composition for the insulating layer of a printed circuit board

Abstract

The objective of the present invention is to provide a composition for use in an insulating layer of a printed circuit board, which has a low dielectric constant and a low dielectric loss tangent, and also has flame retardancy. Contains polybutadiene, The molar ratio of the 1,2 bond structure and the 1,4 bond structure in the above polybutadiene is 60:40 to 100:0, and At one or more carbon atoms in the above polybutadiene, formula (III) (In formula (III), * indicates a bonding position, X1 and X2 each independently represent a single bond or an oxygen atom, and R1 and R2 each independently represent an organic group.) A phosphorus-containing group represented by, bonded to, Resin composition for use in the insulating layer of a printed circuit board.

Description

Technology Field

[0001] The present invention relates to a composition for use in an insulating layer of a printed circuit board.

[0002] The present 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, and incorporates the contents thereof herein by reference. Background Technology

[0003] Various known resins are used to manufacture printed circuit boards included in mobile communication devices such as mobile phones and smartphones, base station devices, network-related electronic devices such as servers and routers, and large computers.

[0004] Recently, in the aforementioned network-related electronic devices, it is necessary to transmit and process large amounts of information at low loss and high speed, and the electrical signals handled by the printed circuit boards of these products are also becoming higher frequency. Since high-frequency electrical signals are prone to attenuation, it is necessary to further reduce transmission loss in the printed circuit boards. Therefore, the resin used when manufacturing printed circuit boards is required to have a low dielectric constant and a low dielectric loss tangent.

[0005] In addition, recently, regulations on flame retardancy in various industrial products have become strict, and materials used in printed circuit boards are also required to have flame retardancy.

[0006] Patent Document 1 discloses that a phosphate-modified polymer having a double bond with a phosphate substituent comprising a phosphate atom directly bonded to a carbon atom has high thermal stability.

[0007] In the same patent document, diene-based rubber and the like are exemplified as polymers, and it is described that a phosphorus substituent reacts with a portion of the double bond of the polymer to add a hydrogen atom and a phosphorus atom to the double bond (hydrophosphonation reaction). This is obtained by reacting a raw material polymer with at least one phosphorus compound selected from phosphoric acid, phosphorous acid, and esters or salts thereof in the presence of a catalyst.

[0008] Therefore, since phosphorus substituents can bind to all double bonds within the polymer, there are no cases where they bind only to the polymer ends.

[0009] It is described that by incorporating the polymer into a rubber composition, improvements in heat generation accompanying improved filler dispersion, improved wet grip accompanying improved hydrophilicity, improved toughness accompanying three-dimensional network formation, and improved wear resistance due to increased gelation rate can be expected.

[0010] The phosphate-modified polymer in question is described only for use as rubber, but there is no description regarding its electrical properties, nor is there any description regarding its use in the insulating layer of a printed circuit board. Prior art literature

[0011] WO 2016 / 063975 Pamphlet The problem to be solved

[0012] The objective of the present invention is to provide a composition for use in an insulating layer of a printed circuit board, which has a low dielectric constant and a low dielectric loss tangent, and also has flame retardancy. means of solving the problem

[0013] As a result of careful examination, the inventors found that the above problem is solved by a composition containing polybutadiene modified by a phosphorus-containing group.

[0014] The present invention relates to the following invention.

[0015] (1) Polybutadiene is contained, wherein the molar ratio of the 1,2 bond structure and the 1,4 bond structure in the polybutadiene is 60:40 to 100:0, and at least one carbon atom in the polybutadiene, formula (III)

[0016] [Chemical Formula 1]

[0017]

[0018] (In Equation (III), * indicates the joint position, and X 1 and X 2 Each independently represents a single bond or an oxygen atom, and R 1 and R 2 A resin composition for use in an insulating layer of a printed circuit board, wherein a phosphorus-containing group represented by (each independently represents an organic group.) is bonded.

[0019] (2) A resin composition described in (1) that additionally contains a polymerization initiator.

[0020] (3) A resin composition described in (1) or (2) in which the phosphorus-containing group is bonded only to the terminal carbon atoms of the polybutadiene.

[0021] (4) A resin composition described in any one of (1) to (3), wherein the weight average molecular weight of the polybutadiene is 1,000 to 8,000.

[0022] (5) A resin composition described in any one of (1) to (4), wherein the molecular weight distribution of the polybutadiene is 1.00 to 3.00.

[0023] (6) A prepreg impregnated with a resin composition described in any one of (1) to (5).

[0024] (7) An adhesive film having a resin composition layer containing a resin composition described in any one of (1) to (5) on a support film.

[0025] (8) A metal foil having a resin composition layer containing a resin composition described in any one of (1) to (5) on a metal foil.

[0026] (9) A laminate having a layer of cured resin composition described in any one of (1) ~ (5) and a metal foil.

[0027] (10) The molar ratio of 1,2 bond structures and 1,4 bond structures in polybutadiene is 60:40 to 100:0, and only the terminal carbon atoms in the polybutadiene, formula (III)

[0028] [Chemical Formula 2]

[0029]

[0030] (In Equation (III), * indicates the joint position, and X 1 and X 2 Each independently represents a single bond or an oxygen atom, and R 1 and R 2 Polybutadiene having a phosphorus-containing group bonded thereto, represented by (each independently representing an organic group).

[0031] (11) A process for anionic polymerization of 1,3-butadiene in the presence of a solvent and anionic initiator,

[0032] After the above process, formula (IV)

[0033] [Chemical Formula 3]

[0034]

[0035] (In Equation (IV), X 1 , X 2 , R 1 and R 2 is identical to the definition in Equation (III), and X 3 silver, halogenogroup, or formula "-OR" 3 Represents the energy represented by 」, and R 3 A process comprising reacting a compound represented by (which indicates an organic group),

[0036] (10) Method for manufacturing polybutadiene as described. Effects of the invention

[0037] In the present invention, the polybutadiene has a phosphorus-containing group, so the cured product of the polybutadiene in the present invention is flame-retardant. Furthermore, although the polybutadiene in the present invention has a phosphate group, the cured product of the polybutadiene in the present invention has electrical properties equivalent to those of the cured product of unmodified polybutadiene, and also has superior moisture resistance compared to the cured product of unmodified polybutadiene. Specific details for implementing the invention

[0038] In this specification, "1,2 combined structure" refers to a repeating unit represented by formula (I).

[0039] [Chemical Formula 4]

[0040]

[0041] In this specification, "1,4 combined structure" refers to a repeating unit represented by formula (II).

[0042] [Chemical Formula 5]

[0043]

[0044] In this specification, the term “terminal” may be an end of one side of polybutadiene or an end of both sides.

[0045] In this specification, "terminal carbon atom" refers to a carbon atom of a repeating unit at the end of polybutadiene.

[0046] <Polybutadiene (hereinafter referred to as "polybutadiene with a phosphorus-containing group attached")>

[0047] The polybutadiene in the present invention has only a 1,2 bond structure, or a 1,2 bond structure and a 1,4 bond structure. Among the total repeating units of the polybutadiene in the present invention, the molar ratio of the 1,2 bond structure to the 1,4 bond structure is 60:40 to 100:0, preferably 70:30 to 100:0, and more preferably 70:30 to 95:5. The polybutadiene in the present invention may have repeating units other than the 1,2 bond structure and the 1,4 bond structure. Examples of repeating units other than the 1,2 bond structure and the 1,4 bond structure include repeating units in which the 1,2 bond structure is hydrogenated, repeating units in which the 1,4 bond structure is hydrogenated, etc.

[0048] The polybutadiene in the present invention has a phosphorus-containing group represented by formula (III) on one or more carbon atoms in the polybutadiene.

[0049] [Chemical Formula 6]

[0050]

[0051] In Equation (III), * indicates the joint position, and X 1 and X 2 Each independently represents a single bond or an oxygen atom, and R 1 and R 2 Each independently represents an organic group.

[0052] R in Equation (III) 1 and R 2 Examples of “organic groups” in this include C1-C10 alkyl groups, C2-C10 alkenyl groups, C2-C10 alkynyl groups, or C6-C10 aryl groups.

[0053] As C1 to C10 alkyl groups, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, isopropyl group, sec-butyl group, isobutyl group, tert-butyl group, neopentyl group, isopentyl group, sec-pentyl group, 1-ethylpropyl group, tert-pentyl group, isohexyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1,1,2,2-tetramethylpropyl group, 1,1,3-trimethylbutyl group, 1-ethylpentyl group, 1,1,3,3-tetramethylbutyl group, 2,2,3,3-tetramethylbutyl group, 1,2,4-trimethylpentyl group, Examples include 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, etc.

[0054] Examples of C2 to C10 alkenyl groups include vinyl groups, 1-propenyl groups, 2-propenyl groups (allyl groups), 1-butenyl groups, 2-butenyl groups, 3-butenyl groups, 1-methyl-2-propenyl groups, 2-methyl-2-propenyl groups, etc.

[0055] Examples of C2 to C10 alkynyl groups include ethinyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-methyl-3-butynyl, 1-phentinyl, 2-phentinyl, 3-phentinyl, 4-phentinyl, 1-methyl-2-butynyl, 2-methyl-3-phentinyl, 1-hexinyl, 1,1-dimethyl-2-butynyl, etc.

[0056] Examples of C6 to C10 aryl groups include phenyl groups and naphthyl groups.

[0057] R 1 and R 2 It is preferable that the group be a C1 to C10 alkyl group or a C6 to C10 aryl group.

[0058] In the present invention, the polybutadiene to which a phosphorus-containing group is attached may have a phosphorus-containing group represented by the above formula (III) attached to one or more carbon atoms in the polybutadiene. As long as it exhibits the effect of an insulating layer of the printed circuit board of the present invention, there is no particular limit to the number of carbon atoms to which a phosphorus-containing group is attached, but for example, five or fewer, three or fewer, or two or fewer may be cited.

[0059] Only the terminal carbon atoms in the polybutadiene may have a phosphorus-containing group represented by the above formula (III).

[0060] The weight average molecular weight (Mw) of the polybutadiene in the present invention is not particularly limited, but examples 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, 1,000 to 3,000, etc.

[0061] The molecular weight distribution of polybutadiene in the present invention (weight average molecular weight (Mw) / number average molecular weight (Mn)) is not particularly limited, but examples include 1.00 to 3.00, 1.00 to 2.00, etc.

[0062] The above weight-average molecular weight or molecular weight distribution was measured using gel permeation chromatography (GPC) with polystyrene as the standard material. The measurement conditions were mobile phase THF (tetrahydrofuran), mobile phase flow rate 1 mL / min, column temperature 40 ℃, sample injection volume 40 μL, and sample concentration 2 wt%.

[0063] In the present invention, the method for producing polybutadiene with a phosphorus-containing group is not particularly limited, but, for example, the method described in the pamphlet of WO 2016 / 063975 may be cited. When produced by the said method, the phosphorus-containing group is bonded to a carbon atom in the polybutadiene.

[0064] In addition, the method for manufacturing polybutadiene in which the phosphorus-containing group is bonded only to the terminal carbon atoms is not particularly limited, but, for example, may include a manufacturing method comprising a process 1 of anionic polymerization of 1,3-butadiene in the presence of a solvent and an anionic initiator, and a process 2 of reacting a compound represented by formula (IV) after the process.

[0065] [Chemical Formula 7]

[0066]

[0067] Among Equation (IV), X 1 , X 2 , R 1 and R 2 is identical to the definition in Equation (III), and X 3 silver, halogenogroup, or formula "-OR" 3 Represents the energy represented by 」, and R 3 Silver represents an organic group.

[0068] X 3 Examples of halogen groups in this include chloro groups, bromo groups, iodine groups, etc.

[0069] R 3 As for the organic group in , R 1 and R 2 One can cite the same thing as the example given.

[0070] As compounds represented by formula (IV), specifically, the following compounds may be cited.

[0071] Trimethylphosphate, triethylphosphate, tripropylphosphate, triisopropylphosphate, tributylphosphate, tri-sec-butylphosphate, tri-tert-butylphosphate, tripentylphosphate, trihexylphosphate, tris(2-ethylhexyl)phosphate, tris(2-butoxyethyl)phosphate, tricyclohexylphosphate, tricyclopentylphosphate, tris(2,2,2-trifluoroethyl)phosphate, tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphate, tribenzylphosphate, trialylphosphate, tris(trimethylsilyl)phosphate, tris(triethylsilyl)phosphate, tris(2-chloroethyl)phosphate, tris(chloropropyl)phosphate, triphenylphosphate, tricrezilphosphate, crezildiphenylphosphate, Trixylenylphosphate, cresildi2,6-xylenylphosphate, 4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]Octane 1-oxide, 2-(2,2,2-trifluoroethoxy)-1,3,2-dioxaphosphoran 2-oxide, dimethylchlorophosphate, diethylchlorophosphate, dipropylchlorophosphate, diisopropylchlorophosphate, dibutylchlorophosphate, di-sec-butylchlorophosphate, di-tert-butylchlorophosphate, dipentylchlorophosphate, dihexylchlorophosphate, bis(2-ethylhexyl)chlorophosphate, bis(2-butoxyethyl)chlorophosphate, dicyclohexylchlorophosphate, dicyclopentylchlorophosphate, bis(2,2,2-trifluoroethyl)chlorophosphate, bis(1,1,1,3,3,3-hexafluoro-2-propyl)chlorophosphate, dibenzylchlorophosphate, Diallyl chlorophosphate, bis(trimethylsilyl)chlorophosphate, bis(triethylsilyl)chlorophosphate, bis(2-chloroethyl)chlorophosphate, bis(chloropropyl)chlorophosphate, diphenylchlorophosphate, dicrezyl chlorophosphate, dixylenyl chlorophosphate, 2-chloro-2-oxo-1,3,2-dioxaphosphorane, bis(dimethylamino)phosphoryl chloride, chlorodiphenylphosphine oxide, dicyclohexylphosphineyl chloride, chlorodimethylphosphine oxide, chlorodiethylphosphine oxide, chlorodipropylphosphine oxide, chlorodiisopropylphosphine oxide, chlorodi-sec-butylphosphine oxide, chlorodi-tert-butylphosphine oxide, etc.

[0072] Examples of solvents include hydrocarbon solvents such as propane, butane, pentane, hexane, heptane, isooctane, cyclopentane, cyclohexane, methylcyclohexane, decane, benzene, and toluene, although they are not particularly limited; and ether solvents such as 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2-methoxymethyltetrahydrofuran, diethyl ether, triethyleneglycol dimethyl ether, and cyclopentylmethyl ether. In order to increase the proportion of 1,2 bond structures in polybutadiene, it is preferable to use an ether solvent or a mixed solvent of an ether solvent and a hydrocarbon solvent as the solvent.

[0073] Anionic polymerization initiators are not particularly limited, but examples include organic lithium compounds such as methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, isobutyl lithium, hexyl lithium, octyl lithium, tetramethylenedilithium, pentamethylenedilithium, hexamethylenedilithium, phenyl lithium, tolylithium, and lithium naphthylide; metallic sodium, etc.

[0074] When a phosphorus-containing group is attached to one end of polybutadiene, an organic lithium compound is used, and when a phosphorus-containing group is attached to both ends of polybutadiene, metallic sodium is used.

[0075] The polymerization temperature in process 1 is not particularly limited, but examples 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, -5°C to 5°C, etc.

[0076] <Resin Composition>

[0077] The resin composition of the present invention is a resin composition for use in the insulating layer of a printed circuit board. Examples of a printed circuit board include a single-sided printed circuit board, a double-sided printed circuit board, a multilayer printed circuit board, a flexible printed circuit board, a build-up board, etc. The above printed circuit board can be manufactured by a known method using a sheet material described below.

[0078] (Polybutadiene with phosphorus-containing groups)

[0079] The resin composition of the present invention contains polybutadiene to which the phosphorus-containing group is bonded.

[0080] The content of polybutadiene combined with a phosphorus-containing group in the resin composition of the present invention is not particularly limited, but may be an amount of 10 to 95 weight%, 10 to 90 weight%, 20 to 90 weight%, 30 to 90 weight%, 10 to 75 weight%, 20 to 75 weight%, or 30 to 75 weight% with respect to the total weight of the resin composition.

[0081] (Polymer initiator)

[0082] The resin composition of the present invention may additionally contain a polymerization initiator. Examples of polymerization initiators used in the resin composition of the present invention include radical polymerization initiators such as azo-based initiators and peroxide-based initiators.

[0083] As azo-based initiators, for example, azobis(isobutyronitrile), 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'-azobis(isobutyronic acid dimethyl), 2,2'-azobis[2-(2-imidazoline-2-yl)propane], Examples include 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}.

[0084] Peroxide-based 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)hexine-3, di-t-butylperoxide, t-butylcumyl peroxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis(t-butylperoxy)butane, and 2,2-bis(t-butylperoxy)octane. Examples include 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide, trimethylsilyltriphenylsilyl peroxide, diisopropylbenzenehydroperoxide, etc.

[0085] The polymerization initiator used in the resin composition of the present invention is preferably a peroxide-based initiator.

[0086] The content of the polymerization initiator in the resin composition of the present invention is not particularly limited, but may be in an amount of 0.1 to 20 weight%, 0.1 to 10 weight%, or 0.1 to 5 weight% with respect to the total weight of the resin composition.

[0087] (Other ingredients)

[0088] The resin composition of the present invention may contain other components as needed, provided that such components do not impede the effects of the present invention. Examples of other components include thermosetting resins, organic solvents, crosslinking agents, thermoplastic resins, inorganic fillers, organic fillers, flame retardants, and other additives.

[0089] (Thermosetting resin)

[0090] As for the thermosetting resin, although not particularly limited, for example, monomers, prepolymers, oligomers, polymers, etc. having vinyl groups, (meth)acryloyl groups, epoxy groups, or oxetanyl groups or maleimide groups may be used. Among these, it is preferable to use a polyfunctional resin. Specific examples of the thermosetting resin include, for example, the following components A-1 to A-5.

[0091] [Ingredient A-1]

[0092] Component A-1 is a maleimide compound. The maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in its molecule. Specific examples thereof include, for instance, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bis(3,5-diethyl-4-maleimidephenyl)methane, polytetramethylene oxide-bis(4-maleimidebenzoate), 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane, 4,4'-diphenylmethane bismaleimide, bis-(3-ethyl-5-methyl-4-maleimidephenyl)methane, 2,2-bis-[4-(4-maleimidephenoxy)phenyl]propane, the following formula Examples include maleimide compounds represented by (IV), prepolymers of these maleimide compounds, and prepolymers of maleimide compounds and amine compounds. In addition, commercially available maleimide compounds may be used. Examples of commercially available products include MIR-3000 (manufactured by Nippon Hwayakusho), MIR-3000-70MT (manufactured by Nippon Hwayakusho), BMI (manufactured by K.I. Chemical Co.), BMI-70 (manufactured by K.I. Chemical Co.), BMI-80 (manufactured by K.I. Chemical Co.), etc. It is also possible to use one or more of these in appropriate mixtures.

[0093] [Chemical Formula 8]

[0094]

[0095] In Equation (IV), n is any integer from 1 to 100. It is preferable that n is 1 to 50, more preferable that n is 1 to 20, and even more preferable that n is 1 to 5.

[0096] [Ingredient A-2]

[0097] 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 repeating units represented by the following formula (V).

[0098] [Chemical Formula 9]

[0099]

[0100] In equation (V), R 4 ~ R 7 Each represents, independently, a hydrogen atom, a C1–C6 alkyl group, a C2–C6 alkenyl group, a C2–C6 alkynyl group, a C1–C6 alkyl carbonyl group, or a C2–C6 alkenyl carbonyl group.

[0101] R 4 ~ R 7 Examples of C1 to C6 alkyl groups in this include methyl groups, ethyl groups, n-propyl groups, i-propyl groups, n-butyl groups, i-butyl groups, s-butyl groups, t-butyl groups, etc.

[0102] R 4 ~ R 7 Examples of C2 to C6 alkenyl groups in this include vinyl groups, 1-propenyl groups, 2-propenyl groups (allyl groups), 1-butenyl groups, 2-butenyl groups, 3-butenyl groups, 1-methyl-2-propenyl groups, 2-methyl-2-propenyl groups, etc.

[0103] R 4 ~ R 7Examples of C2 to C6 alkynyl groups in this include the ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group, 2-methyl-3-butynyl group, 1-phentinyl group, 2-phentinyl group, 3-phentinyl group, 4-phentinyl group, 1-methyl-2-butynyl group, 2-methyl-3-phentinyl group, 1-hexinyl group, 1,1-dimethyl-2-butynyl group, etc.

[0104] R 4 ~ R 7 Examples of C1 to C6 alkyl carbonyl groups in this include acetyl groups, etc.

[0105] R 4 ~ R 7 Examples of C2 to C6 alkenyl carbonyl groups in this include acrylyl groups, methacryloyl groups, etc.

[0106] The polyphenylene ether compound in component A-2 may have its terminals modified. Examples of polyphenylene ether compounds with modified terminals include polyphenylene ether compounds with terminals modified to hydroxyl groups or polyphenylene ether compounds modified to substituents having carbon-carbon unsaturated double bonds.

[0107] Examples of substituents having the above carbon-carbon unsaturated double bond include the group represented by formula (VI), the group represented by formula (VII), an acryloyl group, or a methacryloyl group.

[0108] [Chemical Formula 10]

[0109]

[0110] In equations (VI) and (VII), * indicates a bonding position.

[0111] Polyphenylene ether compounds modified with a substituent having a carbon-carbon unsaturated double bond include, specifically, compounds represented by formula (VIII) or formula (IX).

[0112] [Chemical Formula 11]

[0113]

[0114] Among Equation (VIII), X 4 and X 5 is independently a group represented by formula (VI), a group represented by formula (VII), an acryloyl group, or a methacryloyl group, and S1 and S2 are independently integers from 0 to 20. X 4 and X 5 The group represented by Equation (VI) and the group represented by Equation (VII) in the above are as described above.

[0115] [Chemical Formula 12]

[0116]

[0117] In Equation (IX), X 6 and X 7 is independently a group represented by formula (VI), a group represented by formula (VII), an acryloyl group, or a methacryloyl group, and S3 and S4 are independently integers from 0 to 20, and Y 1 represents a C1–C6 alkylene group. X 6 and X 7 The group represented by Equation (VI) and the group represented by Equation (VII) in Y are as described above. 1 Examples of C1 to C6 alkylene groups in this include methylene groups, ethylene groups, methylmethylene groups, dimethylmethylene groups, etc.

[0118] The number average molecular weight (Mn) of the polyphenylene ether compound in component A-2 is not particularly limited, but may be 1,000 to 7,000, 1,000 to 5,000, 1,000 to 3,000, etc. In addition, the number average molecular weight (Mn) is a value calculated based on the molecular weight of standard polystyrene using data measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.

[0119] The polyphenylene ether compound in component A-2 may be a known or commercially available product. Examples of commercially available products include SA90 (manufactured by SABIC), SA9000 (manufactured by SABIC), OPE-2st (manufactured by Mitsubishi Gas Chemical Co., Ltd.). When synthesizing the polyphenylene ether compound, it may be synthesized by the method described in WO 2014 / 203511, etc. and a method equivalent thereto.

[0120] When the resin composition of the present invention contains a polyphenylene ether compound which is component A-2, the weight ratio of the polybutadiene to the polyphenylene ether compound may be 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, 40:60 to 85:15, etc.

[0121] [Ingredient A-3]

[0122] Component A-3 is a polybutadiene having a molar ratio of 1,2-linked structures to 1,4-linked structures of 80:20 to 100:0. The polybutadiene in Component A-3 may be a polybutadiene in which the main chain and terminals are not modified, or a polybutadiene in which the main chain and terminals are modified (provided that the polybutadiene modified by the phosphorus-containing group is excluded).

[0123] The weight average molecular weight (Mw) of polybutadiene in component A-3 is not particularly limited, but may be 500 to 10,000, 500 to 8,000, 500 to 6,000, 500 to 5,000, etc. The weight average molecular weight (Mw) is a value calculated based on the molecular weight of standard polystyrene using data measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.

[0124] As for the polybutadiene in component A-3, commercially available products may be used. 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.), NISSO-PB B-3000 (manufactured by Nippon Soda Co., Ltd.), etc. These polybutadienes may be used individually or in combination of two or more types.

[0125] [Ingredient A-4]

[0126] Component A-4 is a styrene-butadiene-styrene block copolymer in which the molar ratio of 1,2-link structures to 1,4-link structures in the butadiene block is 80:20 to 100:0 (hereinafter referred to as SBS).

[0127] The weight ratio of the styrene block and butadiene block in SBS in component A-4 is not particularly limited, but examples 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.

[0128] The weight-average molecular weight (Mw) of SBS in component A-4 is not particularly limited, but examples include 2,000 to 100,000, 2,000 to 80,000, 2,000 to 60,000, etc. The molecular weight distribution (Mw / Mn) of SBS is not particularly limited, but examples include 1.00 to 3.00, 1.00 to 2.00, etc. The above weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured by gel permeation chromatography (GPC) using polystyrene as a standard material. The measurement conditions were mobile phase THF (tetrahydrofuran), mobile phase flow rate 1 mL / min, column temperature 40 ℃, sample injection volume 40 μL, and sample concentration 2 wt%.

[0129] The method of manufacturing SBS in component A-4 is not particularly limited. For example, it can be manufactured by the method described in Japanese Patent Publication No. Hei 6-192502, Japanese Patent Publication No. 2000-514122, Japanese Patent Publication No. 2007-302901, WO 2021 / 024679, etc. and by a method equivalent thereto.

[0130] [Ingredient A-5]

[0131] Component A-5 is a polymer having repeating units represented by formula (1) in the molecule.

[0132] [Chemical Formula 13]

[0133]

[0134] A polymer having a repeating unit represented by Formula (1) in a molecule of component A-5 may have a repeating unit represented by Formula (2) and / or a repeating unit represented by Formula (3). When a polymer having a repeating unit represented by Formula (1) in a molecule of component A-5 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 a molecule may be a block copolymer or a random copolymer.

[0135] [Chemical Formula 14]

[0136]

[0137] The weight average molecular weight of the polymer having repeating units represented by Formula (1) among the molecules of component A-5 is preferably 1,200 to 40,000, and more preferably 1,200 to 35,000. The weight average molecular weight (Mw) is a value calculated based on the molecular weight of standard polystyrene using data measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.

[0138] As a polymer having a structural unit represented by Formula (1) among the molecules in component A-5, commercial products may be used. Examples of commercial products include ODV-XET-X03 (manufactured by Nittetsu Chemical & Material Co.), ODV-XET-X04 (manufactured by Nittetsu Chemical & Material Co.), ODV-XET-X05 (manufactured by Nittetsu Chemical & Material Co.), etc.

[0139] (Organic solvent)

[0140] Organic solvents are not particularly limited, but examples include amide, ether, ester, aliphatic hydrocarbon, aromatic hydrocarbon, ketone, and organic halogen compound systems.

[0141] Examples of amide-based organic solvents include N,N-dimethylformamide (DMF) and N,N-dimethylacetamide; ether-based organic solvents include diethyl ether, dipropyl ether, dibutyl ether, diamyl ether, and tetrahydrofuran; 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; aliphatic hydrocarbon-based organic solvents include normal hexane, normal heptane, and cyclohexane; aromatic hydrocarbon-based organic solvents include toluene and xylene; ketone-based organic solvents include methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; organic halide-based organic solvents include trichloroethane and trichloroethylene; and the like. Furthermore, relatively inert organic solvents such as propylene glycol monomethyl ether or propylene glycol monoethyl ether can also be used.

[0142] (Crosslinking agent)

[0143] Examples of crosslinking agents are not particularly limited, but include polyfunctional vinyl compounds such as divinylbenzene, divinylnaphthalene, or divinylbiphenyl; vinylbenzyl ether compounds synthesized from the reaction of phenol and vinylbenzyl chloride; styrene monomers; allyl ether compounds synthesized from the reaction of phenol and allyl chloride; trialalkenyl isocyanurates such as trialyl isocyanurate (TAIC (registered trademark)) and trialyl cyanurate (TAC); (meth)acrylate compounds (methacrylate compounds and acrylate compounds) such as trimethylolpropane; and compounds having an acenaphthylene backbone. Using these crosslinking agents can increase heat resistance. Only one type of crosslinking agent may be used, or two or more types may be used.

[0144] Compounds having the above acenaphtylene skeleton include acenaphtylene; hydroxyacenaphtylene compounds such as 3-hydroxyacenaphtylene, 4-hydroxyacenaphtylene, 5-hydroxyacenaphtylene, and 5,6-dihydroxyacenaphtylene; Alkyl acenaphtylene compounds such as 3-methylacenaphtylene, 3-ethylacenaphtylene, 3-propylacenaphtylene, 4-methylacenaphtylene, 4-ethylacenaphtylene, 4-propylacenaphtylene, 5-methylacenaphtylene, 5-ethylacenaphtylene, 5-propylacenaphtylene, 3,8-dimethylacenaphtylene, 5,6-dimethylacenaphtylene, 3-methoxyacenaphtylene, 3-ethoxyacenaphtylene, 3-butoxyacenaphtylene, 4-methoxyacenaphtylene, 4-ethoxyacenaphtylene, 4-butoxyacenaphtylene, 5-methoxyacenaphtylene, 5-ethoxyacenaphtylene, 5-ethoxyacenaphtylene, 5-butoxyacenaphtylene, etc. Examples include alkoxyacenaphtylene compounds; acenaphtylene halogenated compounds such as 3-chloroacenaphtylene, 3-bromoacenaphtylene, 4-chloroacenaphtylene, 4-bromoacenaphtylene, 5-chloroacenaphtylene, and 5-bromoacenaphtylene.

[0145] (Thermoplastic resin)

[0146] Thermoplastic resins are not particularly limited, but include, for example, 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, fluoropolymer, etc., or known thermoplastic elastomers, for example, styrene-ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene Examples include copolymers, styrene-isoprene copolymers, hydrogenated styrene-butadiene copolymers, hydrogenated styrene-isoprene copolymers, (meth)acrylonitrile-butadiene-(meth)acrylic acid copolymers, (meth)acrylonitrile-butadiene-methyl (meth)acrylate copolymers, methyl (meth)acrylate-butadiene-styrene copolymers (MBS), and (meth)acrylonitrile-butadiene rubber (NBR), linear polyurethanes, polybutadiene, polyisoprene, fluororubber, ethylene-propylene-diene rubber, etc.

[0147] (Weapon filler)

[0148] The materials for the inorganic filler are not particularly limited, but examples include 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 zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferred. In addition, spherical silica is preferred as the silica. The inorganic filler may be used as a single type or in combination of two or more types.

[0149] It is preferable that the inorganic filler be treated with one or more surface treatment agents, such as aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazanes, titanate coupling agents, vinylsilane coupling agents, methacryloxysilane coupling agents, acryloxysilane coupling agents, and styrylsilane coupling agents.

[0150] (Organic filler)

[0151] Organic fillers are not particularly limited, but examples include rubber particles, fluoropolymer particles (fluorinated polymer particles), polyamide microparticles, silicone particles, etc.

[0152] As for the rubber particles, commercially available products may be used, for example, “EXL-2655” manufactured by Dow Chemical Japan Co., Ltd., and “AC3816N” manufactured by Aika Industry Co., Ltd.

[0153] Examples of fluoropolymer particles (fluorine-based polymer particles) include polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylenepropene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene perfluorodioxol copolymer (TFE / PDD), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF), etc. These resins may be used individually or in combination of two or more types.

[0154] As for the fluoropolymer particles (fluorine-based polymer particles), commercially available products may be used, for example, "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., "FluonPTFE L-172JE" manufactured by Asahi Glass Co., Ltd., "FluonPTFE L-173JE" manufactured by Asahi Glass Co., Ltd., "KTL-500F" manufactured by Kitamura Corp., "KTL-2N" manufactured by Kitamura Corp., "KTL-1N" manufactured by Kitamura Corp., and "TLP10F-1" manufactured by Mitsui DuPont Fluorochemicals Co., Ltd.

[0155] Inorganic and organic fillers may include surface-treated particles. Surface treatment may include, for example, surface treatment with a surface treatment agent. The surface treatment agent is not particularly limited. In addition to surfactants such as nonionic surfactants, amphoteric surfactants, cationic surfactants, and anionic surfactants, surface treatment agents may also include inorganic fine particles. From the perspective of affinity, it is preferable to use a fluorine-based surfactant as the surface treatment agent. Specific examples of fluorine-based surfactants include "Suplon (registered trademark) S-243" (perfluoroalkyl ethylene oxide adduct) manufactured by AGC Seimi Chemical Co., Ltd., "Megapac (registered trademark) F-251" manufactured by DIC Co., Ltd., "Megapac F-477" manufactured by DIC Co., Ltd., "Megapac F-553" manufactured by DIC Co., Ltd., "Megapac R-40" manufactured by DIC Co., Ltd., "Megapac R-43" manufactured by DIC Co., Ltd., "Megapac R-94" manufactured by DIC Co., Ltd., "FTX-218" manufactured by Neos Co., Ltd., "Ptergent (registered trademark) 610FM" manufactured by Neos Co., Ltd., and "Ptergent 730LM" manufactured by Neos Co., Ltd.

[0156] (Flame retardant)

[0157] Flame retardants are not particularly limited, but examples include halogen-based flame retardants, phosphorus-based flame retardants, etc.

[0158] Examples of halogen-based flame retardants include ethylene-dipentabromozane, ethylene-bis-tetrabromoimide, decabromodiphenyl oxide, tetradecabromodiphenoxybenzene, etc., which have a melting point of 300°C or higher.

[0159] 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 phosphinate salts of dialkylphosphinate aluminum salts.

[0160] Each of the flame retardants exemplified may be used individually, or two or more may be used in combination.

[0161] (Other additives)

[0162] Other additives include, for example, defoaming agents such as silicone-based defoaming agents and acrylic acid ester-based defoaming agents; organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds; adhesion aids such as leveling agents and silane coupling agents; tackifiers such as heat stabilizers, antistatic agents, preservation stabilizers such as BHT; antioxidants, light stabilizers, UV absorbers, dyes or pigments, lubricants, wetting dispersants, heavy metal inactivators, ion traps, emulsifiers, water dispersion stabilizers, release agents, waxes, rheology control agents, surfactants, etc.

[0163] (Varnish)

[0164] When manufacturing the sheet-like laminated material described below, the resin composition of the present invention can be adjusted onto a varnish to form a resin varnish.

[0165] Resin varnish is prepared, for example, as follows.

[0166] Each component is added to an organic solvent and dissolved. At this time, heating may be performed if necessary. Afterwards, if necessary, a component that is not soluble in organic solvents, such as an inorganic filler, is added, and the resin varnish is prepared by dispersing it using a ball mill, bead mill, planetary mixer, roll mill, etc.

[0167] <Sheet-based laminated material>

[0168] The resin composition of the present invention can be used in sheet-like laminated materials. Examples of sheet-like laminated materials include prepregs, adhesive films, metal foils attached to thermosetting resin compositions, etc., as described below.

[0169] <Prefrag>

[0170] The prepreg of the present invention is characterized by having the resin composition of the present invention impregnated into a substrate.

[0171] Examples of substrates include fibrous substrates such as glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, and lint paper. The thickness of the substrate is not particularly limited, but is preferably 20 to 800 μm, and more preferably 20 to 300 μm.

[0172] The prepreg of the present invention can be manufactured by known methods. For example, a method of impregnating a substrate with the resin composition of the present invention and then drying it may be used.

[0173] A prepreg in a semi-cured state (Stage B) can be obtained by heating a substrate impregnated with a resin composition under desired heating conditions, for example, at 80 to 170°C for 1 to 10 minutes to remove the solvent.

[0174] <Adhesive Film>

[0175] 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 manufactured by a known method. For example, it can be manufactured by applying the resin composition of the present invention to a support film using a die coater, etc., and then forming a resin composition layer by drying an organic solvent by heating or hot air spraying, etc.

[0176] Although the drying conditions are not particularly limited, the resin composition layer is dried such that the content of the organic solvent is 10% by weight or less, preferably 5% by weight or less. 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.

[0177] The thickness of the resin composition layer formed in the adhesive film is not particularly limited, but is preferably 5 to 200 μm. From the perspective of thin film formation, 15 to 80 μm is more preferable.

[0178] Examples of support films include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride; polyester films such as polyethylene terephthalate (hereinafter abbreviated as "PET") and polyethylene naphthalate; polycarbonate films; and various plastic films such as polyimide films. Additionally, release paper or metal foils such as copper foil and aluminum foil may be used. Among these, plastic films are preferred for their versatility, and polyethylene terephthalate films are more preferred. Surface treatments such as matte treatment and corona treatment may be performed on the support and the protective film described below. Additionally, release treatment may be performed using release agents such as silicone resin-based release agents, alkyd resin-based release agents, and fluoropolymer-based release agents.

[0179] The thickness of the support film is not particularly limited, but 10 to 150 μm is preferred, and 25 to 50 μm is more preferred.

[0180] On the surface of the resin composition layer where the support is not in close contact, a protective film equivalent to the support may be additionally laminated. The thickness of the protective film is not particularly limited, but, for example, 1 to 40 μm. By laminating the protective film, the adhesion of dust or the like, or scratches on the surface of the resin composition layer, can be prevented. The adhesive film may also be wound into a roll and stored.

[0181] <Metal foil attached to resin composition>

[0182] The metal foil attached to the resin composition of the present invention is characterized by having a resin composition layer containing the resin composition of the present invention on the metal foil. Examples of metal foils used here include copper foil, aluminum foil, etc. The thickness is not particularly limited, but is preferably in the range of 3 to 200 μm, more preferably 5 to 105 μm.

[0183] The method for manufacturing the metal foil with the resin composition attached according to the present invention is not particularly limited, and for example, a method may be used in which the resin composition is uniformly dissolved or dispersed in a solvent such as an aromatic or ketone-based solvent, or a mixture thereof, and then applied to the metal foil and dried. The application may be repeated multiple times as needed, and at this time, it is also possible to repeat the application using multiple solutions with different compositions or concentrations to finally adjust the resin composition and amount to a desired state.

[0184] The thickness of the resin composition layer formed in the metal foil attached to the resin composition of the present invention is not particularly limited, but is preferably 5 to 200 μm.

[0185] The metal foil attached to the resin composition of the present invention may have a release film on the surface where the metal foil of the layer of the resin composition is not in close contact. As the release film, for example, a resin film having polyolefins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate and polyethylene naphthalate; polyimide; polycarbonate, etc. as main components may be used. The peel strength may be adjusted by applying a silicone resin release agent, etc., to the surface thereof.

[0186] 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.

[0187] The release film may have a matte finish, corona finish, or antistatic finish applied to the surface in contact with the resin sheet.

[0188] <Laminated Material>

[0189] 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 herein include copper foil, aluminum foil, etc. The thickness is not particularly limited, but is in the range of 3 to 200 μm, more preferably 5 to 105 μm.

[0190] The method for manufacturing the laminate of the present invention is not particularly limited, but, for example, may be 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 according to the purpose, and the layers are bonded together under heat and pressure while simultaneously heat-curing. 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 a surface layer or as an intermediate layer. In addition to the above, it is also possible to form a multilayer structure by repeating the lamination and curing multiple times.

[0191] The following describes embodiments of the present invention, but the technical scope of the present invention is not limited to these embodiments.

[0192] Examples

[0193] <Weight Average Molecular Weight (Mw) and Degree of Dispersion (Mw / Mn)>

[0194] The weight-average molecular weight of the polymer obtained in the example was measured using the following apparatus and conditions.

[0195] [device]

[0196] Sample Injection Device: Waters 2695 Alliance

[0197] Separation Columns: ShodexKF-G, 803, 802, 801

[0198] Detector: Waters 2414 Parallax Refraction (RI) Detector

[0199] 2998 Photodiode Array (PDA) Detector

[0200] Column Oven: Waters Inc. manufactured column oven

[0201] [condition]

[0202] Column oven temperature: 40 ℃

[0203] RI detector temperature: 40 ℃

[0204] Mobile phase: Tetrahydrofuran

[0205] Flow rate: 1.0 mL / min

[0206] Standard injection volume: 40 μL

[0207] PDA detector extracted wave: 254.0 nm

[0208] Quantitative Calculation: Standard Polystyrene Conversion

[0209] (Example 1) Method for manufacturing polybutadiene A

[0210] 607 g of cyclopentylmethyl ether and 44 g of n-butyllithium (14.7 wt% concentration hexane solution) were added to a reaction vessel. The temperature of the reaction vessel was set to 0 °C, 100 g of 1,3-butadiene was added dropwise, and the mixture was stirred for 30 minutes to obtain a polymerization solution. At room temperature, the polymerization solution was added dropwise to a cyclopentylmethyl ether solution of triphenylphosphate (the amount of triphenylphosphate in the solution is 67 g) and stirred for 20 minutes to obtain a reaction solution. 400 g of 3% acetic acid water was added to the reaction solution and the mixture was separated. After washing the obtained organic layer twice with water, the solvent was distilled off using an evaporator until the solid content of the organic layer reached 50%. Polybutadiene A was obtained by adding 4 L of methanol dropwise to the organic layer, precipitating the polymer, decanting the supernatant, and drying it using an oven.

[0211] The obtained polybutadiene A was analyzed by gel permeation chromatography (mobile phase THF, polystyrene standard), and 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 polybutadiene A calculated by H-NMR was 78 mol%. Using ICP-OES (Inductively Coupled Plasma Emission Spectroscopy), it was confirmed that a phosphorus-containing group derived from triphenylphosphate was attached to polybutadiene. From the method, it was estimated that the phosphorus-containing group was attached to the single end of polybutadiene.

[0212] (Example 2) Method for manufacturing polybutadiene B

[0213] Polybutadiene B was prepared in the same manner as in Example 1, except that triphenyl phosphate was changed to tributyl phosphate.

[0214] As a result of analyzing polybutadiene B by gel permeation chromatography (mobile phase THF, 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 polybutadiene calculated by H-NMR was 78 mol%. Using ICP-OES, it was confirmed that a phosphorus-containing group derived from tributylphosphate was attached to polybutadiene. From the method, it was estimated that the phosphorus-containing group was attached to the single-terminal end of polybutadiene.

[0215] (Example 3) Method for manufacturing polybutadiene C

[0216] Polybutadiene C was prepared in the same manner as in Example 1, except that triphenylphosphate was changed to chlorodiphenylphosphine oxide.

[0217] As a result of analyzing polybutadiene C by gel permeation chromatography (mobile phase THF, 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 polybutadiene calculated by H-NMR was 78 mol%. Using ICP-OES, it was confirmed that a phosphorus-containing group derived from chlorodiphenylphosphine oxide was attached to polybutadiene. From the method, it was estimated that the phosphorus-containing group was attached to the single-terminal end of polybutadiene.

[0218] (Example 4) Method for manufacturing polybutadiene D

[0219] Polybutadiene D was prepared in the same manner as in Example 1, except that triphenylphosphate was changed to tris(2-ethylhexyl)phosphate.

[0220] As a result of analyzing polybutadiene D by gel permeation chromatography (mobile phase THF, polystyrene standard), it was confirmed that the weight-average molecular weight (Mw) was 2,000 and the molecular weight distribution (Mw / Mn) was 1.09. 1 The 1,2 bond structure in polybutadiene calculated by H-NMR was 76 mol%. Using ICP-OES, it was confirmed that a phosphorus-containing group derived from tris(2-ethylhexyl)phosphate was attached to polybutadiene. From the method, it was estimated that the phosphorus-containing group was attached to the single-terminal end of polybutadiene.

[0221] (Example 5) Method for preparing polybutadiene E

[0222] Polybutadiene E was prepared in the same manner as in Example 1, except that triphenyl phosphate was changed to tricrezil phosphate.

[0223] As a result of analyzing polybutadiene E by gel permeation chromatography (mobile phase THF, polystyrene standard), it was confirmed that the weight-average molecular weight (Mw) was 2,300 and the molecular weight distribution (Mw / Mn) was 1.21. 1 The 1,2 bond structure in polybutadiene calculated by H-NMR was 77 mol%. Using ICP-OES, it was confirmed that a phosphorus-containing group derived from tricrezyl phosphate was attached to polybutadiene. From the method, it was estimated that the phosphorus-containing group was attached to the single-terminal end of polybutadiene.

[0224] (Example 6) Method for preparing a cured product

[0225] Each reagent was mixed according to the compositions (parts by weight) of Tables 1 to 3. A cured product was obtained by curing the resin composition by heat pressing at 200°C for 120 minutes.

[0226]

[0227] · B-3000: Liquid polybutadiene manufactured by Soda Corporation, Japan

[0228] · Percumyl D: Dicumyl peroxide manufactured by Nichiyu Co., Ltd.

[0229]

[0230] · SA9000: Methacryl-modified polyphenylene ether compound manufactured by SABIC Innovative Plastics

[0231] · DOPO: Manufactured by Tokyo Kasei Kogyo Co., Ltd. 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide

[0232] · Percumyl D: Dicumyl peroxide manufactured by Nichiyu Co., Ltd.

[0233]

[0234] · SA9000: Methacryl-modified polyphenylene ether compound manufactured by SABIC Innovative Plastics

[0235] · Percumyl D: Dicumyl peroxide manufactured by Nichiyu Co., Ltd.

[0236] (Example 7) Method for manufacturing varnish

[0237] Each reagent was prepared in the composition (parts by weight) of Table 4, and the mixture was stirred and mixed with a mixed solvent of methyl ethyl ketone and cyclohexanone to homogenize it, thereby preparing a varnish of the resin composition.

[0238]

[0239] · SA9000: Methacryl-modified polyphenylene ether compound manufactured by SABIC Innovative Plastics

[0240] · B-1000: Liquid polybutadiene manufactured by Soda Corporation, Japan

[0241] · DOPO: Manufactured by Tokyo Kasei Kogyo Co., Ltd. 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide

[0242] · Percumyl D: Dicumyl peroxide manufactured by Nichiyu Co., Ltd.

[0243] · SC2300-SVJ : Silica filler manufactured by Admatex Co., Ltd.

[0244] (Example 8) Method for manufacturing prepreg

[0245] A prepreg was manufactured by impregnating the above varnish into a glass cloth (manufactured by Nitto Spinning Co., Ltd., #2116 type, WEA116, E glass, thickness 0.1 mm) and then heat-drying it at 100°C for 15 minutes.

[0246] (Example 9) Method for manufacturing a flame-retardant test specimen

[0247] A cured product was obtained by overlapping 10 sheets of the above prepreg and curing them by heat pressing at 200°C for 120 minutes. A flame-retardant test specimen was prepared by cutting a test piece with a length of 125 mm and a width of 13 mm from the cured product.

[0248] (Test Examples 1–6, Reference Example 1 and Reference Example 2)

[0249] The cured product obtained in Example 6 was measured for the following items, and the results are shown in Tables 5 and 6.

[0250] <Relative permittivity (Dk) and dielectric loss tangent (Df)>

[0251] Measurements were performed at 10 GHz using a cylindrical cavity resonator (TE mode resonator) manufactured by ATE Corp.

[0252] <Dielectric loss tangent (Df) after moisture absorption>

[0253] The cured material used in the measurement of the dielectric loss tangent above 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 material was thoroughly wiped off with a dry, clean cloth. The dielectric loss tangent of this moisture-absorbed cured material (dielectric loss tangent after absorption) was measured in the same manner as the measurement of the dielectric loss tangent before the absorption treatment above.

[0254]

[0255]

[0256] According to Test Example 1, it can be seen 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. In addition, regarding the dielectric loss tangent after moisture absorption, it can be seen that the cured product 1 has excellent moisture resistance as it is superior to the reference cured product 1.

[0257] In addition, according to Test Examples 2 to 6, it can be seen that the cured products of polybutadiene A and SA9000 (cured products 4 to 8) have superior electrical properties and moisture resistance compared to the cured product of SA9000 (reference cured product 3).

[0258] (Test Example 7, Reference Examples 3–5) Flame Retardancy Test

[0259] Test specimens were prepared and flame retardancy tests were conducted in accordance with the UL94 standard. Judgment criteria: Based on the UL94 standard. The results are shown in Table 7.

[0260]

[0261] The judgment criteria are as follows.

[0262]

Claims

Claim 1 Polybutadiene is contained, wherein the molar ratio of the 1,2 bond structure and the 1,4 bond structure in the polybutadiene is 60:40 to 100:0, and at one or more carbon atoms in the polybutadiene, formula (III) (In Equation (III), * indicates the joint position, and X 1 and X 2 Each independently represents a single bond or an oxygen atom, and R 1 and R 2 A resin composition for use in an insulating layer of a printed circuit board, wherein a phosphorus-containing group represented by (each independently represents an organic group.) is bonded. Claim 2 A resin composition according to claim 1, additionally containing a polymerization initiator. Claim 3 A resin composition according to claim 1 or 2, wherein the phosphorus-containing group is bonded only to the terminal carbon atom of the polybutadiene. Claim 4 A resin composition according to claim 1 or 2, wherein the weight average molecular weight of the polybutadiene is 1,000 to 8,000. Claim 5 A resin composition according to claim 1 or 2, wherein the molecular weight distribution of the polybutadiene is 1.00 to 3.

00. Claim 6 A prepreg impregnated with the resin composition described in claim 1 or 2. Claim 7 An adhesive film having a resin composition layer containing the resin composition described in claim 1 or 2 on a support film. Claim 8 A metal foil having a resin composition layer containing the resin composition described in claim 1 or 2 on a metal foil. Claim 9 A laminate comprising a layer of a cured resin composition described in claim 1 or 2 and a metal foil. Claim 10 The molar ratio of the 1,2 bond structure and the 1,4 bond structure in the polybutadiene is 60:40 to 100:0, and only the terminal carbon atoms in the polybutadiene, Formula (III) (In Equation (III), * indicates the joint position, and X 1 and X 2 Each independently represents a single bond or an oxygen atom, and R 1 and R 2 Polybutadiene having a phosphorus-containing group bonded thereto, represented by (each independently representing an organic group). Claim 11 A process of anionic polymerization of 1,3-butadiene in the presence of a solvent and an anionic initiator, and after the process, Formula (IV) (In Equation (IV), X 1 , X 2 , R 1 and R 2 is identical to the definition in Equation (III), and X 3 silver, halogenogroup, or formula "-OR" 3 Represents the energy represented by 」, and R 3 A method for producing polybutadiene as described in claim 10, comprising a process of reacting a compound represented by (which represents an organic group).

Images