Resin composition, dry film and cured product

Abstract

[Problem] To provide a resin composition, a dry film, and a cured product which have excellent film-forming properties and are capable of suppressing plating expansion while maintaining low dielectric characteristics and a low coefficient of thermal expansion. [Solution] The resin composition contains (A) a branched polyphenylene ether, (B) a curing agent component having two or more styrenic double bonds and having a molecular weight of 2500 or less, (C) a radical polymerization initiator, and (D) a filler.

Description

Technical Field

[0001] The present invention relates to a resin composition, a dry film and a cured product. Background Art

[0002] In recent years, with the widespread use of high-capacity, high-speed communications represented by the fifth-generation communication system (5G) and millimeter-wave radar for automotive ADAS (Advanced Driver Assistance Systems), the frequency of signals in electronic devices has been increasing.

[0003] In the printed wiring substrate built into such electronic devices, a curable resin composition with epoxy resin as a main component is used as an interlayer insulating material. The relative dielectric constant (Dk) and dielectric tangent (Df) of the cured product formed by the composition are high, which increases the signal transmission loss in the high-frequency band, resulting in problems such as signal attenuation and heating. Therefore, polyphenylene ether with excellent low dielectric properties has attracted attention.

[0004] For example, Patent Document 1 proposes a curable composition containing polyphenylene ether that improves film-forming properties of the composition by incorporating silica into the curable composition and exhibits excellent low dielectric properties and low thermal expansion coefficient.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2021-54974 Summary of the Invention

[0008] Problems to be solved by the present invention

[0009] However, the technology of Patent Document 1 contains a high proportion of silica in the curable composition, which easily causes the silica to fall off at the interface between the plating and the insulating (cured) layer, resulting in low plating adhesion and the problem of plating expansion (swelling). Plating expansion refers to the phenomenon in which a portion of the insulating layer separates from the substrate during the plating process.

[0010] Therefore, the technical problem to be solved by the present invention is to provide a resin composition that has excellent film-forming properties and can suppress plating expansion while maintaining low dielectric properties and a low thermal expansion coefficient; a dry film having a resin layer formed from the resin composition; and a cured product obtained using the resin layer of the dry film.

[0011] Means of solving the problem

[0012] One embodiment of the present invention is a resin composition comprising: (A) a branched polyphenylene ether; (B) a curing agent component; (C) a free radical polymerization initiator; and (D) a filler, wherein the curing agent component (B) has two or more styrenic double bonds and a molecular weight of 2500 or less.

[0013] In the resin composition of the above embodiment, preferably, the (B) curing agent component has two or more styrenic double bonds, and the molecular weight of the (B) curing agent component is 200 to 1500.

[0014] In the resin composition of the above embodiment, preferably, the (B) curing agent component has two styrenic double bonds, and the molecular weight of the (B) curing agent component is 200 to 1500.

[0015] In the resin composition of the above embodiment, preferably, the curing agent component (B) is a compound represented by the following chemical formula (1):

[0016] Chemical formula (1)

[0017]

[0018] In the chemical formula (1), n ​​is an integer of 1 to 10.

[0019] Another embodiment of the present invention is a dry film having a resin layer formed from the resin composition of the above embodiment.

[0020] Another embodiment of the present invention is a cured product obtained by using the resin composition of the above embodiment or the resin layer of the dry film of the above embodiment.

[0021] In the cured product of the above embodiment, it is preferable that the cured product is obtained by curing the resin composition or the resin layer in an air atmosphere.

[0022] Effects of the Invention

[0023] The present invention provides a resin composition having excellent film-forming properties and capable of suppressing plating expansion while maintaining low dielectric properties and a low thermal expansion coefficient; a dry film having a resin layer formed from the resin composition; and a cured product obtained using the resin layer of the dry film. DETAILED DESCRIPTION

[0024] Hereinafter, embodiments of the present invention will be described in detail. In addition, in this specification, the expression "a to b" in the description of a numerical range means a or more and b or less unless otherwise specified.

[0025] In the case where isomers exist for the described compounds, all possible isomers are contemplated for use in the present invention unless otherwise stated.

[0026] In this specification, phenols used as raw materials of polyphenylene ether (PPE) and capable of becoming constituent units of polyphenylene ether are collectively referred to as "raw material phenols."

[0027] In the present specification, when describing the raw material phenols, when referring to the "ortho position" or "para position" or the like, unless otherwise specified, the position of the phenolic hydroxyl group is used as the reference (proper position).

[0028] In this specification, when simply expressed as "ortho position" etc., it means "at least one of the ortho position" etc. Therefore, as long as no particular contradiction arises, when simply expressed as "ortho position", it can be interpreted as indicating either one of the ortho positions, and can also be interpreted as indicating both ortho positions.

[0029] In this specification, polyphenylene ether in which some or all of its functional groups (e.g., hydroxyl groups) are modified may be simply referred to as "polyphenylene ether." Therefore, when referred to as "polyphenylene ether," both unmodified and modified polyphenylene ethers are included unless there is any particular contradiction.

[0030] In this specification, monohydric phenols are mainly disclosed as raw material phenols, but polyhydric phenols may also be used as raw material phenols within a range not hindering the effects of the present invention.

[0031] In this specification, when the upper limit and the lower limit of a numerical range are described separately, all combinations of the lower limit and the upper limit are substantially described within the range that does not conflict.

[0032] In this specification, the solid content is used to mean a non-volatile component (components other than volatile components such as a solvent).

[0033] In this specification, the components contained in the resin composition and the components contained in the dried coating film of the resin composition, that is, the resin layer, are sometimes described without distinction.

[0034] The weight average molecular weight (number average molecular weight) can be measured using a known measurement method, for example, as a polystyrene-equivalent molecular weight using gel permeation chromatography (GPC).

[0035] 1. Resin composition

[0036] The resin composition of this embodiment comprises: (A) a branched polyphenylene ether; (B) a curing agent; (C) a radical polymerization initiator; and (D) a filler. The resin composition may also contain other components as long as they do not impair the effects of the present invention. Each component is described below.

[0037] 1-1. (A) Branched polyphenylene ether (branched PPE)

[0038] The branched polyphenylene ether (A) of the present embodiment is obtained from raw material phenols, and the raw material phenols include phenols that at least satisfy the following conditions.

[0039] (condition)

[0040] There are hydrogen atoms at the ortho and para positions.

[0041] Since phenols meeting the above conditions have hydrogen atoms at the ortho position, ether bonds can be formed not only at the ortho and para positions but also at the ortho position during oxidative polymerization with phenols. Therefore, polyphenylene ethers obtained using these phenols as raw material phenols can have a branched structure. Specifically, the branched polyphenylene ether (A) has a structure in which a portion of the structure is branched via ether-bonded benzene rings at at least three positions: the ortho, ortho, and para positions.

[0042] (A) Branched polyphenylene ethers include, for example, polyphenylene ethers disclosed in International Publication No. 2020 / 017570.

[0043] (A) Branched polyphenylene ether can be obtained by either (method 1) synthesizing polyphenylene ether using a phenol containing a functional group having an unsaturated carbon bond as a raw material phenol, or (method 2) synthesizing polyphenylene ether using a phenol not containing a functional group having an unsaturated carbon bond as a raw material phenol, modifying the obtained polyphenylene ether, and introducing a functional group having an unsaturated carbon bond into the polyphenylene ether.

[0044] The branched polyphenylene ether (A) of the present embodiment may be a mixture of two or more polyphenylene ethers having different kinds of raw material phenols. In addition, other phenols that do not satisfy the above conditions may be included within a range that does not inhibit the effects of the present invention.

[0045] (A) branched polyphenylene ether of the present embodiment has the functional group comprising unsaturated carbon bond.Unsaturated carbon bond represents multiple bonds (double bonds or triple bonds) between the carbons of olefinic or acetylenic bonds.As the functional group with unsaturated carbon bond, it is not particularly limited, preferably alkenyl (such as vinyl, allyl), alkynyl (such as ethynyl) or (methyl) acryloyl, from the viewpoint of excellent curability, more preferably vinyl, allyl, (methyl) acryloyl, from the viewpoint of excellent low dielectric properties, more preferably allyl.In addition, the carbon number of these functional groups with unsaturated carbon bond can be, for example, less than 15, less than 10, less than 8, less than 5, less than 3, etc.

[0046] The equivalent weight of the functional group having an unsaturated carbon bond in the branched polyphenylene ether (A) of the present embodiment can be appropriately changed depending on the curability and application of the resin composition.

[0047] The weight average molecular weight (Mw) of the branched polyphenylene ether (A) of the present embodiment is preferably 1,000 or more, 1,500 or more, 2,000 or more, and is preferably 150,000 or less, 100,000 or less, 80,000 or less, etc.

[0048] The polydispersity index {PDI: weight average molecular weight (Mw) / number average molecular weight (Mn)} of the branched polyphenylene ether (A) of the present embodiment is preferably 1.5 to 20.

[0049] The amount of the branched polyphenylene ether (A) added in this embodiment is preferably 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, etc., based on the total solid content of the resin composition, and is preferably 60% by mass or less, 50% by mass or less, 45% by mass or less, etc.

[0050] 1-2. (B) Curing agent component

[0051] The (B) curing agent component of the present embodiment has two or more styrenic double bonds. Since the (B) curing agent component has two or more styrenic double bonds, its affinity with the (A) branched polyphenylene ether is relatively high, and a curing reaction is easily carried out, thereby obtaining a resin composition having low dielectric properties and excellent low thermal expansion coefficient.

[0052] The molecular weight (number average molecular weight) of the curing agent component (B) of this embodiment is 2500 or less. By setting the molecular weight of the curing agent component (B) to 2500 or less, the molecular chain has an appropriate length, and the fluidity of the resin composition can be improved.

[0053] The curing agent component (B) of this embodiment is not limited as long as it has two or more styrenic double bonds, and known substances can be used. It is preferred that the number of styrenic double bonds is 2 to 4, and more preferably 2. For example, the compound represented by the following chemical formula (1), divinylfluorene, divinylbiphenyl, divinylnaphthalene, divinylbenzene, and oligophenyl ether compounds containing terminal styrene can be listed. Among them, the compound represented by the following chemical formula (1) is more preferred.

[0054] Chemical formula (1)

[0055]

[0056] (In chemical formula (1), n ​​is an integer from 1 to 10.)

[0057] In the above chemical formula (1), n ​​is preferably an integer of 1 to 10, more preferably an integer of 1 to 8, and even more preferably an integer of 1 to 5. From the viewpoint of the fluidity of the resin composition, n is particularly preferably 2. In the above chemical formula (1), the compound {1,2-bis(vinylphenyl)ethane (BVPE)} wherein n is 2 is represented by the following chemical formula (2). The curing agent component (B) of this embodiment may be used alone or in combination of multiple types.

[0058] Chemical formula (2)

[0059]

[0060] The molecular weight of (B) curing agent component of present embodiment is preferably below 2500, below 2000, below 1500 etc.In addition, be preferably more than 100, more than 150, more than 200 etc.If the molecular weight of curing agent component is within the above-mentioned scope, then can suppress the volatilization of (B) curing agent component, improve the fluidity of resin combination simultaneously.In addition, in the manufacturing process (during heat curing) of solidified material described later, can suppress film thickness to reduce (film deviation).

[0061] The amount of the curing agent component (B) added in this embodiment is based on the total solid content of the resin composition, for example, preferably 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 3% by mass or more, etc., and preferably 40% by mass or less, 30% by mass or less, 25% by mass or less, etc.

[0062] In this embodiment, the mixing ratio of the (B) curing agent component to 100 parts by mass of the (A) branched PPE is preferably 1 part by mass or more, 10 parts by mass or more, etc., and preferably 67 parts by mass or less, 55 parts by mass or less, etc. By adjusting the mixing ratio of the (A) branched PPE to the (B) curing agent component within the above range, a resin composition capable of suppressing plating expansion while maintaining low dielectric properties and a low thermal expansion coefficient can be obtained.

[0063] 1-3. (C) Radical Polymerization Initiator

[0064] The (C) radical polymerization initiator of the present embodiment is a compound that generates active species (also referred to as free radicals) by heat or ultraviolet light, causing the radical polymerizable monomer to undergo a polymerization reaction, thereby easily forming a polymer. As long as it does not hinder the effect of the invention, the (C) radical polymerization initiator is not particularly limited, and a photoradical polymerization initiator, a thermal radical polymerization initiator, etc. can be used. The radical polymerization initiator can be used alone or in combination of two or more. Below, the radical polymerization initiator is described in detail.

[0065] <Thermal Radical Polymerization Initiator>

[0066] The thermal radical polymerization initiator is not particularly limited, and examples thereof include: azo-based polymerization initiators (e.g., 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis(2-methylpropionic acid)dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azobis(2-aminobispropane)dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine)disulfate, 2,2'-azobis(N,N'-dimethylisobutylimide)dihydrochloride, etc.); peroxide-based polymerization initiators (e.g., dibenzoyl peroxide, t-butyl permaleate, lauroyl peroxide, etc.); and redox-based polymerization initiators.

[0067] <Photoradical polymerization initiator>

[0068] There are no particular restrictions on the photoradical polymerization initiator, and examples thereof include benzoin ether-based photopolymerization initiators, acetophenone-based photopolymerization initiators, α-ketol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, photoactive oxime-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators.

[0069] Specific examples of benzoin ether-based photopolymerization initiators include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one [trade name: Omnirad 651, manufactured by Agenmon Resins Co., Ltd.], and aniline.

[0070] Examples of the acetophenone-based photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone [trade name: Omnirad 184, manufactured by Agenmond Resins Co., Ltd.], 4-phenoxydichloroacetophenone, 4-tert-butyldichloroacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one [trade name: Omnirad 2959, manufactured by Agenmond Resins Co., Ltd.], 2-hydroxy-2-methyl-1-phenyl-propane-1-one [trade name: Omnirad 1173, manufactured by Agenmond Resins Co., Ltd.], and methoxyacetophenone.

[0071] Examples of the α-ketol-based photopolymerization initiator include 2-methyl-2-hydroxyacetone and 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methylpropane-1-one.

[0072] Examples of aromatic sulfonyl chloride-based photopolymerization initiators include 2-naphthalenesulfonyl chloride, and examples of photoactive oxime-based photopolymerization initiators include 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime.

[0073] Examples of benzoin-based photopolymerization initiators include benzoin. Examples of benzyl-based photopolymerization initiators include benzyl. Examples of benzophenone-based photopolymerization initiators include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and α-hydroxycyclohexylphenylketone.

[0074] Examples of ketal-based photopolymerization initiators include benzyl dimethyl ketal. Examples of thioxanthone-based photopolymerization initiators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.

[0075] Examples of the acylphosphine oxide-based photopolymerization initiator include bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylpropane-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1-methylpropane-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-tert-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6-dimethoxybenzoyl)octylphosphine oxide, and bis(2-methoxybenzoyl)(2-methylpropane-1-yl)phosphine oxide. Phosphine oxide, bis(2-methoxybenzoyl)(1-methylpropane-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(2-methylpropane-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylpropane-1-yl)phosphine oxide, bis(2,6-dibutoxybenzoyl)(2-methylpropane-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylpropane-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)(2,4-dipentyloxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2- Phenylethylphosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-4-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2 ,3,5,6-tetramethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide, 2,6-dimethoxybenzoyl-2,4,6-trimethylbenzoyl-n-butylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-dibutoxyphenylphosphine oxide, 1,10-bis[bis(2,4,6-trimethylbenzoyl)phosphine oxide]decane, tris(2-methylbenzoyl)phosphine oxide, etc.

[0076] The amount of the radical polymerization initiator (C) added may be 0.01 to 3.0% by mass based on the total solid content of the resin composition.

[0077] 1-4. (D) Filler

[0078] The filler (D) of this embodiment contributes to the adjustment of the physical properties and dielectric constant of the cured product described below. Examples of such fillers (D) include inorganic fillers such as silica, glass fiber, and calcium carbonate, and organic fillers such as PTFE powder.

[0079] <Inorganic filler>

[0080] As inorganic fillers, metal oxides such as aluminum oxide and titanium oxide; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; clay minerals such as talc and mica; fillers having a perovskite crystal structure such as barium titanate and strontium titanate; silicon dioxide, boron nitride, aluminum borate, barium sulfate, calcium carbonate, etc. can be used.

[0081] Among the above-mentioned inorganic fillers, silica improves the film-forming properties of the resin composition and can achieve a high level of low dielectric tangent and low thermal expansion.

[0082] The average particle size of silica is preferably 0.02 to 10 μm, more preferably 0.02 to 3 μm. The average particle size can be determined using a commercially available laser diffraction / scattering particle size distribution measuring apparatus, using the measured values ​​of the particle size distribution obtained by the laser diffraction / scattering method, and using the cumulative distribution as the median diameter (d50, volume basis). The average particle size of silica refers to the value measured as described above for the powdered material before the resin composition is modulated (pre-stirred, mixed).

[0083] Silica having different average particle sizes may be used together. For example, from the perspective of achieving high silica filling, silica having an average particle size of 1 μm or more and nano-scale fine silica having an average particle size of less than 1 μm may be used together.

[0084] Silica can also be surface-treated with a coupling agent. Surface treatment with a silane coupling agent can improve dispersibility with polyphenylene ether and also enhance affinity with organic solvents.

[0085] As silane coupling agents, for example, epoxy silane coupling agents, mercapto silane coupling agents, vinyl silane coupling agents, etc. can be used. As epoxy silane coupling agents, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, etc. can be used. As mercapto silane coupling agents, for example, γ-mercaptopropyltriethoxysilane, etc. can be used. As vinyl silane coupling agents, for example, vinyltriethoxysilane, etc. can be used.

[0086] The amount of the silane coupling agent used may be, for example, 0.1 to 5 parts by mass or 0.5 to 3 parts by mass relative to 100 parts by mass of silica.

[0087] The amount of filler (D) such as silica added can be 30 to 80% by mass based on the total solid content of the resin composition. By setting the amount of filler added within the above range, the warping of the dry film described later can be reduced when the dry film is prepared from the resin composition.

[0088] 1-5. Other ingredients

[0089] As other components, known components may be included, for example: flame retardant enhancers (phosphorus compounds, etc.), cellulose nanofibers, cyanate resins, epoxy resins, phenol-novolac resins, elastomers, dispersants, curing accelerators, cross-linking curing agents (cross-linking agents and cross-linking aids), adhesion imparting agents, solvents and other components.

[0090] <Crosslinking Curing Agent>

[0091] As a cross-linking curing agent (cross-linking agent·cross-linking aid), a substance having good compatibility with polyphenylene ether can be used, such as vinyl benzyl ether compounds synthesized by the reaction of phenol and vinylbenzyl chloride; allyl ether compounds synthesized by the reaction of styrene monomer, phenol and allyl chloride; trienyl isocyanurate, etc.

[0092] More specifically, triallyl isocyanurate having particularly good compatibility with polyphenylene ether is preferred, and specifically triallyl isocyanurate (hereinafter referred to as TAIC (registered trademark)) or triallyl cyanurate (hereinafter referred to as TAC) is preferred. These exhibit low dielectric properties and can improve heat resistance. TAIC (registered trademark) is particularly preferred due to its excellent compatibility with polyphenylene ether. A single cross-linking curing agent may be used, or two or more may be used.

[0093] Since the branched polyphenylene ether (A) of the present embodiment contains a hydrocarbon group having an unsaturated carbon bond, a cured product having excellent low dielectric properties can be obtained by curing it with a cross-linking curing agent.

[0094] The amount of the crosslinking curing agent added may be 3 to 25% by mass based on the total solid content of the resin composition. Within this range, a cured product having excellent low dielectric properties and low thermal expansion coefficient can be obtained.

[0095] Solvents

[0096] The resin composition of the present invention is usually provided or used in a state where the (A) branched polyphenylene ether is dissolved in a solvent.

[0097] As an example of a solvent that can be used in the resin composition of the present embodiment, in addition to conventionally usable solvents such as chloroform, dichloromethane, and toluene, safer solvents such as N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF), cyclohexanone, propylene glycol monomethyl ether acetate (PMA), diethylene glycol monoethyl ether acetate (CA), methyl ethyl ketone, and ethyl acetate can also be cited. The solvent can also be N,N-dimethylformamide (DMF). Only one solvent can be used, or two or more solvents can be used.

[0098] The amount of the solvent added to the resin composition of the present embodiment is not particularly limited and can be appropriately adjusted according to the application of the resin composition.

[0099] 2. Dry film

[0100] The dry film of this embodiment can be produced by coating the resin composition of this embodiment on a first film (e.g., a carrier film) and drying it to form a resin layer as a dry coating film. If necessary, a second film (e.g., a protective film) can be laminated on the resin layer. In other words, the dry film has a resin layer formed from the resin composition.

[0101] The first film is a film that supports the resin layer of the dry film. It is at least the portion that adheres to the resin layer when the dry film is laminated and integrally formed on a substrate such as a substrate by heating or other means. Examples of the first film include films made of thermoplastic resins such as polyester films such as polyethylene terephthalate or polyethylene naphthalate, polyimide films, polyamide-imide films, polyethylene films, polytetrafluoroethylene films, polypropylene films, and polystyrene films, as well as surface-treated paper. Polyester films are preferred for their heat resistance, mechanical strength, and ease of use. The thickness of the first film is not particularly limited and can be appropriately selected within the range of approximately 10 to 150 μm depending on the intended use. The surface of the first film provided with the resin layer may also be subjected to a release treatment. Alternatively, the surface of the first film provided with the resin layer may be sprayed or coated with copper foil.

[0102] The second film is a film provided on the opposite side of the resin layer to the first film for the purpose of preventing dust and the like from adhering to the surface of the resin layer of the dry film and improving operability. When the second film is laminated and integrally formed by contacting the resin layer side of the dry film on a substrate such as a substrate by heating or the like, it is peeled off from the resin layer before lamination. As the second film, for example, films made of the thermoplastic resins exemplified for the first film above, and surface-treated paper, etc. can be used, among which polyester films, polyethylene films, and polypropylene films are preferred. The thickness of the second film is not particularly limited and can be appropriately selected within the range of approximately 10 to 150 μm depending on the intended use. The surface of the second film on which the resin layer is provided can also be subjected to a demolding treatment. In addition, it is preferred that the film has a smaller adhesive force between the resin layer and the second film than between the resin layer and the first film when the second film is peeled off.

[0103] As the film to which the resin composition of the present invention is applied when producing a dry film, either the first film or the second film can be used.

[0104] 3. Cured product

[0105] The cured product of the present embodiment is obtained using the resin composition of the present embodiment or the resin layer of the dry film of the present embodiment.

[0106] The method for curing is not particularly limited, and can be cured by a conventionally known method, for example, by heating at 150 to 230° C. for curing. The method for obtaining a cured product from a resin composition is not particularly limited, and can be appropriately changed according to the composition of the resin composition. As an example, after the process of applying the resin composition (for example, applying it using a coater, etc.) can be implemented on a circuit substrate having a circuit pattern, a drying process for drying the resin composition can be implemented as needed, and a heat curing process for thermally crosslinking the polyphenylene ether by heating (for example, heating using an inert gas furnace, a hot plate, a vacuum furnace, a vacuum press, etc.) can be implemented. In addition, the conditions for implementation in each process (such as coating thickness, drying temperature and time, heating temperature and time, etc.) can be appropriately changed according to the composition or purpose of the resin composition.

[0107] In addition, when a three-layer dry film with a resin layer sandwiched between a first film and a second film is used to obtain a cured product, a printed wiring board can be manufactured by the following method. The second film is peeled off from the dry film, and after heat lamination on a circuit substrate having a circuit pattern, a heat curing process for heat curing is implemented. The heat curing process can be cured in a furnace or cured by a hot plate press. When the substrate having a circuit and the dry film of the present invention are laminated or hot plate pressed, copper foil or a substrate having a circuit can also be laminated at the same time. At a position corresponding to a prescribed position on the substrate having a circuit pattern, a pattern or through hole is formed by laser irradiation or a drill bit to expose the circuit wiring, thereby enabling the manufacture of a printed wiring board. At this time, when there is a component (smear) that is not completely removed and remains on the circuit wiring in the pattern or through hole, a desmear treatment is performed. The first film can be peeled off at any one of the times after lamination, heat curing, laser processing or desmear treatment.

[0108] [Example]

[0109] Next, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0110] <(A) Synthesis of Branched Polyphenylene Ether>

[0111] 19.8 g (0.16 mol) of 2,6-dimethylphenol and 2.42 g (0.018 mol) of 2-allylphenol were added to a 500 mL separable flask, and the resulting mixture was dissolved in 261 g of toluene. The mixture was further adjusted to 0.18 wt% of di-μ-hydroxy-bis[(N,N,N',N'-tetramethylethylenediamine)copper(II)] chloride (Cu / TMEDA) and 0.16 wt% of tetramethylethylenediamine (TMEDA). Dry air was blown into the reaction solution at a flow rate of 75 mL / min while stirring at 200 rpm using four stirring blades. The mixture was reacted at 40°C for a predetermined time to obtain a reaction solution containing polyphenylene ether. After stopping the heating of the reaction solution and the blowing of dry air, di-μ-hydroxy-bis[(N,N,N',N'-tetramethylethylenediamine)copper(II)] chloride (Cu / TMEDA) was removed by filtration and reprecipitated with a mixture of 1200 mL of methanol, 4.0 mL of concentrated hydrochloric acid, and 27.0 mL of water. The solution was removed by vacuum filtration, washed with methanol, and dried at 80°C for 24 hours to obtain a reactive branched polyphenylene ether. The resulting reactive branched polyphenylene ether (branched PPE) had a number average molecular weight (Mn) of 14,000 and a weight average molecular weight (Mw) of 38,000.

[0112] The number average molecular weight (Mn) and weight average molecular weight (Mw) of branched PPE were determined by gel permeation chromatography (GPC). GPC used a Shodex K-805L column, a column temperature of 40°C, a flow rate of 1 mL / min, chloroform as the eluent, and polystyrene as the standard material.

[0113] <Other Curing Agent Components: Synthesis of Synthetic PPE (Non-branched)>

[0114] 2.28 g of bisphenol A and 100 g of 2,6-dimethylphenol were added to a 500 mL separable flask, and the resulting mixture was dissolved in 261 g of toluene. The mixture was further adjusted to 0.18 wt % of di-μ-hydroxy-bis[(N,N,N',N'-tetramethylethylenediamine)copper(II)] chloride (Cu / TMEDA) and 0.16 wt % of tetramethylethylenediamine (TMEDA). Dry air was blown into the reaction mixture at a flow rate of 75 mL / min while stirring at 200 rpm using four stirring blades. The mixture was reacted at 40°C for a predetermined time to obtain a reaction solution containing polyphenylene ether. After stopping the heating of the reaction solution and the blowing of dry air, di-μ-hydroxy-bis[(N,N,N',N'-tetramethylethylenediamine)copper (II)] chloride (Cu / TMEDA) was removed by filtration, and reprecipitated with a mixed solution of 1200 mL of methanol, 4.0 mL of concentrated hydrochloric acid, and 27.0 mL of water. The product was removed by vacuum filtration, washed with methanol, and dried at 80°C for 24 hours to obtain an unmodified PPE with Mn=10000 (PDI=4) as polyphenylene ether.

[0115] To a 1L two-necked eggplant flask equipped with a dropping funnel, 50g of unmodified PPE, 2.25g of 4-chloromethylstyrene as a modifying compound, 3g of tetrabutylammonium bromide as a phase transfer catalyst, and 500mL of toluene were added and heated with stirring at 75°C. To this solution, 15mL of an 8M aqueous sodium hydroxide solution was added dropwise over 20 minutes. The mixture was then stirred at 75°C for an additional 5 hours. The reaction solution was then neutralized with hydrochloric acid and reprecipitated in 5L of methanol. The solution was removed by filtration, washed three times with a mixture of methanol and water at a mass ratio of 80:20, and dried at 80°C for 24 hours to obtain modified PPE (synthetic PPE). The resulting synthetic PPE was unbranched PPE.

[0116] The number average molecular weight (Mn) of the synthesized PPE was determined by gel permeation chromatography (GPC). GPC used a Shodex K-805L column, a column temperature of 40°C, a flow rate of 1 mL / min, chloroform as the eluent, and polystyrene as the standard substance.

[0117] <Preparation of Resin Composition>

[0118] (Example 1)

[0119] 9.7 g of anisole as a solvent was added to 1.60 g (100 parts by mass) of branched PPE and thoroughly stirred with a rotary / orbital mixer until completely dissolved. To the resulting branched PPE resin solution were added 0.48 g (30 parts by mass) of triallyl isocyanurate (trade name "TAIC" manufactured by Mitsubishi Chemical Corporation), a curing agent component; 0.64 g (40 parts by mass) of BVPE (trade name "1,2-bis(4-vinylphenyl)ethane" manufactured by Shandong Xingshun New Materials Co., Ltd.); and 2.64 g (160 parts by mass) of spherical silica slurry (trade name "SC2050-HNF" manufactured by Yaduma Co., Ltd., solids concentration 70%), and stirred with a rotary / orbital mixer. Finally, 48 mg (3 parts by mass) of α,α′-bis(tert-butylperoxy-m-isopropyl)benzene (trade name “PERBUTYL P40” manufactured by NOF Corporation) was added as a radical polymerization initiator, and the mixture was thoroughly stirred with a rotation / revolution mixer to obtain a varnish of the resin composition of Example 1.

[0120] (Examples 2 to 6, Comparative Examples 1 to 6)

[0121] Varnishes of the resin compositions of Examples 2 to 6 and Comparative Examples 1 to 6 were obtained in the same manner as in Example 1, except that the components and contents were set to the values ​​shown in Table 1 below.

[0122] <Preparation of Test Sample Substrates>

[0123] (CZ-treated substrate production process)

[0124] Both surfaces of a substrate (copper-clad laminate, manufactured by Mitsubishi Gas Chemical Co., Ltd., CCL-HL832NX, TYPE A series, thickness 0.4 mm) were roughened using a roughening agent (manufactured by MAG Corporation: trade name "CZ8100") at an etching amount of approximately 1 μm to produce a CZ-treated substrate.

[0125] (Dry film production process)

[0126] The varnish of the resin composition of each example and comparative example was applied to a high-smoothness grade PET film (manufactured by Toray Industries, Ltd.: trade name "R80") having a thickness of 38 μm as the first film, with an applicator, so that the thickness after drying was 35 μm. The film was then dried in a hot air circulation drying oven at 90°C for 15 minutes to obtain a dry film for the test of each example and comparative example.

[0127] (Lamination / Curing Process)

[0128] The test dry films of each example and comparative example were placed on both sides of the CZ-treated substrate obtained in the above manner, so that they were in contact with the resin layer of the dry film. Lamination was performed using a vacuum laminator ("CVP-600" manufactured by Nippon Mining Materials Co., Ltd.) at 140°C and 0.8 MPa. An inert gas constant temperature oven was then completely filled with nitrogen, the temperature was raised to 200°C, and heat-treated for 60 minutes to cure the cured product. Test substrates having cured products of each resin layer were produced.

[0129] (Desmear process)

[0130] The surfaces of each test substrate were desmeared using a commercially available desmear treatment solution. Specifically, the test substrate, with the first film peeled off, was immersed in a swelling solution (manufactured by Atotech Japan Co., Ltd., trade name "Swelling DipSecuriganth P") at 60°C for 5 minutes, then immersed in a roughening solution (manufactured by Atotech Japan Co., Ltd., trade name "Concentrate Compact CP") at 80°C for 20 minutes, and then immersed in a neutralizing solution (manufactured by Atotech Japan Co., Ltd., trade name "Reduction Securiganth P500") at 40°C for 5 minutes.

[0131] (Plating Layer Forming Step)

[0132] Electroless plating and electrolytic plating were performed on the surface of each test substrate after the desmear process to form a copper plating layer. Specifically, as the electroless plating treatment, the substrate was immersed in a cleaning solution (manufactured by Uemura Industry: trade name “CLEANER MCD-PL”) at 40° C. for 5 minutes, immersed in a soft etching solution (manufactured by Uemura Industry Co., Ltd.: trade name “ALCUP MDP-2”) at 25° C. for 2 minutes, immersed in a catalyst imparting solution (manufactured by Uemura Industry Co., Ltd.: trade name “ALCUP MAT-SP”) at 40° C. for 5 minutes, immersed in a reducing solution (manufactured by Uemura Industry Co., Ltd.: trade name “ALCUP MRD-2-C / MAB-4-C / MAB-4-A”) at 35° C. for 3 minutes, immersed in a reaction treatment accelerating solution (manufactured by Uemura Industry Co., Ltd.: trade name “ALCUP MEL-3-A”) at 25° C. for 1 minute, immersed in an electroless plating solution (manufactured by Uemura Industry Co., Ltd.: trade name “SLCUP PEA”) at 40° C. for 5 minutes, immersed in a reducing solution (manufactured by Uemura Industry Co., Ltd.: trade name “ALCUP MRD-2-C / MAB-4-C / MAB-4-A”) at 35° C. for 3 minutes, immersed in a reaction treatment accelerating solution (manufactured by Uemura Industry Co., Ltd.: trade name “ALCUP MEL-3-A”) at 25° C. for 1 minute, immersed in a catalyst imparting solution (manufactured by Uemura Industry Co., Ltd.: trade name “ALCUP PEA”) at 40° C. for 5 minutes, immersed in a catalyst imparting solution (manufactured by Uemura Industry Co., Ltd.: trade name “ALCUP MAT-SP”) at 40° C. for V2”) at 36°C for 20 minutes to perform electroless copper plating. Thereafter, as an electrolytic plating treatment, the film was immersed in an acid cleaning solution (manufactured by Atotech Japan: trade name "Acid Cleaner FR") at 45°C for 5 minutes, immersed in a 10% sulfuric acid aqueous solution at 25°C for 1 minute, immersed in an electrolytic copper plating solution at 23°C for 60 minutes, and immersed in an electrolytic copper plating solution at a current density of 2 A / dm 2Electrolytic copper plating was performed under the conditions of . Finally, as an annealing treatment, heat treatment was performed at 190° C. for 60 minutes in a hot air circulation dry drying furnace. The test sample substrate was obtained by the above production method.

[0133] <Preparation of Test Cured Film>

[0134] The test dry films of each embodiment and comparative example were laminated at 140°C and 0.8 MPa using a vacuum laminator ("CVP-600" manufactured by Nippon Mining Materials Co., Ltd.) so that the resin layer of the dry film was in contact with a smooth copper foil. Then, an inert oven was completely filled with nitrogen, the temperature was raised to 200°C, and the film was cured by heating for 60 minutes. The first film was peeled off, and the copper foil was etched to obtain a cured film for the test.

[0135] <Evaluation of film-forming properties>

[0136] The test cured films of the respective Examples and Comparative Examples produced in the above-mentioned <Production of Test Cured Films> were observed and evaluated based on the following criteria.

[0137] (Evaluation Criteria)

[0138] A: Cured film is uniform

[0139] C: The cured film is uneven or breaks during copper foil etching

[0140] <Measurement / Evaluation of Coefficient of Thermal Expansion (CTE)>

[0141] The test cured films of each example and comparative example prepared in the "Preparation of Test Cured Films" section were cut to a measurement size (3 mm x 30 mm) and the CTE was measured using a TMA (Thermomechanical Analysis) Q400 manufactured by TA Instruments Japan Ltd. The measurement conditions were: in tension mode, with a chuck spacing of 16 mm, a load of 30 mN, and a nitrogen atmosphere. The temperature was increased from -50°C to 300°C at a rate of 10°C / min, followed by a temperature decrease from 300°C to -50°C at a rate of 10°C / min, and then again increased from -50°C to 300°C at a rate of 10°C / min. During the second temperature increase, the average linear thermal expansion coefficient (CTE) from 50°C to 100°C was obtained.

[0142] (Evaluation Criteria)

[0143] A: CTE (α1) less than 25ppm

[0144] B: CTE (α1) is 25 ppm or more and less than 50 ppm

[0145] C: CTE (α1) is 50 ppm or more

[0146] ―: Unable to measure

[0147] <Measurement and Evaluation of Dielectric Tangent (Df)>

[0148] The test cured films of each example and comparative example produced in the "Preparation of Test Cured Films" section were cut into a measurement size (45 mm x 80 mm) and the dielectric tangent (Df) was measured using the SPDR (Split Post Dielectric Resonator) resonator method. A vector network analyzer E5071C and SPDR resonator manufactured by Deutsche Technik GmbH were used as the measurement instrument, and a program developed by QWED was used for the calculation. The measurement conditions were a frequency of 10 GHz and a temperature of 25°C.

[0149] (Evaluation Criteria)

[0150] A: Df is below 0.0020

[0151] B: Df exceeds 0.0020 and is less than 0.0040

[0152] C: Df is above 0.0040

[0153] ―: Unable to measure

[0154] <Evaluation of plating expansion>

[0155] The surfaces of the test sample substrates of each Example and Comparative Example, produced in the above (plating formation step), after plating, were visually observed to evaluate plating expansion. The ratio of the area of ​​expansion in the plating layer on both sides of the substrate was calculated and evaluated using the following evaluation criteria.

[0156] (Evaluation Criteria)

[0157] A: The area where expansion occurs is less than 5%

[0158] C: The area where expansion occurred is 5% or more -: Unable to measure

[0159]

Table 1

[0160]

[0161]

[0162] The details of each component in Table 1 are as follows. The amount of each component blended is parts by mass and is a value of solid content.

[0163] <(A) Branched PPE>

[0164] *1: The above branched PPE

[0165] <Linear PPE>

[0166] *2: Straight chain PPE {manufactured by Sabic High Performance Materials Japan Co., Ltd.: Trade name "SA9000"}

[0167] <Crosslinking aid>

[0168] *3: Triallyl isocyanurate {Mitsubishi Chemical Corporation: Trade name "TAIC"}

[0169] *4: Trivinylcyclohexane (TVCH) {manufactured by Shandong Xingshun New Materials Co., Ltd.: trade name "1,2,4-trivinylcyclohexane"}

[0170] <(B) Curing Agent Component>

[0171] *5: 1,2-bis(vinylphenyl)ethane (BVPE) {manufactured by Shandong Xingshun New Materials Co., Ltd.: trade name "1,2-bis(4-vinylphenyl)ethane", molecular weight (Mn): 234}

[0172] *6: Divinylbenzene {manufactured by Nippon Steel Chemicals & Materials Co., Ltd.: trade name "divinylbenzene", molecular weight (Mn): 130}

[0173] *7: Styrene-terminated oligophenylene ether compound {Mitsubishi Gas Chemical Co., Ltd.: trade name "OPE-2St-1200", molecular weight (Mn): 1200}

[0174] *8: Styrene-terminated oligophenylene ether compound {Mitsubishi Gas Chemical Co., Ltd.: Trade name "OPE-2St-2200", molecular weight (Mn): 2200}

[0175] <Other curing agent ingredients>

[0176] *9: The above-mentioned synthetic PPE {molecular weight (Mn): 10000}

[0177] <Elastomer>

[0178] *10: Elastomer {Asahi Kasei Corporation: Trade name "Tuftec H1051"}

[0179] <(C) Radical Polymerization Initiator>

[0180] *11: α,α'-bis(tert-butylperoxy-m-isopropyl)benzene {manufactured by NOF Corporation: trade name "PERBUTYL P40"}

[0181] (D) Filler

[0182] *12: Silica slurry, solid content 70% by mass, dispersion medium cyclohexanone {manufactured by Yaduma Co., Ltd.: trade name "SC2050-HNF"}

[0183] Industrial applicability

[0184] The resin composition, dry film, and cured product of the present invention have excellent film-forming properties while maintaining low dielectric properties and low thermal expansion coefficient, and can suppress plating expansion. Therefore, they can be used as interlayer insulation materials for printed wiring boards built into electronic devices.

Claims

1. A resin composition, characterized in that Include: (A) branched polyphenylene ether; (B) a curing agent component; (C) a free radical polymerization initiator; (D) filler, The (B) curing agent component has two or more styrenic double bonds and a molecular weight of 2500 or less.

2. The resin composition according to claim 1, wherein The (B) curing agent component has two or more styrenic double bonds, and the molecular weight of the (B) curing agent component is 200 to 1500.

3. The resin composition according to claim 1, wherein The (B) curing agent component has two styrenic double bonds, and the molecular weight of the (B) curing agent component is 200 to 1500.

4. The resin composition according to claim 1, wherein The curing agent component (B) is a compound represented by the following chemical formula (1): Chemical formula (1) In the chemical formula (1), n ​​is an integer of 1 to 10.

5. A dry film, characterized in that A resin layer formed from the resin composition according to claim 1 is provided.

6. A solidified product, characterized in that A cured product obtained by using the resin composition according to claim 1 or the resin layer of the dry film according to claim 5 .

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