The content of the organic solvent in the thermo-radical curable resin composition of the present invention may be adjusted depending on the operation of applying or impregnating / applying the resin varnish to a substrate, and is preferably 30 to 1,000 parts by weight, more preferably 100 to 500 parts by weight, per 100 parts by weight of the resin component (total of the thermo-radical curable resin component and other resin components).

[0215] [Additives] The additives described in the above section 3. Crosslinking agent and resin composition can be used as the additives. The content of the additives in the thermally curable resin composition of the present invention is not particularly limited, and is preferably 0 to 50 parts by weight, more preferably 1 to 20 parts by weight, per 100 parts by weight of the resin components (total of the thermally curable resin component and other resin components).

[0216] The thermo-radical curable resin composition of the present invention can be produced by mixing and / or kneading the thermo-radical curable resin component, the crosslinking agent of the present invention, and, if necessary, other resin components, other crosslinking agents, flame retardants, radical polymerization initiators, inorganic fillers, stress relaxation agents, organic solvents, and additives by a known method. For example, the composition can be produced by mixing and / or kneading a mixture of liquid, powder, bead, flake, or pellet-like components using an extruder (such as a single-screw extruder or a twin-screw extruder), a kneader (such as a Banbury mixer, a pressure kneader, a two-roll mill, or a three-roll mill), or the like.

[0217] (5. Uses of the Resin Composition of the Present Invention) The resin composition described in the above 3. and the thermo-radical curable resin composition described in the above 4. (hereinafter, both will be 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, adhesives, and photosensitive resin cured films.

[0218] [Prepreg] The prepreg of the present invention will now be described. When using the resin composition of the present invention to produce a prepreg for use in RCC or the like, the resin composition of the present invention can be prepared in the form of a varnish and used as a resin varnish. Such a resin varnish can be prepared, for example, as follows. First, each component soluble in an organic solvent (each component contained in the resin composition of the present invention) is added to an organic solvent and dissolved. Heating may be performed as necessary. Then, components insoluble in an organic solvent (each component contained in the resin composition of the present invention), such as an inorganic filler, are added as needed, and the mixture is dispersed using a ball mill, bead mill, planetary mixer, roll mill, or the like until a predetermined dispersion state is achieved, thereby preparing the resin composition of the present invention in the form of a varnish.

[0219] 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 is the resin composition of the present invention in a partially cured state (B-staged state).

[0220] The prepreg of the present invention may be a prepreg comprising a semi-cured product of the resin composition of the present invention (a resin composition in a B-stage state) and a substrate, or may be a prepreg comprising the resin composition of the present invention before curing (a resin composition in an A-stage) and a substrate.

[0221] Examples of substrates used 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 glass cloth materials include ordinary E-glass, as well as D-glass, S-glass, NE-glass, quartz glass, and L-glass. The use of glass cloth results in a laminated board with excellent mechanical strength. Flattened glass cloth is preferred. Flattening can be achieved, for example, by continuously pressing the glass cloth with a press roll at an appropriate pressure to compress the yarns flat. Examples of the thickness of the substrate include 0.02 to 0.3 mm.

[0222] The proportion of the base material in the prepreg is 20 to 80% by weight, preferably 25 to 70% by weight, of the entire prepreg.

[0223] Examples of methods for producing prepregs include a method in which the resin composition of the present invention is prepared in a varnish form and then impregnated or coated onto a substrate. Examples of impregnation and coating methods include immersing the substrate (dipping), coating using a roll, die coating, bar coating, or the like, and spraying using a sprayer. This impregnation and coating can be repeated multiple times as needed. It is also possible to repeat impregnation and coating using multiple resin compositions with different resin component concentrations. After impregnation and coating, the substrate may be dried or heated.

[0224] The substrate impregnated and coated with the resin composition of the present invention can be heated at 80 to 180° C. for 1 to 10 minutes to obtain a semi-cured (B-stage) prepreg.

[0225] Table 1 shows a preferred blend example (excluding organic solvents) when the resin composition of the present invention is used for a prepreg.

[0226]

[0227] By using such prepregs, it is possible to produce metal-clad laminates and printed wiring boards that have excellent electrical properties (for example, dielectric properties), heat resistance, flame retardancy, adhesive strength, and chemical resistance.

[0228] [Resin-Coated Metal Foil] The resin-coated metal foil of the present invention will be described. 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. The resin-coated metal foil of the present invention comprises 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. The resin-coated metal foil of the present invention may also comprise another layer between the resin layer and the metal foil.

[0229] As described above, the resin layer may be a semi-cured product of the resin composition of the present invention (a resin composition in a B-stage state) or the resin composition of the present invention before curing (a resin composition in an A-stage state). The resin layer may or may not contain a substrate. The substrate may be the same as the substrate of the prepreg.

[0230] The metal foil may be, for example, copper foil or aluminum foil, etc. The thickness of the copper foil may be about 12 to 70 μm.

[0231] Examples of methods for producing the resin-coated metal foil of the present invention include a method in which the resin composition of the present invention prepared in the form of a varnish as described above is applied to a metal foil. The application method is not particularly limited as long as it is a method that can apply the resin composition of the present invention to the metal foil. Examples include application methods using a roll, die coater, bar coater, etc., and spraying methods using a sprayer. After application, the composition may be dried or heated.

[0232] The metal foil coated with the resin composition of the present invention can be heated at 80 to 180° C. for 1 to 10 minutes to obtain a resin-coated metal foil in a semi-cured state (B-stage state).

[0233] Preferred formulations (excluding organic solvents) when the resin composition of the present invention is used for a resin-coated metal foil containing a substrate are the same as those for the prepreg described above (see Table 1 above). Furthermore, preferred formulations (excluding organic solvents) when the resin composition of the present invention is used for a resin-coated metal foil not containing a substrate are shown in Table 2.

[0234]

[0235] By using such a resin-coated metal foil, it is possible to produce a metal-clad laminate or a printed wiring board that has excellent electrical properties (e.g., dielectric properties), heat resistance, flame retardancy, adhesive strength, and chemical resistance.

[0236] [Thermosetting Resin Film] The thermosetting resin film of the present invention will be described. The thermosetting resin film of the present invention can be produced by forming 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 applying the resin composition of the present invention onto a support and then drying it. The support is not particularly limited, and examples thereof include metal foils such as copper and aluminum, and organic films such as polyester resins, polyethylene resins, and polyethylene terephthalate resins (PET). The support may be subjected to a release treatment with a silicone-based compound or the like. The resin composition of the present invention can be used in various shapes, and the shape is not particularly limited.

[0237] The method for applying the resin composition of the present invention to a support is not particularly limited, but from the viewpoint of thinning and controlling the film thickness, gravure coating, slot die coating, doctor blade coating, etc. The slot die coating can provide an uncured film of the resin composition (thermosetting resin film of the present invention) having a thickness of 5 to 300 μm after heat curing.

[0238] Drying conditions can be appropriately set depending on the type and amount of organic solvent used in the resin composition of the present invention, the coating thickness, etc. For example, drying conditions can be set to 50 to 120°C and 1 to 60 minutes. The thermosetting resin film of the present invention obtained in this manner has good storage stability. The thermosetting resin film can be peeled off from the support at any desired time.

[0239] The thermosetting resin film of the present invention can be cured, for example, at 150 to 230°C for 30 to 180 minutes. The thermosetting resin film of the present invention can be cured after sandwiching the thermosetting resin film between substrates on which wiring such as copper foil is formed, or after appropriately laminating a thermosetting resin film on which wiring such as copper foil is formed. The thermosetting resin film can also be used as a coverlay film to protect wiring on a substrate, and the curing conditions for this are similar. The thermosetting resin film of the present invention can also be suitably used for flexible copper-clad laminates (FCCLs) for flexible printed circuit boards (FPCs), copper-clad laminates (CCLs) for multilayer substrates, build-up materials, and the like.

[0240] Preferred formulation examples (excluding organic solvents) when the resin composition of the present invention is used in a thermosetting resin film are shown in Table 3. When an organic solvent is added, it is preferable to add it appropriately so that the viscosity is in the range of 200 to 3000 mPa s.

[0241]

[0242] [Metal-clad laminate] The metal-clad laminate of the present invention will be described. The metal-clad laminate of the present invention comprises an insulating layer containing a cured product of the resin composition of the present invention and a metal foil. The metal-clad laminate comprises a metal foil on the surface of the insulating layer. The metal-clad laminate may also comprise another layer between the insulating layer and the metal foil. The insulating layer may or may not comprise a substrate. The substrate may be the same as the substrate of the prepreg. The metal foil may be the same as the metal foil of the resin-coated metal foil.

[0243] Examples of methods for producing metal-clad laminates include the method using the prepreg described above. Methods for producing metal-clad laminates using prepregs include stacking one or more prepregs, then stacking a metal foil such as copper foil on both or either of the upper and lower surfaces of the prepreg, and then heat-pressing and molding the resulting laminate to form an integrated laminate. This method allows for the production of laminates clad on both or one side with metal foil. Heat-press conditions can be appropriately set depending on the thickness of the metal-clad laminate to be produced and the composition of the resin composition used in the prepreg. For example, conditions such as a temperature of 170 to 220°C, a pressure of 1.5 to 5.0 MPa, and a time of 60 to 150 minutes can be used. Metal-clad laminates can also be produced without using prepregs. Examples include a method in which a varnish-like resin composition of the present invention is applied to a metal foil to form a layer containing the resin composition of the present invention on the metal foil, followed by heat-pressure molding, or a method in which a thermosetting resin film is cured using a metal foil as a support.

[0244] Preferred formulations (excluding organic solvents) when the resin composition of the present invention is used in a metal-clad laminate containing a substrate are the same as those for the prepreg described above (see Table 1 above). Also, preferred formulations (excluding organic solvents) when the resin composition of the present invention is used in a metal-clad laminate not containing a substrate are the same as those for the resin-coated metal foil not containing a substrate described above (see Table 2 above).

[0245] By using such a metal-clad laminate, it is possible to produce a printed wiring board that is excellent in electrical properties (for example, dielectric properties, etc.), heat resistance, flame retardancy, adhesive strength, and chemical resistance.

[0246] [Printed Wiring Board] The printed wiring board of the present invention will be described. The printed wiring board of the present invention comprises an insulating layer containing a cured product of the resin composition of the present invention or a cured product of the thermosetting film of the present invention, and wiring. The printed wiring board of the present invention comprises wiring on the surface of the insulating layer. The printed wiring board of the present invention may also comprise another layer between the insulating layer and the wiring. The insulating layer may or may not comprise a substrate. The substrate may be the same as the substrate of a prepreg. The printed wiring board of the present invention comprises an insulating layer containing 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 thus has excellent electrical properties (e.g., dielectric properties, etc.) and high flame retardancy.

[0247] The wiring is not particularly limited as long as it is wiring that can be provided on a printed wiring board. For example, wiring formed by partially removing a metal foil laminated on an insulating layer can be used. In addition, wiring formed by a subtractive method, an additive method, a semi-additive method, a chemical mechanical polishing (CMP), a trench method, an inkjet method, a squeegee method, a transfer method, or the like can be used.

[0248] Examples of methods for producing printed wiring boards include a method using the above-mentioned metal-clad laminate. Methods for producing printed wiring boards using metal-clad laminates include a method of forming a circuit by etching the metal foil on the surface of the metal-clad laminate. This method allows for the production of a printed wiring board in which a conductor pattern is provided as a circuit on the surface of the metal-clad laminate.

[0249] Preferred formulations (excluding organic solvents) when the resin composition of the present invention is used in a printed wiring board containing a substrate in the insulating layer are the same as those for the prepreg described above (see Table 1 above).Preferable formulations (excluding organic solvents) when the resin composition of the present invention is used in a printed wiring board containing no substrate in the insulating layer are the same as those for the resin-coated copper foil containing no substrate described above (see Table 2 above).

[0250] The printed wiring board obtained in this manner has excellent electrical properties (e.g., dielectric properties, etc.), heat resistance, flame retardancy, and chemical resistance, and is sufficiently prevented from peeling off of the circuit. Furthermore, even when it is used in the form of a package to which a semiconductor chip is bonded, it is easy to mount, has consistent quality, and is excellent in signal speed and impedance.

[0251] [Resin Plate] The resin composition of the present invention can also be used as a resin plate cured into a plate shape. For example, a resin plate can be obtained by applying the resin composition of the present invention in a varnish form to a plate, drying it, and then curing it. Further, the resin plate can also be an unclad plate obtained by removing the metal foil from the metal-clad laminate.

[0252] [Semiconductor Device] The use of the resin composition of the present invention in a semiconductor device will be described. A semiconductor device can be manufactured by using and curing the resin composition of the present invention or the thermosetting resin film of the present invention. This semiconductor device is suitable for high-frequency applications because it has excellent electrical properties (e.g., dielectric properties) and high flame retardancy due to the cured product of the resin composition of the present invention or the cured product of the thermosetting resin film of the present invention. A semiconductor device refers to any device that can function by utilizing semiconductor properties, and includes electronic components, semiconductor circuits, modules incorporating these, electronic devices, etc.

[0253] [Adhesive] The adhesive of the present invention will be described. 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. In particular, it is preferred as an adhesive between a metal and a material selected from metals, inorganic materials, and resin materials.

[0254] Examples of the metal include copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof. Among these metals, copper is preferred. Examples of the metal form include plates, foils, and plated films made of these metals.

[0255] Examples of the inorganic material include silicon, ceramic, carbon used as a filler, inorganic salts, glass, etc. Specifically, silicon compounds such as silicon, silicon carbide, silica, glass, diatomaceous earth, calcium silicate, talc, glass beads, sericite activated clay, bentonite, aluminosilicate, mica, etc.; oxides such as alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, etc.; hydroxides such as magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, etc.; carbonates such as calcium carbonate, zinc carbonate, hydrotalcite, magnesium carbonate, etc.; sulfates such as barium sulfate, gypsum, etc.; titanates such as barium titanate, etc.; nitrides such as aluminum nitride, silicon nitride, etc.; graphites such as flake graphite (natural graphite), expanded graphite, expanded graphite (synthetic graphite), activated carbon, carbon fibers, carbon black, etc. Among these inorganic materials, silicon, ceramics (alumina, silicon carbide, aluminum nitride, silicon nitride, barium titanate, etc.), glass, and inorganic salts are preferred.

[0256] Examples of the resin material include nylon, acrylate resin, epoxy resin, olefin resin, benzoxazine resin, polybenzoxazole resin, silicone resin, polyamide resin, polyimide resin, bismaleimide resin, maleimide resin, cyanate resin, polyphenylene ether resin, polyphenylene oxide resin, fluorine-containing resin, polyether resin, polyetherimide resin, polyether ether ketone resin, polyester resin, silicone resin, liquid crystal resin, etc., and these may be mixed or modified and combined. Among these resin materials, acrylate resin, epoxy resin, olefin resin, benzoxazine resin, polybenzoxazole resin, bismaleimide resin, polyphenylene ether resin, fluorine-containing resin, polyether resin, liquid crystal resin, silicone resin, and polyimide resin are preferred.

[0257] Materials can be bonded using an adhesive by known methods, specifically, (1) a method in which an adhesive is applied to the surface of a material selected from metals, inorganic materials, and resin materials, and another material is pressure-bonded to part or all of the applied adhesive to bond (cure), and (2) a method in which a sheet of semi-cured adhesive is attached to the surface of a material selected from metals, inorganic materials, and resin materials, and another material is pressure-bonded to part or all of the other surface of the adhesive to bond (cure).

[0258] The adhesive can be cured by a known method. Examples include a method of applying heat and pressure using a heat press, or a method of first drying the applied adhesive and then heat treating it. Heating and pressing conditions can be, 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 time of about 1 minute to 10 hours (particularly, about 30 minutes to 5 hours).

[0259] The adhesive of the present invention can be used to bond two materials, particularly two materials of different properties, and can therefore be suitably used in various electronic devices such as electrical or electronic components, semiconductor wafers, printed wiring boards, and flexible metal-clad laminates.

[0260] A preferred example of the composition (excluding the organic solvent) when the resin composition of the present invention is used as an adhesive is the same as that for the thermosetting resin film described above (see Table 3 above).

[0261] [Photosensitive Resin Cured Film] A photosensitive resin cured film using the resin composition of the present invention (particularly, the resin composition of the present invention using a polyimide precursor as a resin component) will be described. This photosensitive resin cured film can be produced using the resin composition of the present invention. The production method includes, for example, the following steps (1) to (5): (1) a step of applying the resin composition of the present invention onto a substrate to form a photosensitive resin layer on the substrate; (2) a step of heating and drying the obtained photosensitive resin layer; (3) a step of exposing the photosensitive resin layer after heating and drying; (4) a step of developing the photosensitive resin layer after exposure; and (5) a step of heat-treating the photosensitive resin layer after development to form a photosensitive resin cured film (polyimide cured film).

[0262] In step (1), the resin composition of the present invention is applied to a substrate and dried as necessary to form a photosensitive resin layer. As the application method, a method conventionally used for applying a photosensitive resin composition, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, or the like, or spray application using a spray coater, can be used.

[0263] In the step (2), the photosensitive resin layer is heated and dried by methods such as air drying, heat drying in an oven or on a hot plate, and vacuum drying.

[0264] In step (3), the photosensitive resin layer after heating and drying is exposed to light. Examples of exposure devices include contact aligners, mirror projection devices, and steppers. Exposure can be performed through a photomask or reticle having a pattern, or directly. Examples of light used for exposure include ultraviolet light sources. After exposure, post-exposure baking (PEB) and / or pre-development baking may be performed at any combination of temperature and time, as necessary, for the purpose of improving photosensitivity, etc.

[0265] In step (4), the exposed photosensitive resin layer is developed to form a relief pattern. When the resin composition of the present invention is a negative type, the unexposed portion of the exposed photosensitive resin layer is developed and removed. As a development method for developing the exposed (irradiated) photosensitive resin layer, any method can be selected from conventionally known photoresist development methods, such as a rotary spray method, a paddle method, and an immersion method accompanied by ultrasonic treatment.

[0266] In step (5), the relief pattern obtained by development is heated to dissolve the photosensitive component and imidize the polyimide precursor, converting it into a cured relief pattern made of polyimide. Various methods can be selected for heat curing, including those using a hot plate, an oven, or a temperature-programmable heating oven. Heating can be performed, for example, at 160°C to 400°C for 30 minutes to 5 hours. Air or an inert gas such as nitrogen or argon can be used as the atmospheric gas during heat curing. In this manner, a photosensitive resin cured film (cured relief pattern) can be produced.

[0267] This photosensitive resin cured film (cured relief pattern) can be used in a semiconductor device. In this case, the semiconductor device has a substrate that is a semiconductor element and a photosensitive resin cured film (cured relief pattern) formed on the substrate. This semiconductor device can be manufactured by forming the photosensitive resin cured film (cured relief pattern) as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and combining it with a known method for manufacturing a semiconductor device.

[0268] Table 4 shows preferred formulations (excluding organic solvents) when the resin composition of the present invention is used to form a photosensitive resin cured film.

[0269]

[0270] By using the resin composition of the present invention (particularly the resin composition of the present invention using a polyimide precursor as a resin component), it is possible to obtain a cured photosensitive resin film that has high resolution in a thick film and a low dielectric loss tangent. Therefore, the resin composition of the present invention can be suitably used as a photosensitive material in the electrical and electronic fields, such as semiconductor devices and multilayer wiring boards.

[0271] In this specification, the terms "comprise" and "have" include the concepts of "consist essentially of" and "consist of."

[0272] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. The main raw materials used in the synthesis of the crosslinking agent are as follows.

[0273] [Main raw materials, etc.] ・1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene (see chemical formula (II-2), manufactured by Tokyo Chemical Industry Co., Ltd.) ・(2-bromoethyl)benzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ・4-vinylphenol (synthesized in accordance with the method described in "Journal of Medicinal Chemistry (2023), 66(1), 306-332".) ・(4-vinylphenyl)methanol (synthesized in accordance with the method described in "Nature Communications (2020), 11(1), 4032".) ・methanesulfonic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ・toluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ・sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ・potassium t-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) ・potassium iodide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Dimethyl sulfoxide (Fujifilm Wako Pure Chemical Industries, Ltd.) Dimethylacetamide (Fujifilm Wako Pure Chemical Industries, Ltd.) Dimethylformamide (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0274] The main raw materials used in preparing the resin composition are as follows. (i) Thermal radical curable resin component: Polyphenylene ether resin (manufactured by Mitsubishi Gas Chemical Company, Inc., trade name "OPE-2St 2200", molecular weight: 2200) (ii) Crosslinking agent: A mixture of compounds represented by chemical formulas (I-1) to (I-4) (hereinafter referred to as "Crosslinking agent 1"; synthesized and used according to the synthesis of Crosslinking agent 1 described below). Triallyl isocyanurate (see chemical formula (VIII); manufactured by Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as "Crosslinking agent 2") Divinylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as "Crosslinking agent 3") 2,4,6-trimethyl-1,3,5-tris[(4-ethenylphenoxy)methyl]benzene (see chemical formula (IX); hereinafter referred to as "Crosslinking agent 4"; synthesized and used according to the synthesis of Crosslinking agent 4 described below). 2,4,6-trimethyl-1,3,5-tris[(4-ethenylphenylmethoxy)methyl]benzene (see chemical formula (X); hereinafter referred to as "crosslinker 5"; synthesized and used according to the synthesis of crosslinker 5 described below).

[0275]

[0276] (iii) Radical polymerization initiator: α,α'-di(t-butylperoxy)diisopropylbenzene (manufactured by NOF Corporation, trade name "Perbutyl P") (iv) Organic solvent: Toluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0277] The evaluation tests (measurement method for glass transition temperature, dielectric properties, evaluation of water absorption resistance) employed in the evaluation of the resin compositions are as follows.

[0278] (1) Measurement of Glass Transition Temperature (Tg) The resin composition was poured into a mold set to a thickness of 1 mm using a 1 mm silicone spacer, and then the toluene was distilled off until constant weight was reached in a fan oven heated to 80°C. The mixture was then heated at 120°C for 30 minutes, 150°C for 30 minutes, and 200°C for 1 hour to obtain a 1 mm thick plate-shaped cured product. A 20 mm long x 5 mm wide x 1 mm thick test piece cut from the cured product was placed in a solid torsion jig of a dynamic viscoelasticity measuring apparatus (DMA) (UBM "Rheosol-G5000") and subjected to dynamic viscoelasticity measurements 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-top temperature of the loss tangent. The higher the glass transition temperature, the more excellent the heat resistance of the cured product.

[0279] (2) Measurement of Dielectric Properties (Dielectric Loss Tangent Df) The resin composition was poured into a mold set to a thickness of 1 mm using a 1 mm silicone spacer, and then the toluene was distilled off until constant weight was reached in a fan oven heated to 80 ° C. The mixture was then heated at 120 ° C for 30 minutes, 150 ° C for 30 minutes, and 200 ° C for 1 hour to obtain a 1 mm thick plate-shaped cured product. A 50 mm long x 2 mm wide x 1 mm thick test piece cut from the cured product was dried under vacuum at 60 ° C for 12 hours, and the dielectric loss tangent Df before humidification was measured using a network analyzer (Agilent Technologies "E8361A") by cavity resonance at a measurement frequency (10 GHz). The smaller the dielectric loss tangent Df, the better the dielectric properties of the cured product.

[0280] (3) Evaluation of Water Absorption Resistance A cured product was prepared using the same procedure as in (2). This cured product was immersed in ion-exchanged water and allowed to stand for 24 hours, after which the dielectric loss tangent Df after water absorption was measured under the same conditions as in (2). The change in the dielectric loss tangent Df before and after water absorption was calculated using the following formula: Change = Dielectric loss tangent Df after water absorption - Dielectric loss tangent Df before water absorption The smaller this change, the better the water absorption resistance of the cured product is judged to be.

[0281] <Synthesis of Crosslinking Agent 1> 25.93 g (65.0 mmol) of 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene, 108.26 g (585.0 mmol) of (2-bromoethyl)benzene, and 4.48 g (46.6 mmol) of methanesulfonic acid were charged into a 1 L reactor, heated to 130°C, and stirred at the same temperature for 14 hours. After that, the mixture was cooled to room temperature, and 390.00 g of toluene was added, followed by washing with water. The organic layer was concentrated under reduced pressure with heating to obtain 40.37 g of a compound (precursor) having a bromoethyl group. The reaction formula is shown in the next paragraph. The obtained precursor １ H-NMR chart (CDCl ３ ) is shown in Figure 1. １ Signals derived from bromoethyl groups were observed at 3.47-3.57 ppm and 3.06-3.15 ppm in the H-NMR chart.

[0282]

[0283] A 2 L reactor was charged with 77.88 g (109.5 mmol) of the precursor synthesized above, 389.40 g of toluene, 58.41 g of water, 584.1 g of dimethyl sulfoxide, and 22.31 g (557.8 mmol) of sodium hydroxide, and the mixture was heated to 40°C and stirred at the same temperature for 18 hours. The mixture was then cooled to room temperature, and 390.00 g of toluene was added, followed by washing with water. The organic layer was concentrated under reduced pressure with heating to obtain 39.95 g of the title compound (Crosslinking Agent 1) having a vinyl group as a brown liquid. The reaction formula is shown in the next paragraph. Furthermore, the obtained crosslinking agent 1 １ H-NMR chart (CDCl ３ ) and IR charts are shown in Figs. 2 and 3. １ Signals derived from vinyl groups were observed at 6.63-6.72 ppm and 5.63-5.73 ppm in the H-NMR chart.

[0284]

[0285] <Synthesis of Crosslinker 4> A 1 L reactor was charged with 22.00 g (55.1 mmol) of 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene, 165 mL of dimethylacetamide, 23.19 g (193.0 mmol) of 4-vinylphenol, 915.00 mg (5.5 mmol) of potassium iodide, and 7.28 g (182.0 mmol) of sodium hydroxide, and the mixture was stirred at 25°C for 30 minutes. The mixture was then heated to 50°C and stirred at the same temperature for 14 hours. After that, the mixture was cooled to room temperature, and 300 mL of toluene was added, followed by washing with water. The organic layer was concentrated under heating and reduced pressure, and the precipitated solid was washed with methanol and dried under reduced pressure, yielding 25.01 g of a yellow powder (yield 87.8%).

[0286] This yellow powder １ The H-NMR spectrum data was as follows: 1 H-NMR (d6-DMSO) δ: 7.36-7.39 (m, 6H), 6.96-6.99 (m, 6H), 6.68 (dd, 3H), 5.62 (d, 3H), 5.14 (d, 3H), 5.10 (s, 6H), 2.44 (s, 9H). From this spectral data, the obtained yellow powder was identified as the compound represented by chemical formula (IX) (crosslinker 4).

[0287] <Synthesis of Crosslinking Agent 5> A 1 L reactor was charged with 26.57 g (198.0 mmol) of (4-vinylphenyl)methanol and 230 mL of dimethylformamide under a nitrogen atmosphere and cooled to -5°C. 22.22 g (198.0 mmol) of potassium t-butoxide was added in portions so that the temperature did not exceed 0°C. After stirring at 0°C for 30 minutes, 23.90 g (59.9 mmol) of 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene was added so that the temperature did not exceed 0°C. The mixture was then heated to 25°C and stirred at the same temperature for 14 hours. 300 mL of toluene was then added, and the mixture was washed with water. The organic layer was concentrated under heating and reduced pressure, and the precipitated solid was washed with ethanol and dried under reduced pressure, yielding 22.80 g of a yellow powder (yield: 68.0%).

[0288] This yellow powder １ The H-NMR spectrum data was as follows:1 H-NMR (d6-DMSO) δ: 7.30-7.40 (m, 12H), 6.71 (dd, 3H), 5.74 (d, 3H), 5.24 (d, 3H), 4.54-4.56 (m, 12H), 2.36 (s, 9H). From this spectral data, the obtained yellow powder was identified as the compound represented by chemical formula (X) (crosslinker 5).

[0289] <Evaluation of Resin Compositions> [Preparation and Evaluation of Resin Composition 1] A resin composition (hereinafter referred to as Resin Composition 1) was prepared by mixing 70 parts by weight of OPE-2St 2200 as a thermal radical curable resin component, 30 parts by weight of Crosslinking Agent 1 as a crosslinking agent, 1 part by weight of Perbutyl P as a radical polymerization initiator, and 50 parts by weight of toluene as an organic solvent. Evaluation tests (measurement of glass transition temperature, dielectric properties, evaluation of water absorption resistance) were carried out on this Resin Composition 1, and the obtained test results are shown in Table 5.

[0290] [Preparation and Evaluation of Resin Compositions 2 to 6] Resin compositions (resin compositions 2 to 6) having the compositions shown in Table 5 were prepared in the same manner as in the preparation of resin composition 1, and evaluation tests were performed on these resin compositions. The test results obtained are as shown in Table 5.

[0291]

[0292] From Table 5, it was confirmed that when crosslinking agent 1 was used as the crosslinking agent (resin composition 1), the glass transition temperature (Tg) of the cured product was higher than when no crosslinking agent was used (resin composition 2) and when conventional crosslinking agents were used (resin compositions 3 to 6), and therefore heat resistance was excellent. Furthermore, the dielectric loss tangent Df before and after water absorption was low and the amount of change was small, confirming excellent electrical properties and water absorption resistance. Therefore, it is believed that the compound of the present invention is more suitable as a crosslinking agent for resins than conventional crosslinking agents.

[0293] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2023-104804) filed on June 27, 2023, the contents of which are incorporated herein by reference.

[0294] The resin composition containing the crosslinking agent of the present invention can be used, for example, as an insulating material for printed wiring boards. In addition to being used as an insulating material for printed wiring boards, it can also be used as a raw material for prepregs.

Claims

1. Tris[(ethenylphenyl)methyl]benzenes represented by chemical formula (I). (In formula (I), R may be the same or different and represents an alkyl group having 1 to 6 carbon atoms.) 2. A method for synthesizing tris[(ethenylphenyl)methyl]benzenes according to claim 1, which comprises reacting a compound represented by chemical formula (II) with a compound represented by chemical formula (III) and then reacting the compound with a base. (In formula (II), R is the same as above. X １ represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. (In formula (III), X ２ represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

3. A crosslinking agent containing the tris[(ethenylphenyl)methyl]benzene compound according to claim 1.

4. A resin composition comprising the tris[(ethenylphenyl)methyl]benzene compound according to claim 1 and a resin component.

5. A prepreg comprising the resin composition according to claim 4 and a substrate.

6. A resin-coated metal foil comprising a resin layer containing the resin composition according to claim 4 or a semi-cured product of said resin composition, and a 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 containing a cured product of the resin composition according to claim 4 and a metal foil.

9. A printed wiring board comprising an insulating layer containing the cured product of the resin composition according to claim 4 or the cured product of the thermosetting resin film according to claim 7, and wiring.

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

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