Composition for insulating layer of printed wiring board

Abstract

The present invention addresses the problem of providing a composition for use in an insulating layer of a printed wiring board, said composition having a low dielectric constant, a low dielectric loss tangent, and flame retardancy.　This resin composition for use in an insulating layer of a printed wiring board includes a polybutadiene, wherein the molar ratio of 1,2 bond structures to 1,4 bond structures in the polybutadiene is 60:40 to 100:0, and bonded to at least one carbon atom in the polybutadiene is a phosphorus-including group represented by formula (III) (in formula (III), * represents a bond location, X1 and X2 each independently represent a single bond or an oxygen atom, and R1 and R2 each independently represent an organic group).

Description

Composition for insulating layer of printed wiring board

[0001] The present invention relates to a composition for use in an insulating layer of a printed wiring board. This application claims priority to Japanese Patent Application No. 2023-203637 filed on December 1, 2023, and Japanese Patent Application No. 2024-035351 filed on March 7, 2024, the contents of which are incorporated herein by reference.

[0002] Various known resins are used to manufacture printed wiring boards and the like included in mobile communication devices such as mobile phones and smartphones, their base station equipment, network-related electronic devices such as servers and routers, and large computers. In recent years, these network-related electronic devices have been required to transmit and process large volumes of information at high speed with low loss, and the electrical signals handled by the printed wiring boards of these products have become increasingly higher in frequency. Because high-frequency electrical signals are prone to attenuation, it is necessary to further reduce transmission loss in printed wiring boards. Therefore, resins used to manufacture printed wiring boards are required to have low dielectric constants and low dielectric dissipation factors. Furthermore, in recent years, regulations regarding flame retardancy in various industrial products have become stricter, and materials used for printed wiring boards are also required to be flame-retardant.

[0003] Patent Document 1 discloses that a phosphoric acid-modified polymer having a phosphorus substituent containing a phosphorus atom directly bonded to a carbon atom and a double bond has high thermal stability. The patent document cites diene rubber as an example of the polymer, and describes how the phosphorus substituent reacts with a portion of the double bond in the polymer, resulting in the addition of a hydrogen atom and a phosphorus atom to the double bond (hydrophosphonation reaction). The polymer is obtained by reacting a raw polymer with at least one phosphorus compound selected from phosphoric acid, phosphorous acid, and their esters or salts in the presence of a catalyst. Therefore, the phosphorus substituent can bond to any double bond in the polymer, rather than being bonded exclusively to the polymer end. It also describes that blending the polymer into a rubber composition can be expected to reduce heat buildup due to improved filler dispersion, improve wet grip due to improved hydrophilicity, improve toughness due to the ability to build a three-dimensional network, and improve abrasion resistance due to an increased gelation rate. The patent document only describes the use of the phosphoric acid-modified polymer as a rubber, but does not describe its electrical properties or its use in insulating layers of printed wiring boards.

[0004] WO2016 / 063975 Pamphlet

[0005] An object of the present invention is to provide a composition for use in an insulating layer of a printed wiring board, which has a low dielectric constant, a low dielectric loss tangent, and flame retardancy.

[0006] As a result of extensive research, the present inventors have found that the above problems can be solved by a composition containing polybutadiene modified with a phosphorus-containing group.

[0007] The present invention relates to the following inventions: (1) A polymeric resin containing polybutadiene, in which the molar ratio of 1,2 bond structures to 1,4 bond structures in the polybutadiene is 60:40 to 100:0, and one or more carbon atoms in the polybutadiene have a group represented by formula (III) (In formula (III), * indicates a bonding position, and X １ and X ２ each independently represents a single bond or an oxygen atom, R １ and R ２each independently represents an organic group. A resin composition for use in an insulating layer of a printed wiring board, wherein a phosphorus-containing group represented by the following formula (I) is bonded to the insulating layer. (2) The resin composition according to (1), further comprising a polymerization initiator. (3) The resin composition according to (1) or (2), wherein the phosphorus-containing group is bonded only to a terminal carbon atom in the polybutadiene. (4) The resin composition according to any one of (1) to (3), wherein the weight-average molecular weight of the polybutadiene is 1,000 to 8,000. (5) The resin composition according to any one of (1) to (4), wherein the molecular weight distribution of the polybutadiene is 1.00 to 3.00.

[0008] (6) A prepreg impregnated with the resin composition according to any one of (1) to (5). (7) An adhesive film having a resin composition layer containing the resin composition according to any one of (1) to (5) on a support film. (8) A metal foil with a resin composition having a resin composition layer containing the resin composition according to any one of (1) to (5) on a metal foil. (9) A laminate comprising a layer of a cured product of the resin composition according to any one of (1) to (5) and a metal foil.

[0009] (10) A polybutadiene having a molar ratio of 1,2 bond structure to 1,4 bond structure of 60:40 to 100:0, wherein only terminal carbon atoms in the polybutadiene are bonded to a group represented by the formula (III) (In formula (III), * indicates a bonding position, and X １ and X ２ each independently represents a single bond or an oxygen atom, R １ and R ２ (11) A process for anionically polymerizing 1,3-butadiene in the presence of a solvent and an anionic initiator, (In formula (IV), X １ , X ２ , R １ and R ２ is the same as defined in formula (III), and X ３ represents a halogeno group or a group of the formula "-OR ３ ", and R ３(11) The method for producing polybutadiene according to (10), comprising a step of reacting a compound represented by the formula (I) with a compound represented by the formula (I) above.

[0010] The polybutadiene of the present invention has phosphorus-containing groups, so that the cured product of the polybutadiene of the present invention has flame retardancy. Furthermore, despite the polybutadiene of the present invention having phosphate groups, the cured product of the polybutadiene of the present invention has electrical properties equivalent to those of a cured product of unmodified polybutadiene and is more moisture resistant than a cured product of unmodified polybutadiene.

[0011] In this specification, the "1,2 bond structure" refers to a repeating unit represented by formula (I).

[0012]

[0013] In this specification, the "1,4 bond structure" refers to a repeating unit represented by formula (II).

[0014]

[0015] In this specification, the term "end" may refer to either one end of the polybutadiene or both ends.

[0016] In this specification, the term "terminal carbon atom" refers to the carbon atom of the repeating unit at the end of the polybutadiene.

[0017] <Polybutadiene (hereinafter, may be referred to as "polybutadiene having a phosphorus-containing group bonded thereto")> The polybutadiene of the present invention has only 1,2-bond structures, or 1,2-bond structures and 1,4-bond structures. The molar ratio of 1,2-bond structures to 1,4-bond structures among all repeating units of the polybutadiene of the present invention is 60:40 to 100:0, preferably 70:30 to 100:0, and more preferably 70:30 to 95:5. The polybutadiene of the present invention may have repeating units other than the 1,2-bond structures and the 1,4-bond structures. Examples of repeating units other than the 1,2-bond structures and the 1,4-bond structures include repeating units in which 1,2-bond structures are hydrogenated and repeating units in which 1,4-bond structures are hydrogenated.

[0018] The polybutadiene in the present invention has a phosphorus-containing group represented by formula (III) on one or more carbon atoms in the polybutadiene.

[0019]

[0020] In formula (III), * indicates a bonding position, and X １ and X ２ each independently represents a single bond or an oxygen atom, R １ and R ２ each independently represents an organic group.

[0021] R in formula (III) １ and R ２ Examples of the "organic group" in the formula include a C1 to C10 alkyl group, a C2 to C10 alkenyl group, a C2 to C10 alkynyl group, and a C6 to C10 aryl group.

[0022] Examples of the C1 to C10 alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an isopropyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 1-ethylpropyl group, a tert-pentyl group, an isohexyl group, a 3-methylpentyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 1,1,2,2-tetramethylpropyl group, a 1,1,3-trimethylbutyl group, a 1-ethylpentyl group, a 1,1,3,3-tetra ...-ethylpentyl butyl group, 2,2,3,3-tetramethylbutyl group, 1,2,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, 2,2,4-trimethylpentyl group, 1-ethyl-4-methylpentyl group, 3-ethyl-3-methylpentyl group, 3-ethyl-4-methylpentyl group, 1-ethyl-1-methylpentyl group, 1,1-dimethylhexyl group, 3,3-dimethylhexyl group, 4,4-dimethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 6-methylheptyl group, 1,3,5-trimethylhexyl group, 1,1,3-trimethylhexyl group, 1-methylheptyl group, and the like.

[0023] Examples of C2 to C10 alkenyl groups include vinyl, 1-propenyl, 2-propenyl (allyl), 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, and 2-methyl-2-propenyl groups.

[0024] Examples of C2 to C10 alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-methyl-3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 2-methyl-3-pentynyl, 1-hexynyl, and 1,1-dimethyl-2-butynyl.

[0025] Examples of the C6 to C10 aryl group include a phenyl group and a naphthyl group.

[0026] R １ and R ２ is preferably a C1 to C10 alkyl group or a C6 to C10 aryl group.

[0027] The polybutadiene having a phosphorus-containing group bonded thereto in the present invention may have the phosphorus-containing group represented by formula (III) bonded to one or more carbon atoms in the polybutadiene. The number of carbon atoms having the phosphorus-containing group bonded thereto is not particularly limited as long as the polybutadiene exhibits the effect as an insulating layer of the printed wiring board of the present invention, and examples thereof include 5 or less, 3 or less, and 2 or less. The polybutadiene may have the phosphorus-containing group represented by formula (III) only on a terminal carbon atom.

[0028] The weight average molecular weight (Mw) of the polybutadiene in the present invention is not particularly limited, and examples thereof include 500 to 8,000, 500 to 6,000, 500 to 5,000, 500 to 4,000, 500 to 3,000, 1,000 to 8,000, 1,000 to 6,000, 1,000 to 5,000, 1,000 to 4,000, and 1,000 to 3,000. The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polybutadiene in the present invention is not particularly limited, and examples thereof include 1.00 to 3.00 and 1.00 to 2.00. The weight average molecular weight and molecular weight distribution were measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The measurement conditions were as follows: mobile phase THF (tetrahydrofuran), mobile phase flow rate 1 mL / min, column temperature 40° C., sample injection amount 40 μL, and sample concentration 2 wt %.

[0029] In the present invention, the method for producing the polybutadiene having a phosphorus-containing group bonded thereto is not particularly limited, but examples thereof include the method described in WO 2016 / 063975. When produced by this method, the phosphorus-containing group is bonded to any carbon atom in the polybutadiene.

[0030] Furthermore, the method for producing polybutadiene in which the phosphorus-containing group is bonded only to the terminal carbon atom is not particularly limited, and examples thereof include a production method including: Step 1 of anionically polymerizing 1,3-butadiene in the presence of a solvent and an anionic initiator; and Step 2 of reacting the compound represented by formula (IV) after the step 1.

[0031] In formula (IV), X １ , X ２ , R １ and R ２ is the same as defined in formula (III), and X ３ represents a halogeno group or a group of the formula "-OR ３ ", and R ３ represents an organic group. ３ Examples of the halogeno group in R include a chloro group, a bromo group, and an iodo group. ３The organic group in １ and R ２ The same examples as those exemplified in the above can be mentioned.

[0032] Specific examples of the compound represented by formula (IV) include the following compounds: trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, tri-sec-butyl phosphate, tri-tert-butyl phosphate, tripentyl phosphate, trihexyl phosphate, tris(2-ethylhexyl)phosphate, tris(2-butoxyethyl)phosphate, tricyclohexyl phosphate, tricyclopentyl phosphate, tris(2,2,2-trifluoroethyl)phosphate, tris(1,1,1,3,3,3-hexafluoro-2-propyl ... Benzyl phosphate, triallyl phosphate, tris(trimethylsilyl) phosphate, tris(triethylsilyl) phosphate, tris(2-chloroethyl) phosphate, tris(chloropropyl) phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trixylenyl phosphate, cresyl di-2,6-xylenyl phosphate, 4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxide, 2-(2,2,2-trifluoroethoxy)-1,3,2-dioxaphosphorane 2-oxide, dimethyl chlorophosphate, diethyl chlorophosphate, dipropyl chlorophosphate, diisopropyl chlorophosphate, dibutyl chlorophosphate, di-sec-butyl chlorophosphate, di-tert-butyl chlorophosphate, dipentyl chlorophosphate, dihexyl chlorophosphate, bis(2-ethylhexyl) chlorophosphate, bis(2-butoxyethyl) chlorophosphate, dicyclohexyl chlorophosphate, dicyclopentyl chlorophosphate, bis(2,2,2-trifluoroethyl) chlorophosphate, bis(1,1,1,3,3,3-hexafluoro-2-propyl)chlorophosphate, dibenzyl chlorophosphate, diallyl chlorophosphate, bis(trimethylsilyl)chlorophosphate, bis(triethylsilyl)chlorophosphate, bis(2-chloroethyl)chlorophosphate, bis(chloropropyl)chlorophosphate, diphenyl chlorophosphate, dicresyl chlorophosphate, dixylenyl chlorophosphate, 2-chloro-2-oxo-1,3,2-dioxaphosphorane, bis(dimethylamino)phosphoryl chloride, chlorodiphenylphosphine oxide, dicyclohexylphosphinyl chloride, chlorodimethylphosphine oxide, chlorodiethylphosphine oxide, chlorodipropylphosphine oxide, chlorodiisopropylphosphine oxide, chlorodi-sec-butylphosphine oxide, chlorodi-tert-butylphosphine oxide, etc.

[0033] The solvent is not particularly limited, and examples thereof include hydrocarbon solvents such as propane, butane, pentane, hexane, heptane, isooctane, cyclopentane, cyclohexane, methylcyclohexane, decane, benzene, and toluene; and ether solvents such as 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2-methoxymethyltetrahydrofuran, diethyl ether, triethylene glycol dimethyl ether, and cyclopentyl methyl ether. From the viewpoint of increasing the proportion of 1,2 bond structures in the polybutadiene, it is preferable to use an ether solvent or a mixed solvent of an ether solvent and a hydrocarbon solvent as the solvent.

[0034] The anionic polymerization initiator is not particularly limited, and examples thereof include organolithium compounds such as methyllithium, ethyllithium, propyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, isobutyllithium, hexyllithium, octyllithium, tetramethylenedilithium, pentamethylenedilithium, hexamethylenedilithium, phenyllithium, tolyllithium, and lithium naphthylide; metallic sodium, etc. When a phosphorus-containing group is to be bonded to one terminal of polybutadiene, an organolithium compound is used, and when phosphorus-containing groups are to be bonded to both terminals of polybutadiene, metallic sodium is used.

[0035] The polymerization temperature in step 1 is not particularly limited, and examples thereof include −78° C. to 70° C., −78° C. to 35° C., −78° C. to 25° C., −78° C. to 10° C., −10° C. to 70° C., −10° C. to 35° C., −10° C. to 25° C., −10° C. to 10° C., −5° C. to 70° C., −5° C. to 35° C., −5° C. to 25° C., −5° C. to 10° C., and −5° C. to 5° C.

[0036] <Resin Composition> The resin composition of the present invention is a resin composition for use in an insulating layer of a printed wiring board. Examples of printed wiring boards include single-sided printed boards, double-sided printed boards, multilayer printed boards, flexible printed boards, and build-up boards. The printed wiring board can be produced by a known method using a sheet material described below.

[0037] (Polybutadiene having a phosphorus-containing group bonded thereto) The resin composition of the present invention contains the polybutadiene having a phosphorus-containing group bonded thereto. The content of the polybutadiene having a phosphorus-containing group bonded thereto in the resin composition of the present invention is not particularly limited, but examples of the content of the polybutadiene having a phosphorus-containing group bonded thereto relative to the total weight of the resin composition include 10 to 95 wt%, 10 to 90 wt%, 20 to 90 wt%, 30 to 90 wt%, 10 to 75 wt%, 20 to 75 wt%, and 30 to 75 wt%.

[0038] (Polymerization initiator) The resin composition of the present invention may further contain a polymerization initiator. Examples of the polymerization initiator used in the resin composition of the present invention include radical polymerization initiators such as azo-based initiators and peroxide-based initiators.

[0039] Examples of the azo initiator include azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis[2-(hydroxymethyl)propionitrile], 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobisisobutyric acid dimethyl, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], and 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}.

[0040] Examples of peroxide initiators include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, α,α'-di(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, di-t-butyl peroxide, t-butylcumyl peroxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di( Examples of suitable peroxides include 2,2-bis(t-butylperoxy)hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide, trimethylsilyltriphenylsilyl peroxide, and diisopropylbenzene hydroperoxide.

[0041] The polymerization initiator used in the resin composition of the present invention is preferably a peroxide-based initiator.

[0042] The content of the polymerization initiator in the resin composition of the present invention is not particularly limited, but examples thereof include an amount of 0.1 to 20 wt %, 0.1 to 10 wt %, or 0.1 to 5 wt % relative to the total weight of the resin composition.

[0043] (Other Components) The resin composition of the present invention may contain other components as needed within the range that does not impair the effects of the present invention. Examples of other components include a thermosetting resin, an organic solvent, a crosslinking agent, a thermoplastic resin, an inorganic filler, an organic filler, a flame retardant, and other additives.

[0044] (Thermosetting resin) The thermosetting resin is not particularly limited, but for example, a monomer, prepolymer, oligomer, polymer, etc. having a vinyl group, a (meth)acryloyl group, an epoxy group, an oxetanyl group, or a maleimide group can be used. Among them, it is preferable to use a polyfunctional resin. Specific examples of the thermosetting resin include the following components A-1 to A-5.

[0045] [Component A-1] Component A-1 is a maleimide compound. There are no particular limitations on the maleimide compound, as long as it is a compound having one or more maleimide groups in the molecule. Specific examples include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, polytetramethyleneoxide-bis(4-maleimidobenzoate), 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, and 4,4'-diphenylmethane. Examples of the maleimide compound include bismaleimide, bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane, 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane, maleimide compounds represented by the following formula (IV), prepolymers of these maleimide compounds, and prepolymers of maleimide compounds and amine compounds. Commercially available maleimide compounds can be used. Examples of commercially available maleimide compounds include MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.), MIR-3000-70MT (manufactured by Nippon Kayaku Co., Ltd.), BMI (manufactured by K.I. Kasei Co., Ltd.), BMI-70 (manufactured by K.I. Kasei Co., Ltd.), and BMI-80 (manufactured by K.I. Kasei Co., Ltd.). These compounds can also be used alone or in combination.

[0046] In formula (IV), n is an integer of 1 to 100. n is preferably 1 to 50, more preferably 1 to 20, and even more preferably 1 to 5.

[0047] [Component A-2] Component A-2 is a polyphenylene ether compound. The polyphenylene ether compound in Component A-2 is not particularly limited as long as it is a polymer having a repeating unit represented by the following formula (V).

[0048] In formula (V), R ４ ~R ７R each independently represents a hydrogen atom, a C1 to C6 alkyl group, a C2 to C6 alkenyl group, a C2 to C6 alkynyl group, a C1 to C6 alkylcarbonyl group, or a C2 to C6 alkenylcarbonyl group. ４ ~R ７ Examples of the C1 to C6 alkyl group in R include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and a t-butyl group. ４ ~R ７ Examples of the C2 to C6 alkenyl group in R include a vinyl group, a 1-propenyl group, a 2-propenyl group (allyl group), a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-methyl-2-propenyl group, and a 2-methyl-2-propenyl group. ４ ~R ７ Examples of the C2 to C6 alkynyl group in R include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-methyl-2-propynyl group, a 2-methyl-3-butynyl group, a 1-pentynyl group, a 2-pentynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-methyl-2-butynyl group, a 2-methyl-3-pentynyl group, a 1-hexynyl group, and a 1,1-dimethyl-2-butynyl group. ４ ~R ７ Examples of the C1-C6 alkylcarbonyl group in R include an acetyl group. ４ ~R ７ Examples of the C2-C6 alkenylcarbonyl group in the formula include an acryloyl group and a methacryloyl group.

[0049] The polyphenylene ether compound in Component A-2 may be terminally modified. Examples of terminally modified polyphenylene ether compounds include polyphenylene ether compounds terminally modified with hydroxyl groups and polyphenylene ether compounds modified with a substituent having a carbon-carbon unsaturated double bond.

[0050] Examples of the substituent having a carbon-carbon unsaturated double bond include a group represented by formula (VI), a group represented by formula (VII), an acryloyl group, or a methacryloyl group.

[0051] In formula (VI) and formula (VII), * indicates the bonding position.

[0052] Specific examples of the polyphenylene ether compound modified with a substituent having a carbon-carbon unsaturated double bond include compounds represented by formula (VIII) or formula (IX).

[0053] In formula (VIII), X ４ and X ５ each independently represents a group represented by formula (VI), a group represented by formula (VII), an acryloyl group, or a methacryloyl group, and S1 and S2 each independently represent an integer of 0 to 20. ４ and X ５ The group represented by formula (VI) and the group represented by formula (VII) are as described above.

[0054] In formula (IX), X ６ and X ７ each independently represents a group represented by formula (VI), a group represented by formula (VII), an acryloyl group, or a methacryloyl group; S3 and S4 each independently represent an integer of 0 to 20; Y １ represents a C1-C6 alkylene group. ６ and X ７ The group represented by formula (VI) and the group represented by formula (VII) in Y are as described above. １ Examples of the C1-C6 alkylene group in the formula include a methylene group, an ethylene group, a methylmethylene group, and a dimethylmethylene group.

[0055] The number average molecular weight (Mn) of the polyphenylene ether compound in Component A-2 is not particularly limited, and examples thereof include 1,000 to 7,000, 1,000 to 5,000, and 1,000 to 3,000. The number average molecular weight (Mn) is a value obtained by converting data measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent based on the molecular weight of standard polystyrene.

[0056] The polyphenylene ether compound in Component A-2 may be a known compound or a commercially available product. Examples of commercially available products include SA90 (manufactured by SABIC), SA9000 (manufactured by SABIC), and OPE-2st (manufactured by Mitsubishi Gas Chemical Company, Inc.). When synthesizing a polyphenylene ether compound, it can be synthesized by the method described in WO2014 / 203511 or a method similar thereto.

[0057] When the resin composition of the present invention contains a polyphenylene ether compound as Component A-2, the weight ratio of the polybutadiene to the polyphenylene ether compound may be, for example, 10:90 to 90:10, 20:80 to 90:10, 20:80 to 85:15, 30:70 to 90:10, 30:70 to 85:15, 40:60 to 90:10, or 40:60 to 85:15.

[0058] [Component A-3] Component A-3 is a polybutadiene having a molar ratio of 1,2 bond structures to 1,4 bond structures of 80:20 to 100:0. The polybutadiene in component A-3 may be a polybutadiene whose main chain and terminals are not modified, or a polybutadiene whose main chain and terminals are modified (excluding polybutadiene modified with the aforementioned phosphorus-containing group). The weight-average molecular weight (Mw) of the polybutadiene in component A-3 is not particularly limited, but examples include 500 to 10,000, 500 to 8,000, 500 to 6,000, and 500 to 5,000. The weight-average molecular weight (Mw) is a value obtained by converting data measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent based on the molecular weight of standard polystyrene. Commercially available polybutadiene can be used as the polybutadiene in component A-3. Examples of commercially available polybutadienes include NISSO-PB B-1000 (manufactured by Nippon Soda Co., Ltd.), NISSO-PB B-2000 (manufactured by Nippon Soda Co., Ltd.), and NISSO-PB B-3000 (manufactured by Nippon Soda Co., Ltd.). These polybutadienes can be used alone or in combination of two or more.

[0059] [Component A-4] Component A-4 is a styrene-butadiene-styrene block copolymer (hereinafter sometimes referred to as SBS) in which the molar ratio of 1,2-bond structures to 1,4-bond structures in the butadiene block is 80:20 to 100:0. The weight ratio of the styrene block to the butadiene block in the SBS in component A-4 is not particularly limited, but examples thereof include 10:90 to 80:20, 10:90 to 70:30, 10:90 to 60:40, 20:80 to 80:20, 30:70 to 80:20, and 40:60 to 80:20. The weight average molecular weight (Mw) of the SBS in component A-4 is not particularly limited, but examples thereof include 2,000 to 100,000, 2,000 to 80,000, and 2,000 to 60,000. The molecular weight distribution (Mw / Mn) of the SBS is not particularly limited, but examples include 1.00 to 3.00 and 1.00 to 2.00. The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The measurement conditions were: mobile phase THF (tetrahydrofuran), mobile phase flow rate 1 mL / min, column temperature 40°C, sample injection volume 40 μL, and sample concentration 2 wt%. The method for producing SBS in component A-4 is not particularly limited. For example, SBS can be produced by the methods described in JP-A-6-192502, JP-A-2000-514122, JP-A-2007-302901, WO 2021 / 024679, or methods equivalent thereto.

[0060] [Component A-5] Component A-5 is a polymer having a repeating unit represented by formula (1) in the molecule.

[0061]

[0062] The polymer in Component A-5 having a repeating unit represented by formula (1) in the molecule may also have a repeating unit represented by formula (2) and / or a repeating unit represented by formula (3). When the polymer in Component A-5 having a repeating unit represented by formula (1) in the molecule has a repeating unit represented by formula (2) and / or a repeating unit represented by formula (3), the polymer having a repeating unit represented by formula (1) in the molecule may be a block copolymer or a random copolymer.

[0063]

[0064] The weight-average molecular weight of the polymer in Component A-5 having a repeating unit represented by formula (1) in the molecule is preferably 1,200 to 40,000, and more preferably 1,200 to 35,000. The weight-average molecular weight (Mw) is a value obtained by converting data measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent based on the molecular weight of standard polystyrene.

[0065] As the polymer having a structural unit represented by formula (1) in the molecule of Component A-5, commercially available products can be used, such as ODV-XET-X03 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), ODV-XET-X04 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), and ODV-XET-X05 (manufactured by Nippon Steel Chemical & Material Co., Ltd.).

[0066] (Organic Solvent) The organic solvent is not particularly limited, and examples thereof include amide-based organic solvents, ether-based organic solvents, ester-based organic solvents, aliphatic hydrocarbon-based organic solvents, aromatic hydrocarbon-based organic solvents, ketone-based organic solvents, and organic halogen compound-based organic solvents. Examples of amide-based organic solvents include N,N-dimethylformamide (DMF) and N,N-dimethylacetamide; examples of ether-based organic solvents include diethyl ether, dipropyl ether, dibutyl ether, diamyl ether, and tetrahydrofuran; examples of ester-based organic solvents include ethyl acetate, propyl acetate, butyl acetate, amyl acetate, heptyl acetate, ethyl butyrate, isoamyl isovalerate, and propylene glycol methyl ether acetate; examples of aliphatic hydrocarbon-based organic solvents include normal hexane, normal heptane, and cyclohexane; examples of aromatic hydrocarbon-based organic solvents include toluene and xylene; examples of ketone-based organic solvents include methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and examples of organic halogenide-based organic solvents include trichloroethane and trichloroethylene. Furthermore, relatively inactive organic solvents such as propylene glycol monomethyl ether and propylene glycol monoethyl ether can also be used.

[0067] (Crosslinking Agent) The crosslinking agent is not particularly limited, but examples thereof include polyfunctional vinyl compounds such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl; vinylbenzyl ether compounds synthesized by the reaction of phenol and vinylbenzyl chloride; styrene monomers; allyl ether compounds synthesized by the reaction of phenol and allyl chloride; trialkenyl isocyanurates such as triallyl isocyanurate (TAIC (registered trademark)) and triallyl cyanurate (TAC); (meth)acrylate compounds (methacrylate compounds and acrylate compounds) such as trimethylolpropane; and compounds having an acenaphthylene skeleton. The use of these crosslinking agents can improve heat resistance. Only one crosslinking agent may be used, or two or more crosslinking agents may be used.

[0068] Examples of the compound having an acenaphthylene skeleton include acenaphthylene; hydroxyacenaphthylene compounds such as 3-hydroxyacenaphthylene, 4-hydroxyacenaphthylene, 5-hydroxyacenaphthylene, and 5,6-dihydroxyacenaphthylene; alkylacenaphthylene compounds such as 3-methylacenaphthylene, 3-ethylacenaphthylene, 3-propylacenaphthylene, 4-methylacenaphthylene, 4-ethylacenaphthylene, 4-propylacenaphthylene, 5-methylacenaphthylene, 5-ethylacenaphthylene, 5-propylacenaphthylene, 3,8-dimethylacenaphthylene, and 5,6-dimethylacenaphthylene; alkoxyacenaphthylene compounds such as 3-methoxyacenaphthylene, 3-ethoxyacenaphthylene, 3-butoxyacenaphthylene, 4-methoxyacenaphthylene, 4-ethoxyacenaphthylene, 4-butoxyacenaphthylene, 5-methoxyacenaphthylene, 5-ethoxyacenaphthylene, and 5-butoxyacenaphthylene; Examples include halogenated acenaphthylene compounds such as 3-chloroacenaphthylene, 3-bromoacenaphthylene, 4-chloroacenaphthylene, 4-bromoacenaphthylene, 5-chloroacenaphthylene, and 5-bromoacenaphthylene.

[0069] (Thermoplastic Resin) The thermoplastic resin is not particularly limited, but examples thereof include polyacrylate resin, polymethacrylate resin, polystyrene resin, polyphenylene ether resin, polyetherimide resin, polyethersulfone resin, polyphenylene sulfide resin, polycyclopentadiene resin, polycycloolefin resin, polycycloolefin copolymer resin, polyarylate resin, polyether resin, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polycarbonate resin, polyetheretherketone resin, polyester resin, liquid crystal polyester resin, fluorine Examples of the thermoplastic elastomer include resins and the like, and known thermoplastic elastomers, such as styrene-ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, (meth)acrylonitrile-butadiene-(meth)acrylic acid copolymer, (meth)acrylonitrile-butadiene-methyl(meth)acrylate copolymer, methyl(meth)acrylate-butadiene-styrene copolymer (MBS), as well as (meth)acrylonitrile-butadiene rubber (NBR), linear polyurethane, polybutadiene, polyisoprene, fluorine-based rubber, and ethylene-propylene-diene rubber.

[0070] (Inorganic filler) The material of the inorganic filler is not particularly limited, but can be exemplified by silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate.Among these, silica is particularly suitable.Furthermore, as the silica, spherical silica is preferred.The inorganic filler may be used alone, or two or more may be used in combination.

[0071] The inorganic filler is preferably treated with one or more surface treatment agents such as an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an organosilazane compound, a titanate coupling agent, a vinylsilane coupling agent, a methacryloxysilane coupling agent, an acryloxysilane coupling agent, and a styrylsilane coupling agent.

[0072] (Organic Filler) The organic filler is not particularly limited, but examples thereof include rubber particles, fluororesin particles (fluorine-based polymer particles), polyamide fine particles, silicone particles, and the like.

[0073] As the rubber particles, commercially available products may be used, such as "EXL-2655" manufactured by Dow Chemical Japan Co., Ltd. and "AC3816N" manufactured by Aica Kogyo Co., Ltd.

[0074] Examples of fluororesin particles (fluorine-based polymer particles) include polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylenepropene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluorodioxole copolymer (TFE / PDD), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF), etc. These resins may be used alone or in combination of two or more. As the fluororesin particles (fluoropolymer particles), commercially available products may be used, and examples thereof include "Lubron (registered trademark) L-2" manufactured by Daikin Industries, Ltd., "Lubron L-5" manufactured by Daikin Industries, Ltd., "Lubron L-5F" manufactured by Daikin Industries, Ltd., "Fluon (registered trademark) PTFE L-170JE" manufactured by Asahi Glass Co., Ltd., "Fluon PTFE L-172JE" manufactured by Asahi Glass Co., Ltd., "Fluon PTFE L-173JE" manufactured by Asahi Glass Co., Ltd., "KTL-500F" manufactured by Kitamura Co., Ltd., "KTL-2N" manufactured by Kitamura Co., Ltd., "KTL-1N" manufactured by Kitamura Co., Ltd., and "TLP10F-1" manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd.

[0075] The inorganic filler and organic filler may contain surface-treated particles. Examples of the surface treatment include surface treatment with a surface treatment agent. The surface treatment agent is not particularly limited. Examples of the surface treatment agent include surfactants such as nonionic surfactants, amphoteric surfactants, cationic surfactants, and anionic surfactants, as well as inorganic fine particles. From the viewpoint of affinity, it is preferable to use a fluorine-based surfactant as the surface treatment agent. Specific examples of fluorine-based surfactants include "Surflon (registered trademark) S-243" (perfluoroalkyl ethylene oxide adduct) manufactured by AGC Seimi Chemical Co., Ltd., "Megafac (registered trademark) F-251" manufactured by DIC Corporation, "Megafac F-477" manufactured by DIC Corporation, "Megafac F-553" manufactured by DIC Corporation, "Megafac R-40" manufactured by DIC Corporation, "Megafac R-43" manufactured by DIC Corporation, "Megafac R-94" manufactured by DIC Corporation, "FTX-218" manufactured by Neos Corporation, "Ftergent (registered trademark) 610FM" manufactured by Neos Corporation, and "Ftergent 730LM" manufactured by Neos Corporation.

[0076] (Flame Retardant) The flame retardant is not particularly limited, and examples thereof include halogen-based flame retardants and phosphorus-based flame retardants. Examples of halogen-based flame retardants include ethylene dipentabromobenzene, ethylene bistetrabromoimide, decabromodiphenyl oxide, and tetradecabromodiphenoxybenzene, each of which has a melting point of 300°C or higher. Examples of phosphorus-based flame retardants include phosphate ester-based flame retardants such as condensed phosphate esters of dixylenyl phosphate, phosphazene-based flame retardants such as phenoxyphosphazene, and phosphinate-based flame retardants such as metal phosphinates of aluminum dialkylphosphinate. Each of the exemplified flame retardants may be used alone, or two or more may be used in combination.

[0077] (Other Additives) Examples of other additives include antifoaming agents such as silicone-based antifoaming agents and acrylate-based antifoaming agents, organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds, leveling agents, adhesion aids such as silane coupling agents, tackifiers such as tackifiers, heat stabilizers, antistatic agents, storage stabilizers such as BHT, antioxidants, light stabilizers, ultraviolet absorbers, dyes and pigments, lubricants, wetting and dispersing agents, heavy metal deactivators, ion trapping agents, emulsifiers, water dispersion stabilizers, release agents, waxes, rheology control agents, surfactants, and the like.

[0078] (Varnish) When producing a sheet-like laminate material described later, the resin composition of the present invention can be prepared as a varnish to form a resin varnish. The resin varnish is prepared, for example, as follows: Each component is added to an organic solvent and dissolved. Heating may be performed as necessary. Thereafter, if necessary, components that are insoluble in organic solvents, such as inorganic fillers, are added, and the mixture is dispersed using a ball mill, bead mill, planetary mixer, roll mill, or the like to prepare the resin varnish.

[0079] <Sheet-Like Laminated Material> The resin composition of the present invention can be used for a sheet-like laminated material, such as a prepreg, an adhesive film, or a metal foil with a thermosetting resin composition, which will be described later.

[0080] <Prepreg> The prepreg of the present invention is characterized in that a substrate is impregnated with the resin composition of the present invention. Examples of the substrate include fibrous substrates such as glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, and linter paper. The thickness of the substrate is not particularly limited, but is preferably 20 to 800 μm, more preferably 20 to 300 μm. The prepreg of the present invention can be produced by a known method. For example, a method in which the resin composition of the present invention is impregnated into the substrate and then dried can be used. The substrate impregnated with the resin composition can be heated under desired heating conditions, for example, at 80 to 170°C for 1 to 10 minutes to remove the solvent, thereby obtaining a semi-cured (B-stage) prepreg.

[0081] <Adhesive Film> The adhesive film of the present invention is characterized by having a resin composition layer containing the resin composition of the present invention on a support film. The adhesive film of the present invention can be produced by a known method. For example, the adhesive film can be produced by applying the resin composition of the present invention to a support film using a die coater or the like, and then drying the organic solvent by heating or blowing hot air or the like to form a resin composition layer.

[0082] The drying conditions are not particularly limited, but drying is carried out so that the content of the organic solvent in the resin composition layer becomes 10% by weight or less, preferably 5% by weight or less. Although this varies depending on the amount of organic solvent in the resin composition and the boiling point of the organic solvent, for example, a resin composition containing 30 to 60% by weight of organic solvent can be dried at 50 to 150°C for about 3 to 10 minutes to form a resin composition layer containing the resin composition of the present invention.

[0083] The thickness of the resin composition layer formed in the adhesive film is not particularly limited, but is preferably 5 to 200 μm, and from the viewpoint of thinning, more preferably 15 to 80 μm.

[0084] Examples of the support film include various plastic films such as polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride; polyester films such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate; polycarbonate films; and polyimide films. Release paper and metal foils such as copper foil and aluminum foil may also be used. Among these, plastic films are preferred from the viewpoint of versatility, and polyethylene terephthalate films are more preferred. The support and the protective film described below may be subjected to surface treatments such as mud treatment and corona treatment. Furthermore, they may be subjected to release treatment using a release agent such as a silicone resin-based release agent, an alkyd resin-based release agent, or a fluororesin-based release agent.

[0085] The thickness of the support film is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm.

[0086] A protective film conforming to the support can be further laminated on the surface of the resin composition layer that is not in close contact with the support. The thickness of the protective film is not particularly limited, but is, for example, 1 to 40 μm. By laminating the protective film, it is possible to prevent the adhesion of dust and the like to the surface of the resin composition layer and scratches. The adhesive film can also be wound into a roll for storage.

[0087] <Metal foil with resin composition> The metal foil with resin composition of the present invention is characterized by having a resin composition layer containing the resin composition of the present invention on a metal foil. Examples of the metal foil used here include copper foil and aluminum foil. The thickness of the metal foil is not particularly limited, but is preferably in the range of 3 to 200 μm, more preferably 5 to 105 μm.

[0088] The method for producing the resin composition-coated metal foil of the present invention is not particularly limited, and examples include a method in which the resin composition is uniformly dissolved or dispersed in an aromatic solvent, ketone solvent, or a mixture thereof, and then coated on the metal foil and dried. The coating can be repeated multiple times as needed, and in this case, it is also possible to repeat the coating using multiple solutions with different compositions and concentrations to adjust the final resin composition and resin amount to the desired one. The thickness of the resin composition layer formed in the resin composition-coated metal foil of the present invention is not particularly limited, but is preferably 5 to 200 μm.

[0089] The metal foil with a resin composition of the present invention may have a release film on the side of the resin composition layer that is not in contact with the metal foil. Examples of the release film that can be used include resin films primarily composed of polyolefins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate and polyethylene naphthalate; polyimides; and polycarbonates. The surface of these films may be coated with a silicone resin release agent or the like to adjust the peel strength. The thickness of the release film is preferably 1 to 300 μm, more preferably 5 to 200 μm, even more preferably 10 to 150 μm, and even more preferably 20 to 120 μm. The surface of the release film that comes into contact with the resin sheet may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0090] <Laminate> The metal foil-attached laminate of the present invention comprises a layer of the resin composition of the present invention and a metal foil. Examples of the metal foil used here include copper foil and aluminum foil. The thickness of the metal foil is not particularly limited, but is in the range of 3 to 200 μm, more preferably 5 to 105 μm.

[0091] The method for producing the laminate of the present invention is not particularly limited, but examples include a method in which the sheet-like laminate material of the present invention described above and a metal foil are laminated in a layer configuration appropriate for the purpose, and the layers are bonded together under heat and pressure while simultaneously thermosetting. In the metal foil-attached laminate of the present invention, a layer of the thermosetting resin of the present invention and a metal foil are laminated in any layer configuration. The metal foil can be used as both a surface layer and an intermediate layer. In addition to the above, it is also possible to create a multilayer structure by repeating the lamination and curing process multiple times.

[0092] Examples of the present invention will be described below, but the technical scope of the present invention is not limited to these examples.

[0093] <Weight-average molecular weight (Mw) and dispersity (Mw / Mn)> The weight-average molecular weight of the polymers obtained in the examples was measured using the following apparatus and conditions. [Apparatus] Sample injection apparatus: Waters 2695 Alliance Separation column: Shodex KF-G, 803, 802, 801 Detector: Waters 2414 differential refractive index (RI) detector 2998 photodiode array (PDA) detector Column oven: Waters column oven [Conditions] Column oven temperature: 40°C RI detector temperature: 40°C Mobile phase: tetrahydrofuran Flow rate: 1.0 mL / min Standard injection volume: 40 μL PDA detector extraction wavelength: 254.0 nm Quantitative calculation: standard polystyrene equivalent

[0094] Example 1: Method for producing polybutadiene A 607 g of cyclopentyl methyl ether and 44 g of n-butyllithium (14.7 wt % hexane solution) were added to a reaction vessel. The internal temperature of the reaction vessel was adjusted to 0°C, and 100 g of 1,3-butadiene was added dropwise. The mixture was stirred for 30 minutes to obtain a polymerization solution. At room temperature, the polymerization solution was added dropwise to a cyclopentyl methyl ether solution of triphenyl phosphate (the amount of triphenyl phosphate in the solution was 67 g), and the mixture was stirred for 20 minutes to obtain a reaction solution. 400 g of 3% aqueous acetic acid was added to the reaction solution, and the layers were separated. The obtained organic layer was washed twice with water, and then the solvent was distilled off using an evaporator until the solids concentration of the organic layer reached 50%. 4 L of methanol was added dropwise to the organic layer to precipitate the polymer, and the supernatant was decanted and dried in an oven to obtain polybutadiene A. The resulting polybutadiene A was analyzed by gel permeation chromatography (THF mobile phase, polystyrene standard) to confirm that it had a weight average molecular weight (Mw) of 1,700 and a molecular weight distribution (Mw / Mn) of 1.13. １ The 1,2 bond structure in polybutadiene A calculated by H-NMR was 78 mol%. Using ICP-OES (inductively coupled plasma optical emission spectroscopy), it was confirmed that a phosphorus-containing group derived from triphenyl phosphate was bonded to the polybutadiene. Based on the manufacturing method, it was estimated that the phosphorus-containing group was bonded to one end of the polybutadiene.

[0095] (Example 2) Production method of polybutadiene B Except for changing triphenyl phosphate to tributyl phosphate, polybutadiene B was produced in the same manner as in Example 1. When polybutadiene B was analyzed by gel permeation chromatography (THF mobile phase, polystyrene standard), it was confirmed that the weight average molecular weight (Mw) was 1,700 and the molecular weight distribution (Mw / Mn) was 1.13. １ The 1,2 bond structure in the polybutadiene calculated by H-NMR was 78 mol%. ICP-OES confirmed that a phosphorus-containing group derived from tributyl phosphate was bonded to the polybutadiene. Based on the manufacturing method, it was estimated that the phosphorus-containing group was bonded to one end of the polybutadiene.

[0096] (Example 3) Production method of polybutadiene C Polybutadiene C was produced in the same manner as in Example 1, except that triphenyl phosphate was changed to chlorodiphenylphosphine oxide. When polybutadiene C was analyzed by gel permeation chromatography (THF mobile phase, polystyrene standard), it was confirmed that the weight average molecular weight (Mw) was 1,100 and the molecular weight distribution (Mw / Mn) was 1.26. １ The 1,2 bond structure in the polybutadiene calculated by H-NMR was 78 mol%. ICP-OES confirmed that a phosphorus-containing group derived from chlorodiphenylphosphine oxide was bonded to the polybutadiene. Based on the manufacturing method, it was estimated that the phosphorus-containing group was bonded to one end of the polybutadiene.

[0097] Example 4: Production method of polybutadiene D Polybutadiene D was produced in the same manner as in Example 1, except that triphenyl phosphate was replaced with tris(2-ethylhexyl) phosphate. Analysis of polybutadiene D by gel permeation chromatography (THF mobile phase, polystyrene standard) confirmed that the weight average molecular weight (Mw) was 2,000 and the molecular weight distribution (Mw / Mn) was 1.09. The 1,2 bond structure in the polybutadiene calculated by 1H-NMR was 76 mol%. ICP-OES confirmed that a phosphorus-containing group derived from tris(2-ethylhexyl) phosphate was bonded to the polybutadiene. Based on the production method, it was estimated that the phosphorus-containing group was bonded to one end of the polybutadiene.

[0098] (Example 5) Production method of polybutadiene E Polybutadiene E was produced in the same manner as in Example 1, except that triphenyl phosphate was changed to tricresyl phosphate. Analysis of polybutadiene E by gel permeation chromatography (THF mobile phase, polystyrene standard) confirmed that the weight average molecular weight (Mw) was 2,300 and the molecular weight distribution (Mw / Mn) was 1.21. 1H-NMR calculation revealed that the 1,2 bond structure in the polybutadiene was 77 mol%. ICP-OES confirmed that a phosphorus-containing group derived from tricresyl phosphate was bonded to the polybutadiene. Based on the production method, it was estimated that the phosphorus-containing group was bonded to one end of the polybutadiene.

[0099] (Example 6) Manufacturing method of cured product Each reagent was mixed according to the composition (parts by weight) shown in Tables 1 to 3. The resin composition was cured by heat pressing at 200°C for 120 minutes to obtain a cured product.

[0100] B-3000: Liquid polybutadiene manufactured by Nippon Soda Co., Ltd. Percumyl D: Dicumyl peroxide manufactured by NOF Corporation

[0101] SA9000: Methacrylic-modified polyphenylene ether compound manufactured by SABIC Innovative Plastics DOPO: 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide manufactured by Tokyo Chemical Industry Co., Ltd. Percumyl D: Dicumyl peroxide manufactured by NOF Corporation

[0102] SA9000: Methacrylate-modified polyphenylene ether compound manufactured by SABIC Innovative Plastics. Percumyl D: Dicumyl peroxide manufactured by NOF Corporation.

[0103] (Example 7) Method for producing varnish Each reagent was blended in the composition (parts by weight) shown in Table 4, and this was stirred and mixed with a mixed solvent of methyl ethyl ketone and cyclohexanone to homogenize, thereby preparing a varnish of a resin composition. SA9000: Methacrylate-modified polyphenylene ether compound manufactured by SABIC Innovative Plastics B-1000: Liquid polybutadiene manufactured by Nippon Soda DOPO: 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide manufactured by Tokyo Chemical Industry Co., Ltd. Percumyl D: Dicumyl peroxide manufactured by NOF Corporation SC2300-SVJ: Silica filler manufactured by Admatechs Co., Ltd.

[0104] (Example 8) Manufacturing method of prepreg A glass cloth (manufactured by Nitto Boseki Co., Ltd., #2116 type, WEA116, E glass, thickness 0.1 mm) was impregnated with the varnish and then thermally dried at 100°C for 15 minutes to manufacture a prepreg.

[0105] (Example 9) Manufacturing Method of Flame Retardant Test Piece Ten sheets of the above prepreg were stacked and cured by heat pressing at 200° C. for 120 minutes to obtain a cured product. A test piece measuring 125 mm in length and 13 mm in width was cut out from the cured product to manufacture a flame retardant test piece.

[0106] (Test Examples 1 to 6, Reference Examples 1 and 2) The cured product obtained in Example 6 was measured for the following items, and the results are shown in Tables 5 and 6. <Dielectric constant (Dk) and dielectric loss tangent (Df)> Measurements were carried out at 10 GHz using a cylindrical cavity resonator (TE mode resonator) manufactured by AET Corporation. <Dielectric loss tangent (Df) after moisture absorption> The cured product used in the above-mentioned dielectric loss tangent measurement was treated for 72 hours under conditions of a temperature of 85°C and a relative humidity of 85%. After the moisture absorption treatment, the moisture on the cured product was thoroughly wiped off with a dry, clean cloth. The dielectric loss tangent of this moisture-absorbed cured product (dielectric loss tangent after moisture absorption) was measured in the same manner as in the measurement of the dielectric loss tangent before the moisture absorption treatment.

[0107]

[0108]

[0109] Test Example 1 shows that the cured product of polybutadiene A (Cured Product 1) has electrical properties equivalent to those of the cured product of B-3000 (Reference Cured Product 1), which is known to have excellent electrical properties. Furthermore, the dielectric dissipation factor after moisture absorption of Cured Product 1 was superior to that of Reference Cured Product 1, demonstrating that Cured Product 1 has excellent moisture absorption resistance. Test Examples 2 to 6 also show that the cured products of polybutadiene A and SA9000 (Cured Products 4 to 8) have superior electrical properties and moisture absorption resistance to those of the cured product of SA9000 (Reference Cured Product 3).

[0110] (Test Example 7, Reference Examples 3 to 5) Flame Retardancy Test Test specimens were prepared in accordance with the UL94 flame retardancy standard, and a flame retardancy test was carried out. Evaluation criteria: Based on the UL94 standard. The results are shown in Table 7. The criteria for judgment are as follows:

Claims

1. A method for producing a tertiary amine comprising the steps of: (a) providing a tertiary amine having a molar ratio of 1,2 bond structure to 1,4 bond structure in a polybutadiene of 60:40 to 100:0; and (b) providing a tertiary amine having a molar ratio of 1,2 bond structure to 1,4 bond structure in a polybutadiene of 60:40 to 100:0; and (c (In formula (III), * indicates a bond position, and X １ and X ２ each independently represents a single bond or an oxygen atom; R １ and R ２ each independently represents an organic group.

2. The resin composition according to claim 1, further comprising a polymerization initiator.

3. The resin composition according to claim 1 or 2, wherein the phosphorus-containing group is bonded only to a terminal carbon atom in the polybutadiene.

4. The resin composition according to claim 1 or 2, wherein the weight average molecular weight of the polybutadiene is 1,000 to 8,000.

5. The resin composition according to claim 1 or 2, wherein the molecular weight distribution of the polybutadiene is 1.00 to 3.

00.

6. A prepreg impregnated with the resin composition according to claim 1 or 2.

7. An adhesive film having a resin composition layer containing the resin composition according to claim 1 or 2 on a support film.

8. A metal foil with a resin composition, comprising a resin composition layer containing the resin composition according to claim 1 or 2 on the metal foil.

9. A laminate comprising a layer of the cured resin composition according to claim 1 or 2, and a metal foil.

10. The molar ratio of 1,2 bond structure to 1,4 bond structure in the polybutadiene is 60:40 to 100:0, and only the terminal carbon atoms in the polybutadiene are bonded to the olefin represented by formula (III). (In formula (III), * indicates a bond position, and X １ and X ２ each independently represents a single bond or an oxygen atom; R １ and R ２ each independently represents an organic group.

11. A process for anionically polymerizing 1,3-butadiene in the presence of a solvent and an anionic initiator, (In formula (IV), X １ , X ２ , R １ and R ２ is the same as defined in formula (III), and X ３ is a halogeno group or a group of the formula "-OR ３ ", R ３ The method for producing polybutadiene according to claim 10, comprising reacting a compound represented by the formula (I) with a compound represented by the formula (I):

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