JP7230421B2 - resin composition - Google Patents

Description

The present invention provides a resin composition containing an epoxy resin and a curing agent; a cured product of the resin composition; a resin sheet having a resin composition layer containing the resin composition; and a printed wiring containing a cured product of the resin composition. Regarding the board.

In recent years, the demand for small, high-performance electronic devices such as smartphones and tablet devices has increased, and along with this, the insulating materials (insulating layers) for semiconductor packages used in these small electronic devices are also required to have higher functionality. It is Such an insulating layer is known to be formed by curing a resin composition (see Patent Documents 1 and 2, for example).

JP 2017-179013 A JP 2007-081151 A

2. Description of the Related Art In recent years, electronic devices are becoming lighter, thinner, shorter and smaller. Along with this, there is a demand for flexible wiring boards that can be folded and accommodated in electronic devices, and therefore insulating materials that are excellent in flexibility are demanded. In order to obtain an insulating layer with excellent flexibility, it is conceivable to use a low-elasticity material, but as a result of investigations by the present inventors, when a low-elasticity material is applied to the insulating layer, a haloing phenomenon occurs after the via hole is formed. I found out. Here, the haloing phenomenon means that peeling occurs between the insulating layer and the inner layer substrate around the via hole. Such a haloing phenomenon usually occurs when the resin around the via hole deteriorates and the deteriorated portion is eroded during the roughening treatment. The deteriorated portion is usually observed as a discolored portion.

The present invention includes a resin composition capable of obtaining a cured product capable of suppressing the haloing phenomenon; a cured product of the resin composition; a resin sheet having a resin composition layer containing the resin composition; and the cured product. To provide a printed wiring board.

In order to achieve the object of the present invention, as a result of intensive studies, the present inventors have found that (A) an epoxy resin, (B) a curing agent, and (C) a phosphazene compound, and (D) a silane coupling agent on the surface. When the total content of the treated inorganic filler and (D') inorganic filler not surface-treated with a silane coupling agent is 50% by mass or less and component (D) is not included, component (D') By using a resin composition with a content of 4% by mass or less, it is possible to obtain a cured product that can suppress the haloing phenomenon even when the elastic modulus is low. This led to the completion of the present invention. rice field.

That is, the present invention includes the following contents.
[1] (A) an epoxy resin, (B) a curing agent, and (C) a phosphazene compound,
Further (D) contains or does not contain an inorganic filler surface-treated with a silane coupling agent,
Further (D') contains or does not contain an inorganic filler that is not surface-treated with a silane coupling agent,
When the total content of component (D) and component (D') is 50% by mass or less when the non-volatile component in the resin composition is 100% by mass, and component (D) is not included, A resin composition in which the content of component (D') is 4% by mass or less when the non-volatile component in the resin composition is taken as 100% by mass.
[2] The resin composition according to [1], containing 10% by mass or more of the component (D) based on 100% by mass of non-volatile components in the resin composition.
[3] The resin composition according to [1] or [2], containing 90% by mass or more of the component (D) when the total of the components (D) and (D') is 100% by mass.
[4] The resin composition according to any one of [1] to [3], which does not contain component (D').
[5] The resin composition according to [1], which does not contain component (D).
[6] Any one of [1] to [5], wherein the content of component (C) is 1 to 15% by mass when the non-volatile component in the resin composition is 100% by mass. of the resin composition.
[7] The resin composition according to any one of [1] to [6], wherein the specific surface area of component (D) and component (D') is 0.5 to 50 m ² /g.
[8] of [1] to [7], wherein the silane coupling agent is a silane coupling agent selected from the group consisting of aminosilane coupling agents, epoxysilane coupling agents, and methacrylsilane coupling agents. The resin composition according to any one of items 1 and 2.
[9] The resin composition according to any one of [1] to [8], further comprising one or more components selected from (E) an elastomer and (F) a thermoplastic resin.
[10] Component (C) has the following formula (1):

[In the formula, R ¹ and R ² each independently represent an optionally substituted aryl group, and n represents an integer of 1-23. ]
The resin composition according to any one of [1] to [9], which is a compound represented by
[11] R ¹ and R ² each independently represent an alkyl group, an alkoxy group, a cyano group, a halogen atom, and —X—R ³ (X is a single bond, —(alkylene group)—, —O— , -S-, -CO-, -SO ₂ -, -NHCO-, -CONH-, -OCO-, or -COO-, and R ³ is an alkyl group, an alkoxy group, a cyano group, or a halogen atom. represents an aryl group optionally having 1 to 3 substituents selected from the group consisting of ) optionally having 1 to 3 substituents selected from the group consisting of The resin composition according to [10], which is an aryl group.
[12] Any one of [1] to [11], wherein the cured product obtained by heat curing at 180 ° C. for 1 hour has a tensile modulus at 23 ° C. measured in accordance with JIS K7127 of 5 GPa or less. The resin composition according to .
[13] The resin composition according to [12], wherein the tensile modulus is 2 GPa or less.
[14] The resin composition according to any one of [1] to [13], which is used for forming an insulating layer for forming a conductor layer.
[15] The resin composition according to [14], which is for forming an insulating layer for forming a conductor layer after roughening treatment.
[16] A cured product of the resin composition according to any one of [1] to [15].
[17] A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of [1] to [13] provided on the support.
[18] A printed wiring board comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,
A printed wiring board, wherein the insulating layer is a cured product of the resin composition according to any one of [1] to [13].
[19] The printed wiring board of [18], wherein the insulating layer has via holes.

According to the present invention, a resin composition capable of obtaining a cured product capable of suppressing the haloing phenomenon; the cured product; a resin sheet having a resin composition layer containing the resin composition; and a printed wiring containing the cured product. boards can be provided.

FIG. 1 is a partial cross-sectional view schematically showing an example of a printed wiring board. FIG. 2 is a cross-sectional view schematically showing an insulating layer obtained by curing the resin composition of the present invention into a sheet, together with an inner layer substrate. FIG. 3 is a plan view schematically showing the surface of the insulating layer obtained by curing the resin composition of the present invention into a sheet, opposite to the conductor layer. FIG. 4 is a cross-sectional view schematically showing an insulating layer after roughening treatment, which is obtained by curing the resin composition of the present invention into a sheet, together with an inner layer substrate.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents.

<Resin composition>
The resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent, and (C) a phosphazene compound. Furthermore, (D) an inorganic filler surface-treated with a silane coupling agent and (D') an inorganic filler not surface-treated with a silane coupling agent are optionally included. In addition, the total content of the component (D) and the component (D') is 50% by mass or less when the non-volatile component in the resin composition is 100% by mass, and the component (D) is not included. , (D') component content is 4% by mass or less when the non-volatile component in the resin composition is 100% by mass.

By using such a resin composition, it is possible to achieve the desired effect of the present invention that a cured product capable of suppressing the haloing phenomenon can be obtained.

The resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent, (C) a phosphazene compound, and (D) and (D') inorganic fillers, as well as optional components. good too. Examples of optional components include (E) elastomers, (F) thermoplastic resins, (G) organic fillers, (H) curing accelerators, (I) organic solvents, and (J) other additives. be done. Each component contained in the resin composition will be described in detail below.

<(A) Epoxy resin>
The resin composition of the present invention contains (A) an epoxy resin.

(A) Epoxy resins include, for example, bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, and trisphenol type epoxy resins. Epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin , cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane Examples include dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin and the like. Epoxy resins may be used singly or in combination of two or more.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as (A) the epoxy resin. From the viewpoint of obtaining the desired effects of the present invention remarkably, the ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the non-volatile components of the epoxy resin (A) is preferably 50% by mass. % or more, more preferably 60 mass % or more, and particularly preferably 70 mass % or more.

Epoxy resins include liquid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “liquid epoxy resins”) and solid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “solid epoxy resins”). ). In one embodiment, the resin composition of the present invention contains a liquid epoxy resin as the epoxy resin. In one embodiment, the resin composition of the present invention contains a solid epoxy resin as the epoxy resin. The resin composition of the present invention may contain only a liquid epoxy resin as an epoxy resin, or may contain only a solid epoxy resin, and may contain a combination of a liquid epoxy resin and a solid epoxy resin. is preferred.

A liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.

Examples of liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolak type epoxy resin, ester skeleton. An alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferable.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC; "828US", "828EL", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation; ", "Epikote 828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase ChemteX Corporation "EX-721" (glycidyl ester type epoxy resin) manufactured by Daicel; "Celoxide 2021P" manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); "PB-3600" manufactured by Daicel; "JP-100", "JP-200" (epoxy resin having a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; DIC's "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" ( Naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; YX8800" (anthracene type epoxy resin); "YX7700" (xylene structure-containing novolac type epoxy resin) manufactured by Mitsubishi Chemical; "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" (bisphenol AF type epoxy resin); "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; jER1031S" (tetraphenylethane type epoxy resin) and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

(A) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the ratio by mass (liquid epoxy resin: solid epoxy resin) is preferably 20:1 to 1:20. , more preferably 10:1 to 1:10, particularly preferably 5:1 to 1:5. The desired effect of the present invention can be remarkably obtained by setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range.

The epoxy equivalent of the epoxy resin is preferably 50 g/eq. ~5000g/eq. , more preferably 50 g/eq. ~3000g/eq. , more preferably 80 g/eq. ~2000 g/eq. , even more preferably 110 g/eq. ~1000g/eq. is. Within this range, the crosslink density of the cured product of the resin sheet is sufficient, and an insulating layer with a small surface roughness can be obtained. Epoxy equivalent weight is the mass of resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, still more preferably 400 to 1500, from the viewpoint of significantly obtaining the desired effects of the present invention. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

(A) The content of the epoxy resin is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the desired effect of the present invention, it is preferably It is 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 25% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 45% by mass or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

<(B) Curing agent>
The resin composition of the present invention contains (B) a curing agent.

(B) The curing agent is not particularly limited as long as it has the function of curing the epoxy resin. Curing agents, cyanate ester curing agents, and carbodiimide curing agents are included. The curing agent may be used singly or in combination of two or more. The (B) curing agent of the resin composition of the present invention preferably contains a phenol-based curing agent or an acid anhydride-based curing agent from the viewpoint of significantly obtaining the desired effects of the present invention.

As the phenolic curing agent and the naphtholic curing agent, a phenolic curing agent having a novolac structure or a naphtholic curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to adherends, a nitrogen-containing phenolic curing agent or a nitrogen-containing naphthol curing agent is preferable, and a triazine skeleton-containing phenolic curing agent or a triazine skeleton-containing naphthol curing agent is more preferable. Among them, a triazine skeleton-containing phenol novolak resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700", "MEH-7810" and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN" manufactured by Nippon Kayaku Co., Ltd., "CBN", "GPH", Nippon Steel & Sumikin Chemical Co., Ltd. "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395", DIC "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090" ”, “TD-2090-60M” and the like.

Acid anhydride curing agents include curing agents having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid. anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride mellitic acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'- Diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1 , 3-dione, ethylene glycol bis(anhydrotrimellitate), polymer-type acid anhydrides such as styrene/maleic acid resin obtained by copolymerizing styrene and maleic acid. Commercially available acid anhydride curing agents include "HNA-100" and "MH-700" manufactured by Shin Nippon Rika.

The active ester-based curing agent is not particularly limited, but generally contains an ester group with high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolak are preferred. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentalene-phenylene.

Commercially available active ester curing agents include, as active ester compounds containing a dicyclopentadiene type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", " HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65TM" (manufactured by DIC); active ester compounds containing naphthalene structures: "EXB9416-70BK" and "EXB -8150-65T" (manufactured by DIC Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated phenol novolak; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated phenol novolac "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent that is an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent that is a benzoylated product of phenol novolak; YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation); and the like.

Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; Examples include "Fa".

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate (oligo(3-methylene-1,5-phenylenecyanate)), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4, 4′-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5- Difunctional cyanate resins such as dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, Polyfunctional cyanate resins derived from phenol novolak, cresol novolak, etc., and prepolymers obtained by partially triazine-forming these cyanate resins. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230" and "BA230S75" (part of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. or a prepolymer that is entirely triazined to form a trimer), and the like.

Specific examples of carbodiimide curing agents include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd., and the like.

When a curing agent is included, the ratio of the epoxy resin to the curing agent is [total number of epoxy groups in the epoxy resin]:[total number of reactive groups in the curing agent], which is 1:0.2 to 1:1:0.2. A range of 2 is preferred, 1:0.3 to 1:1.5 is more preferred, and 1:0.4 to 1:1.2 is even more preferred. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, and varies depending on the type of curing agent. The total number of epoxy groups in the epoxy resin is the sum of the values obtained by dividing the mass of the non-volatile components of each epoxy resin by the epoxy equivalent, and the total number of reactive groups in the curing agent is It is a value obtained by dividing the non-volatile component mass of each curing agent by the reactive group equivalent and totaling all the curing agents. By setting the ratio of the epoxy resin to the curing agent within this range, the heat resistance of the resulting cured product is further improved.

(B) The content of the curing agent is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the desired effect of the present invention, it is preferably It is 0.1% by mass or more, more preferably 1.5% by mass or more, still more preferably 2% by mass or more, and particularly preferably 2.5% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

<(C) Phosphazene compound>
The resin composition of the present invention contains (C) a phosphazene compound.

(C) A phosphazene compound refers to a compound having a structural unit represented by -P=N- as a basic skeleton. Examples of the phosphazene compound include cyclophosphazene compounds having a cyclic structure consisting of structural units represented by -P=N-, polyphosphazene compounds having a chain structure consisting of structural units represented by -P=N-, and the like. is mentioned. In the present invention, the phosphazene compound is preferably a cyclophosphazene compound having a cyclic structure composed of structural units represented by -P=N-.

In the present invention, the phosphazene compound has the following formula (1):

[In the formula, R ¹ and R ² each independently represent an optionally substituted aryl group, and n represents an integer of 1-23. ]
A compound represented by is preferred.

R ¹ and R ² are preferably each independently a hydroxy group, an alkyl group, an alkoxy group, a cyano group, a halogen atom, and —X—R ³ (X is a single bond, —(alkylene group)—, -O-, -S-, -CO-, -SO ₂ -, -NHCO-, -CONH-, -OCO- or -COO-, and R ³ is a hydroxy group, an alkyl group, an alkoxy group, a cyano an aryl group optionally having 1 to 3 substituents selected from the group consisting of a group consisting of a group and a halogen atom. represents an aryl group that may be

In the present invention, the phosphazene compound preferably does not contain a functional group that reacts with the component (A) or the component (B) from the viewpoint of effectively suppressing the haloing phenomenon. Examples of such functional groups include a hydroxy group and the like. Therefore, R ¹ and R ² are more preferably each independently an alkyl group, an alkoxy group, a cyano group, a halogen atom, and —X—R ³ (X is a single bond, —(alkylene group)—, —O—, —S—, —CO—, —SO ₂ —, —NHCO—, —CONH—, —OCO—, or —COO—, and R ³ is an alkyl group, an alkoxy group, a cyano group, and an aryl group optionally having 1 to 3 substituents selected from the group consisting of halogen atoms.) having 1 to 3 substituents selected from the group consisting of represents an aryl group that may be R ¹ and R ² are more preferably each independently an aryl group optionally having 1 to 3 substituents selected from the group consisting of an alkyl group, an alkoxy group, a cyano group and a halogen atom. indicates R ¹ and R ² are particularly preferably each independently an (unsubstituted) aryl group.

In one embodiment, preferably R ¹ is an (unsubstituted) aryl group and R ² are each independently a hydroxy group, an alkyl group, an alkoxy group, a cyano group, a halogen atom, and -X- R ³ (X is a single bond, -(alkylene group)-, -O-, -S-, -CO-, -SO ₂ -, -NHCO-, -CONH-, -OCO- or -COO- and R ³ represents an aryl group optionally having 1 to 3 substituents selected from the group consisting of a hydroxy group, an alkyl group, an alkoxy group, a cyano group, and a halogen atom.) an aryl group optionally having 1 to 3 substituents selected from the group consisting of the group consisting of, more preferably R ¹ is an (unsubstituted) aryl group and R ² is each independently, an alkyl group, an alkoxy group, a cyano group, a halogen atom, and —X—R ³ (X is a single bond, —(alkylene group)—, —O—, —S—, —CO—, —SO ₂ -, -NHCO-, -CONH-, -OCO-, or -COO-, and R ³ is 1 to 3 substituents selected from the group consisting of an alkyl group, an alkoxy group, a cyano group, and a halogen atom It is an aryl group optionally having 1 to 3 substituents selected from the group consisting of groups represented by the following.

An aryl group refers to a monovalent aromatic hydrocarbon group. An aryl group having 6 to 14 carbon atoms is preferred, and an aryl group having 6 to 10 carbon atoms is more preferred. Examples thereof include phenyl group, 1-naphthyl group, 2-naphthyl group and the like, preferably phenyl group.

An alkyl group refers to a linear or branched monovalent aliphatic saturated hydrocarbon group. An alkyl group having 1 to 6 carbon atoms is preferred, and an alkyl group having 1 to 3 carbon atoms is more preferred. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl and the like.

An alkoxy group refers to a monovalent group (alkyl-O-) formed by bonding an alkyl group to an oxygen atom. An alkoxy group having 1 to 6 carbon atoms is preferred, and an alkoxy group having 1 to 3 carbon atoms is more preferred. Examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy and the like.

An alkylene group refers to a linear or branched divalent saturated aliphatic hydrocarbon group. An alkylene group having 1 to 6 carbon atoms is preferred, and an alkylene group having 1 to 3 carbon atoms is more preferred. For example, -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH(CH ₃ )-, -CH(CH ₃ ) -CH ₂ -, -C(CH ₃ ) ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH(CH ₃ )-, -CH ₂ -CH(CH ₃ ) -CH ₂ -, -CH(CH ₃ )-CH ₂ -CH ₂ -, -CH ₂ -C(CH ₃ ) ₂ -, -C(CH ₃ ) ₂ -CH ₂ - and the like.

Halogen atoms include, for example, fluorine, chlorine, and bromine atoms.

n is preferably an integer of 1 to 13, more preferably an integer of 1 to 8, still more preferably 1 or 2, particularly preferably 1.

Specific examples of the (C) phosphazene compound include compounds represented by the following formulas (2) to (9), but the component (C) is not limited to these.

(In the formula, n is the same as above.)

Commercially available products can be used as the component (C). ), “SPB-100”, “SPE-100”, “FP-100” manufactured by Fushimi Pharmaceutical Co., Ltd. (compound represented by the above formula (2)), “FP-110” , “FP-300” (the compound represented by the above formula (3)), “FP-390” (the compound represented by the above formula (4)), “FP-400” and the like.

Although the content of (C) the phosphazene compound is not particularly limited, it is preferably 0 from the viewpoint of effectively suppressing the haloing phenomenon when the non-volatile component in the resin composition is 100% by mass. 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and particularly preferably 1.2% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less, from the viewpoint of improving the reflow resistance of the resin composition.

<(D)/(D') inorganic filler>
The resin composition of the present invention optionally contains (D) an inorganic filler surface-treated with a silane coupling agent and (D') an inorganic filler not surface-treated with a silane coupling agent.

The material of the inorganic filler is not particularly limited, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, 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. Silica or alumina is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Spherical silica is preferred as silica, and spherical alumina is preferred as alumina. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types.

Examples of commercially available inorganic fillers include "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials; YA010C"; Denka's "UFP-30"; Tokuyama's "Sylfil NSS-3N", "Silfil NSS-4N", "Sylfil NSS-5N"; Admatechs' "SC2500SQ", "SO- C4”, “SO-C2”, “SO-C1”; “DAW-01” manufactured by Denka Co., Ltd., and the like.

The average particle size of the inorganic filler is preferably 20 µm or less, more preferably 3 µm or less, and even more preferably 2 µm or less, from the viewpoint of significantly obtaining the desired effects of the present invention. The lower limit of the average particle size of the inorganic filler is preferably 0.01 µm or more, more preferably 0.05 µm or more, and still more preferably 0.1 µm or more, from the viewpoint of obtaining the desired effects of the present invention remarkably. The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement. A measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes. A measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, the volume-based particle size distribution of the inorganic filler is measured by the flow cell method, and from the obtained particle size distribution The average particle diameter was calculated as the median diameter. Examples of the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.

The inorganic filler of component (D) is treated with a silane coupling agent. Silane coupling agents include, for example, alkoxysilane compounds, aminosilane coupling agents, epoxysilane coupling agents, methacrylsilane coupling agents, vinylsilane coupling agents, styrylsilane coupling agents, and acrylsilane coupling agents. Silane coupling agents selected from ring agents, isocyanurate-based silane coupling agents, ureido-based silane coupling agents, mercaptosilane-based coupling agents, and isocyanate-based silane coupling agents can be used. Among them, silane coupling agents selected from the group consisting of aminosilane coupling agents, epoxysilane coupling agents, and methacrylsilane coupling agents are preferred. Silane coupling agents may be used singly or in combination of two or more.

The alkoxysilane compound is R _a SiX _4-a (wherein R is (i) a hydrogen atom; (ii) an alkyl group optionally having a substituent selected from an alkoxy group and a halogen atom; and ( iii) represents an aryl group optionally having a substituent selected from an alkyl group, an alkoxy group and a halogen atom, X represents an alkoxy group, and a represents an integer of 0 to 3.) For example, methyltrimethoxysilane (e.g., Shin-Etsu Chemical Co., Ltd. "KBM-13"), dimethyldimethoxysilane (e.g., Shin-Etsu Chemical Co., Ltd. "KBM-22"), phenyltrimethoxysilane (e.g., Shin-Etsu Chemical Co., Ltd. "KBM103"), methyltriethoxysilane (e.g., Shin-Etsu Chemical Co., Ltd. "KBE-13"), dimethyldiethoxysilane (e.g., Shin-Etsu Chemical Co., Ltd. "KBE-22") , phenyltriethoxysilane (e.g., Shin-Etsu Chemical Co., Ltd. "KBE-103"), n-propyltrimethoxysilane (e.g., Shin-Etsu Chemical Co., Ltd. "KBM-3033"), n-propyltriethoxysilane (e.g., Shin-Etsu Chemical Co., Ltd. "KBE-3033"), hexyltrimethoxysilane (e.g., Shin-Etsu Chemical Co., Ltd. "KBM-3063"), hexyltriethoxysilane (e.g., Shin-Etsu Chemical Co., Ltd. "KBE-3063"), Octyltriethoxysilane (e.g., Shin-Etsu Chemical Co., Ltd. "KBE-3083"), decyltrimethoxysilane (e.g., Shin-Etsu Chemical Co., Ltd. "KBM-3103C"), 1,6-bis(trimethoxysilyl)hexane ( Examples include "KBM-3066" manufactured by Shin-Etsu Chemical Co., Ltd.), 3,3,3-trifluoropropyltrimethoxysilane (eg, "KBM-7103" manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

The aminosilane-based coupling agent means an alkoxysilane compound having an amino group. ), N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (e.g., Shin-Etsu Chemical Co., Ltd. "KBM-603"), 3-aminopropyltrimethoxysilane (e.g., Shin-Etsu Chemical Co., Ltd. "KBM -903”), 3-aminopropyltriethoxysilane (for example, “KBE-903” manufactured by Shin-Etsu Chemical Co., Ltd.), 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) propylamine (for example, Shin-Etsu "KBE-9103" manufactured by Chemical Industry Co., Ltd.), N-phenyl-3-aminopropyltrimethoxysilane (for example, "KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.), N-(vinylbenzyl)-2-aminoethyl-3 -Aminopropyltrimethoxysilane hydrochloride (eg, "KBM-575" manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

The epoxysilane-based coupling agent means an alkoxysilane compound having an epoxy structure, such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (eg, "KBM-303" manufactured by Shin-Etsu Chemical Co., Ltd.). , 3-glycidoxypropylmethyldimethoxysilane (eg, "KBM-402" manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyltrimethoxysilane (eg, "KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.), 3 -glycidoxypropylmethyldiethoxysilane (eg, "KBE-402" manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyltriethoxysilane (eg, "KBE-403" manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. be done.

The methacrylsilane-based coupling agent means an alkoxysilane compound having a methacryloyl group, such as 3-methacryloxypropylmethyldimethoxysilane (eg, "KBM-502" manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyl Trimethoxysilane (eg, "KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropylmethyldiethoxysilane (eg, "KBE-502" manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltriethoxysilane (For example, "KBE-503" manufactured by Shin-Etsu Chemical Co., Ltd.).

A vinylsilane-based coupling agent means an alkoxysilane compound having a vinyl group, and examples thereof include vinyltrimethoxysilane (eg, "KBM-1003" manufactured by Shin-Etsu Chemical Co., Ltd.), vinyltriethoxysilane (eg, Shin-Etsu Chemical Co., Ltd. "KBE-1003" manufactured by Co., Ltd.) and the like. The styrylsilane-based coupling agent means an alkoxysilane compound having a styryl group, and examples thereof include p-styryltrimethoxysilane (eg, "KBM-1403" manufactured by Shin-Etsu Chemical Co., Ltd.). The acrylsilane-based coupling agent means an alkoxysilane compound having an acryloyl group, and examples thereof include 3-acryloxypropyltrimethoxysilane (eg, “KBM-5103” manufactured by Shin-Etsu Chemical Co., Ltd.).

The isocyanurate silane-based coupling agent means an alkoxysilane compound having an isocyanurate structure, such as tris-(trimethoxysilylpropyl) isocyanurate (eg, "KBM-9659" manufactured by Shin-Etsu Chemical Co., Ltd.). mentioned. The ureidosilane-based coupling agent means an alkoxysilane compound having a ureido group, and examples thereof include 3-ureidopropyltrialkoxysilane (eg, “KBE-585” manufactured by Shin-Etsu Chemical Co., Ltd.). The mercaptosilane-based coupling agent means an alkoxysilane compound having a mercapto group, such as 3-mercaptopropylmethyldimethoxysilane (eg, "KBM-802" manufactured by Shin-Etsu Chemical Co., Ltd.), 3-mercaptopropyltrimethoxy Examples include silane (eg, “KBM-803” manufactured by Shin-Etsu Chemical Co., Ltd.). The isocyanate-based silane coupling agent means an alkoxysilane compound having an isocyanate structure, and examples thereof include 3-isocyanatopropyltriethoxysilane (eg, "KBE-9007N" manufactured by Shin-Etsu Chemical Co., Ltd.).

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the silane coupling agent of component (D) is preferably within a predetermined range. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2-5 parts by mass of a surface treatment agent, and is surface-treated with 0.2-3 parts by mass. preferably 0.3 parts by mass to 2 parts by mass of the surface treatment.

The degree of surface treatment with the component (D), the silane coupling agent, can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and more preferably 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and further preferably 0.5 mg/m ² or less. preferable.

(D) The amount of carbon per unit surface area of the inorganic filler surface-treated with a silane coupling agent can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). can. Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.

From the viewpoint of further improving the effects of the present invention, the specific surface area of the inorganic filler is preferably 0.5 m ² /g or more, more preferably 1 m ² /g or more, still more preferably 1.5 m ² /g or more, especially It is preferably 2 m ² /g or more. Although there is no particular upper limit, it is preferably 50 m ² /g or less, 45 m ² /g or less, or 40 m ² /g or less. The specific surface area of the inorganic filler is determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and calculating the specific surface area using the BET multipoint method. obtained by

The total content of the component (D) and the component (D') is 50% by mass or less from the viewpoint of increasing the flexibility of the resin composition when the non-volatile component in the resin composition is 100% by mass. It is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 38% by mass or less.

The content of component (D) alone is preferably 50% by mass or less, more preferably 45% by mass, from the viewpoint of increasing the flexibility of the resin composition when the non-volatile component in the resin composition is 100% by mass. % or less, more preferably 40 mass % or less, and particularly preferably 38 mass % or less.

The content of component (D') alone is preferably 50% by mass or less, more preferably 45% by mass, from the viewpoint of increasing the flexibility of the resin composition when the non-volatile component in the resin composition is 100% by mass. % by mass or less, more preferably 40% by mass or less, particularly preferably 38% by mass or less.

A first preferred embodiment contains component (D). In this embodiment, the content of component (D) is preferably 60% by mass or more, more preferably 70% by mass or more, when the total of components (D) and (D') is 100% by mass, More preferably 80% by mass or more, particularly preferably 90% by mass or more. In this embodiment, the content of the component (D) is, for example, 10% by mass or more, 20% by mass or more, from the viewpoint of increasing the reflow resistance when the non-volatile component in the resin composition is 100% by mass. It can be 30% by mass or more. On the other hand, in the embodiment, the content of the component (D') is preferably 4% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, from the viewpoint of increasing flexibility, especially Preferably, it is 1% by mass or less. In this embodiment, it is particularly preferred not to contain component (D').

A second preferred embodiment does not contain component (D). In the embodiment, the content of the component (D') is 4% by mass or less, preferably 4% by mass or less, from the viewpoint of increasing the flexibility of the resin composition when the non-volatile component in the resin composition is 100% by mass. It is 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less. In this embodiment, it is particularly preferred not to contain both the (D) component and the (D') component.

The content of the resin component in the resin composition is preferably 50% by mass or more, more preferably 50% by mass or more, from the viewpoint of increasing the flexibility of the resin composition when the nonvolatile component in the resin composition is 100% by mass. It is 55% by mass or more, more preferably 60% by mass or more, and particularly preferably 62% by mass or more. As used herein, the term "resin component" means all remaining components after removing the inorganic filler from the resin composition, regardless of whether or not the resin composition has been surface-treated. Therefore, the "resin component" may also include low-molecular-weight compounds.

<(E) Elastomer>
In one embodiment, the resin composition of the present invention may further contain (E) an elastomer as an optional component.

In the present invention, (E) an elastomer means a resin having flexibility, which is an amorphous resin component that dissolves in an organic solvent, and is preferably a resin having rubber elasticity or a resin exhibiting rubber elasticity when polymerized with another component. . Examples of rubber elasticity include resins exhibiting an elastic modulus of 1 GPa or less when subjected to a tensile test at a temperature of 25° C. and a humidity of 40% RH according to Japanese Industrial Standards (JIS K7161).

In one embodiment, component (E) is selected from polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkyleneoxy structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure in the molecule. It is preferable that the resin has one or more structures selected from polybutadiene structures and polycarbonate structures from the viewpoint of obtaining flexible materials. In addition, "(meth)acrylate" refers to methacrylate and acrylate.

In another embodiment, the component (E) is preferably one or more selected from resins having a glass transition temperature (Tg) of 25°C or lower and resins that are liquid at 25°C or lower. The glass transition temperature of the resin having a glass transition temperature (Tg) of 25° C. or lower is preferably 20° C. or lower, more preferably 15° C. or lower. Although the lower limit of the glass transition temperature is not particularly limited, it is usually −15° C. or higher. The resin that is liquid at 25°C is preferably a resin that is liquid at 20°C or lower, more preferably a resin that is liquid at 15°C or lower.

In a more preferred embodiment, the component (E) is one or more selected from resins having a glass transition temperature of 25° C. or less and being liquid at 25° C., and having a polybutadiene structure and a polysiloxane structure in the molecule. , a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure.

The polybutadiene structure includes not only a structure formed by polymerizing butadiene but also a structure formed by hydrogenating the structure. Also, the butadiene structure may be partially hydrogenated or entirely hydrogenated. Furthermore, the polybutadiene structure may be contained in the main chain or the side chain in component (E).

Preferred examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxyl group-containing polybutadiene resins, phenolic hydroxyl group-containing polybutadiene resins, carboxyl group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, and isocyanate group-containing polybutadiene resins. containing polybutadiene resin, urethane group-containing polybutadiene resin, and the like. Among them, a phenolic hydroxyl group-containing polybutadiene resin is more preferable. Here, the "hydrogenated polybutadiene skeleton-containing resin" refers to a resin in which at least a portion of the polybutadiene skeleton is hydrogenated, and does not necessarily have to be a resin in which the polybutadiene skeleton is completely hydrogenated. Examples of hydrogenated polybutadiene skeleton-containing resins include hydrogenated polybutadiene skeleton-containing epoxy resins. Examples of the phenolic hydroxyl group-containing polybutadiene resin include resins having a polybutadiene structure and having a phenolic hydroxyl group.

Specific examples of polybutadiene resins, which are resins having a polybutadiene structure in the molecule, include “Ricon 657” (epoxy group-containing polybutadiene), “Ricon 130MA8”, “Ricon 130MA13”, “Ricon 130MA20”, “Ricon 130MA20” manufactured by Clay Valley. Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", "Ricon 184MA6" (acid anhydride group-containing polybutadiene), "GQ-1000" (hydroxyl group- and carboxyl group-introduced polybutadiene), "G-1000 ”, “G-2000”, “G-3000” (both hydroxyl-terminated polybutadiene), “GI-1000”, “GI-2000”, “GI-3000” (both hydroxyl-terminated hydrogenated polybutadiene), manufactured by Daicel "PB3600", "PB4700" (polybutadiene skeleton epoxy compound), "Epofriend A1005", "Epofriend A1010", "Epofriend A1020" (epoxy compound of styrene, butadiene and styrene block copolymer), Nagase ChemteX Co., Ltd. "FCA-061L" (hydrogenated polybutadiene skeleton epoxy compound), "R-45EPT" (polybutadiene skeleton epoxy compound), and the like manufactured by the company.

Examples of preferred polybutadiene resins include linear polyimides made from hydroxyl group-terminated polybutadiene, diisocyanate compounds and polybasic acids or their anhydrides (Japanese Patent Application Laid-Open No. 2006-37083, International Publication No. 2008/153208). polyimide). The polybutadiene structure content of the polyimide resin is preferably 60% to 95% by mass, more preferably 75% to 85% by mass. Details of the polyimide resin can be referred to in JP-A-2006-37083 and WO 2008/153208, the contents of which are incorporated herein.

The number average molecular weight of the hydroxyl-terminated polybutadiene is preferably 500-5,000, more preferably 1,000-3,000. The hydroxyl group-terminated polybutadiene preferably has a hydroxyl group equivalent weight of 250 to 1,250.

Examples of diisocyanate compounds include aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylylene diisocyanate and diphenylmethane diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate; and alicyclic compounds such as isophorone diisocyanate. diisocyanates of the formula: Among these, aromatic diisocyanates are preferred, and toluene-2,4-diisocyanate is more preferred.

Examples of polybasic acids or anhydrides thereof include ethylene glycol bis-trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, naphthalenetetracarboxylic acid, 5-(2,5-dioxotetrahydrofuryl)- Tetrabasic acids such as 3-methyl-cyclohexene-1,2-dicarboxylic acid and 3,3′-4,4′-diphenylsulfonetetracarboxylic acid and their anhydrides, and tribasic acids such as trimellitic acid and cyclohexanetricarboxylic acid Acids and their anhydrides, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho(1,2-C)furan-1,3 - dione and the like.

Also, the polybutadiene structure includes a polystyrene structure having a structure obtained by polymerizing styrene.

Specific examples of polystyrene resins, which are resins having a polystyrene structure in the molecule, include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene- Styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-butylene-styrene block copolymer polymer (SBBS), styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, hydrogenated styrene-butadiene random copolymer and the like.

Commercially available polystyrene resins may be used, for example, hydrogenated styrene thermoplastic elastomer "H1041", "Tuftec H1043", "Tuftec P2000", "Tuftec MP10" (manufactured by Asahi Kasei Corporation); epoxidized styrene-butadiene Thermoplastic elastomers "Epofriend AT501" and "CT310" (manufactured by Daicel); Modified styrene elastomer having hydroxyl group "Septon HG252" (manufactured by Kuraray); Modified styrene elastomer having carboxyl group "Tuftec N503M", amino modified styrene elastomer "Tuftec N501" having an acid anhydride group; modified styrene elastomer "Tuftec M1913" (manufactured by Asahi Kasei Chemicals); unmodified styrene elastomer "Septon S8104" (manufactured by Kuraray Co., Ltd.); be able to. (C) component may be used individually by 1 type, and may be used in combination of 2 or more types.

A polysiloxane structure is a structure containing siloxane bonds, and is included in, for example, silicone rubber. The polysiloxane structure may be contained in the main chain or in the side chains of component (E).

Specific examples of the polysiloxane resin, which is a resin having a polysiloxane structure in the molecule, include "SMP-2006", "SMP-2003PGMEA", and "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd., amine group-terminated polysiloxane, Linear polyimides made from basic acid anhydrides (International Publication No. 2010/053185) and the like can be mentioned.

A poly(meth)acrylate structure is a structure formed by polymerizing acrylic acid or an acrylic acid ester, and includes a structure formed by polymerizing methacrylic acid or a methacrylic acid ester. The (meth)acrylate structure may be contained in the main chain or may be contained in the side chain in the component (E).

Preferable examples of poly(meth)acrylate resins, which are resins having a poly(meth)acrylate structure in the molecule, include hydroxyl group-containing poly(meth)acrylate resins, phenolic hydroxyl group-containing poly(meth)acrylate resins, and carboxyl group-containing poly(meth)acrylate resins. Poly(meth)acrylate resins, acid anhydride group-containing poly(meth)acrylate resins, epoxy group-containing poly(meth)acrylate resins, isocyanate group-containing poly(meth)acrylate resins, urethane group-containing poly(meth)acrylate resins, etc.) mentioned.

Specific examples of poly(meth)acrylate resins include Teisan Resin "SG-70L", "SG-708-6", "WS-023", "SG-700AS" and "SG-280TEA" manufactured by Nagase ChemteX Corporation. ”(Carboxy group-containing acrylic acid ester copolymer resin, acid value 5-34 mgKOH / g, weight average molecular weight 400,000-900,000, Tg-30 ° C.-5 ° C.), “SG-80H”, “SG-80H- 3”, “SG-P3” (epoxy group-containing acrylic acid ester copolymer resin, epoxy equivalent 4761-14285 g/eq, weight average molecular weight 350,000-850,000, Tg 11° C.-12° C.), “SG-600TEA”, "SG-790"" (hydroxy group-containing acrylic acid ester copolymer resin, hydroxyl value 20-40 mgKOH/g, weight average molecular weight 500,000-1,200,000, Tg -37°C to -32°C), manufactured by Negami Kogyo Co., Ltd. "ME-2000", "W-116.3" (carboxy group-containing acrylic ester copolymer resin), "W-197C" (hydroxyl group-containing acrylic ester copolymer resin), "KG-25", " KG-3000" (epoxy group-containing acrylic acid ester copolymer resin) and the like.

The polyalkylene structure preferably has a given number of carbon atoms. Specifically, the number of carbon atoms in the polyalkylene structure is preferably 2 or more, more preferably 3 or more, particularly preferably 5 or more, and preferably 15 or less, more preferably 10 or less, and particularly preferably 6 or less. Moreover, the polyalkylene structure may be contained in the main chain or the side chain in the component (E).

The polyalkyleneoxy structure preferably has a given number of carbon atoms. Specifically, the number of carbon atoms in the polyalkyleneoxy structure is preferably 2 or more, preferably 3 or more, more preferably 5 or more, preferably 15 or less, more preferably 10 or less, and particularly preferably 6 or less. The polyalkyleneoxy structure in component (E) may be contained in the main chain or may be contained in the side chain.

Specific examples of the polyalkylene resin that is a resin having a polyalkylene structure in the molecule and the polyalkyleneoxy resin that is a resin having a polyalkyleneoxy structure in the molecule include "PTXG-1000" and "PTXG" manufactured by Asahi Kasei Fibers Co., Ltd. -1800”, “YX-7180” manufactured by Mitsubishi Chemical Corporation (resin containing an alkylene structure having an ether bond), “EXA-4850-150”, “EXA-4816”, “EXA-4822” manufactured by DIC Corporation ”, “EP-4000”, “EP-4003”, “EP-4010”, “EP-4011” manufactured by ADEKA, “BEO-60E” manufactured by New Japan Chemical Co., Ltd., “BPO-20E”, Mitsubishi Chemical "YL7175" and "YL7410" manufactured by the company.

The polyisoprene structure in component (E) may be contained in the main chain or may be contained in the side chain. Specific examples of the polyisoprene resin, which is a resin having a polyisoprene structure in its molecule, include "KL-610" and "KL-613" manufactured by Kuraray Co., Ltd., and the like.

The polyisobutylene structure may be contained in the main chain or in the side chain of component (E). Specific examples of polyisobutylene resins, which are resins having a polyisobutylene structure in the molecule, include Kaneka's "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene- isobutylene diblock copolymer) and the like.

The polycarbonate structure may be contained in the main chain or in the side chains of component (E).

Preferable examples of polycarbonate resins, which are resins having a polycarbonate structure in the molecule, include hydroxyl group-containing polycarbonate resins, phenolic hydroxyl group-containing polycarbonate resins, carboxy group-containing polycarbonate resins, acid anhydride group-containing polycarbonate resins, and epoxy group-containing polycarbonate resins. , isocyanate group-containing polycarbonate resins, urethane group-containing polycarbonate resins, and the like.

Specific examples of polycarbonate resins include "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Chemicals, and "C-1090", "C-2090" and "C-3090" (polycarbonate diols) manufactured by Kuraray Co., Ltd. etc.

Examples of preferred polycarbonate resins also include linear polyimides made from hydroxyl group-terminated polycarbonates, diisocyanate compounds and polybasic acids or their anhydrides. The linear polyimide has a urethane structure and a polycarbonate structure. The polycarbonate structure content of the polyimide resin is preferably 60% to 95% by mass, more preferably 75% to 85% by mass. Details of the polyimide resin can be referred to in International Publication No. 2016/129541, the content of which is incorporated herein.

The number average molecular weight of the hydroxyl group-terminated polycarbonate is preferably 500-5,000, more preferably 1,000-3,000. The hydroxyl group-terminated polycarbonate preferably has a hydroxyl group equivalent weight of 250 to 1,250.

(E) It is preferable that the component further has an imide structure. By having an imide structure, the heat resistance of the component (E) can be enhanced and the crack resistance can be effectively enhanced.

The (E) component may have any structure of linear, branched, or cyclic, but preferably linear.

Component (E) preferably further has a functional group capable of reacting with component (A). The functional groups also include reactive groups that appear upon heating. (E) By having a functional group, the mechanical strength of the cured product of the resin composition can be improved.

Functional groups include carboxy groups, hydroxy groups, acid anhydride groups, phenolic hydroxyl groups, epoxy groups, isocyanate groups, urethane groups, and the like. Among them, from the viewpoint of significantly obtaining the effects of the present invention, the functional group has one or more functional groups selected from a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group. is preferred, and a phenolic hydroxyl group is particularly preferred.

(E) component may be used individually by 1 type, and may be used in combination of 2 or more types.

The component (E) preferably has a high molecular weight from the viewpoint of exhibiting flexibility. Specific number average molecular weight Mn of component (E) is preferably 4000 or more, more preferably 4500 or more, still more preferably 5000 or more, particularly preferably 5500 or more, preferably 100000 or less, more preferably 95000 or less, Particularly preferably, it is 90,000 or less. (E) The number average molecular weight Mn of the component is a polystyrene equivalent number average molecular weight measured using GPC (gel permeation chromatography).

Further, the specific weight average molecular weight of component (E) is preferably 5,500 to 100,000, more preferably 10,000 to 90,000, still more preferably 15,000 to 80,000, from the viewpoint of obtaining flexibility. The weight average molecular weight of the component (E) is the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

When component (E) has a functional group, the functional group equivalent of component (E) is preferably 100 or more, more preferably 200 or more, still more preferably 1000 or more, particularly preferably 2500 or more, and preferably 50000 or less. , more preferably 30,000 or less, still more preferably 10,000 or less, and particularly preferably 5,000 or less. Functional group equivalent weight is the number of grams of resin containing one gram equivalent of functional group. For example, the epoxy group equivalent can be measured according to JIS K7236. Further, for example, the hydroxyl equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured according to JIS K1557-1.

(E) When the elastomer is contained, the content of (E) the elastomer is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of obtaining flexibility, It is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 25% by mass or more. (E) When a large amount of elastomer is contained, the elastic modulus of the cured resin composition can be lowered, so that an insulating layer that can be applied to a flexible wiring board can be obtained. Generally, when the modulus of elasticity of the cured product is low, it has been found that the haloing phenomenon tends to occur, but the resin composition of the present invention can suppress the haloing phenomenon. (E) The upper limit of the elastomer content is preferably 60% by mass or less, more preferably 55% by mass or less, even more preferably 50% by mass or less, and particularly preferably It is 45% by mass or less.

<(F) Thermoplastic resin>
In one embodiment, the resin composition of the present invention may further contain (F) a thermoplastic resin as an optional component.

(F) Thermoplastic resins include, for example, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, and polycarbonate resins. , polyetheretherketone resin, polyester resin, etc., and phenoxy resin is preferred. The thermoplastic resin may be used singly or in combination of two or more.

(F) The polystyrene equivalent weight average molecular weight of the thermoplastic resin is preferably 38,000 or more, more preferably 40,000 or more, and even more preferably 42,000 or more. The upper limit is preferably 100,000 or less, more preferably 70,000 or less, even more preferably 60,000 or less. (F) The polystyrene equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin (F) is measured by LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P/K-804L manufactured by Showa Denko Co., Ltd. as a column. /K-804L can be calculated by using chloroform or the like as a mobile phase, measuring the column temperature at 40° C., and using a standard polystyrene calibration curve.

Examples of phenoxy resins include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, and terpene. and a phenoxy resin having one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of phenoxy resins include Mitsubishi Chemical's "1256" and "4250" (both phenoxy resins containing bisphenol A skeleton), "YX8100" (phenoxy resin containing bisphenol S skeleton), and "YX6954" (bisphenolacetophenone). skeleton-containing phenoxy resin), and in addition, "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; ”, “YL6794”, “YL7213”, “YL7290” and “YL7482”.

Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of polyvinyl acetal resins include Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, Denka Butyral 6000-EP, and Sekisui. S-lec BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, BM series manufactured by Kagaku Kogyo Co., Ltd. may be mentioned.

Specific examples of the polyimide resin include "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin Nippon Rika. Specific examples of polyimide resins also include linear polyimides obtained by reacting bifunctional hydroxyl group-terminated polybutadiene, diisocyanate compounds and tetrabasic acid anhydrides (polyimides described in JP-A-2006-37083), and polysiloxane skeletons. Examples include modified polyimides such as polyimide containing (polyimides described in JP-A-2002-12667 and JP-A-2000-319386).

Specific examples of polyamide-imide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamideimide resins include modified polyamideimides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamideimides) manufactured by Hitachi Chemical Co., Ltd.

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like. Specific examples of the polyphenylene ether resin include oligophenylene ether/styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, Inc., and the like.

Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

(F) When containing a thermoplastic resin, the content of the (F) thermoplastic resin is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, the content of the present invention From the viewpoint of significantly obtaining the desired effect, the content is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and particularly preferably 20% by mass or more. (F) When the thermoplastic resin is contained in a large amount, the elastic modulus of the cured product of the resin composition can be lowered, so that an insulating layer applicable to a flexible wiring board can be obtained. Generally, when the modulus of elasticity of the cured product is low, it has been found that the haloing phenomenon tends to occur, but the resin composition of the present invention can suppress the haloing phenomenon. (F) The upper limit of the content of the thermoplastic resin is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, from the viewpoint of significantly obtaining the desired effects of the present invention. Preferably, it is 25% by mass or less.

<(G) Organic filler>
The resin composition of the present invention optionally contains (G) an organic filler.

(G) As the organic filler, any organic filler that can be used for sealing electronic parts may be used. Examples include rubber particles, polyamide fine particles, silicone particles, and the like. is preferred.

The rubber particles are not particularly limited as long as they are fine particles of a resin that is made insoluble and infusible in an organic solvent by chemically cross-linking a resin exhibiting rubber elasticity. Examples include acrylonitrile-butadiene rubber particles, butadiene rubber particles, Examples include acrylic rubber particles. Specific examples of rubber particles include XER-91 (manufactured by Japan Synthetic Rubber Co., Ltd.), Staphyloid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (manufactured by Aica Kogyo Co., Ltd.), PARALOID EXL2655, EXL2602 ( (manufactured by Dow Chemical Co., Ltd.) and the like.

(G) The average particle size of the organic filler is preferably in the range of 0.005 μm to 1 μm, more preferably in the range of 0.1 μm to 0.6 μm. (G) The average particle size of the organic filler can be measured using a dynamic light scattering method. For example, the organic filler is uniformly dispersed in an appropriate organic solvent by ultrasonic waves or the like, and the particle size distribution of the organic filler is measured on a mass basis using a concentrated particle size analyzer ("FPAR-1000" manufactured by Otsuka Electronics Co., Ltd.). It can be measured by creating and using the median diameter as the average particle diameter.

(G) When containing an organic filler, the content of the (G) organic filler is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, From the viewpoint of significantly obtaining the desired effect, the content is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less.

<(H) Curing accelerator>
The resin composition of the present invention optionally contains (H) a curing accelerator.

(H) Curing accelerators include, for example, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like. Among them, phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, and metallic curing accelerators are preferred, and amine curing accelerators, imidazole curing accelerators, and metallic curing accelerators are more preferred. The curing accelerator may be used singly or in combination of two or more.

Phosphorus curing accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1, 8-diazabicyclo(5,4,0)-undecene, etc., and 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferred.

Examples of imidazole curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and the like, and adducts of imidazole compounds and epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole-based curing accelerator, a commercially available product may be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Guanidine curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being preferred.

Metal-based curing accelerators include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. organic zinc complexes such as iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate; Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

When the resin composition contains (H) curing accelerator, the content of (H) curing accelerator is not particularly limited, but when the resin component in the resin composition is 100% by mass, From the viewpoint of significantly obtaining the desired effects of the present invention, the content is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.05% by mass or more. The upper limit is preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less.

(H) When containing a curing accelerator, the content of (H) curing accelerator is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, the present invention From the viewpoint of significantly obtaining the desired effect, the content is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, still more preferably 0.01% by mass or more, and particularly preferably 0.1% by mass or more. . The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

<(I) Organic solvent>
The resin composition of the present invention may further contain (I) an organic solvent as an optional component.

Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate and ethyl diglycol acetate; cellosolve and butyl Carbitol solvents such as carbitol; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and trimethylbenzene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. can. The organic solvent may be used singly or in combination of two or more at any ratio.

<(J) Other additives>
The resin composition may further contain other additives as optional components in addition to the components described above. Examples of such additives include thickeners, antifoaming agents, leveling agents, adhesion imparting agents, polymerization initiators, flame retardants and the like. These additives may be used singly or in combination of two or more. Each content can be appropriately set by those skilled in the art.

<Method for producing resin composition>
The resin composition of the present invention can be produced, for example, by uniformly dispersing the ingredients by stirring them with a stirring device such as a rotary mixer.

<Characteristics of resin composition>
Although it has been found that low-elasticity materials are generally susceptible to haloing, the resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent, and (C) a phosphazene compound, and The content of (D) an inorganic filler surface-treated with a silane coupling agent and (D') an inorganic filler not surface-treated with a silane coupling agent is 50% by mass or less, and component (D) is When it is not contained, the content of the component (D') is 4% by mass or less, so the haloing phenomenon can be suppressed even when the elastic modulus of the cured product is low.

Therefore, the resin composition of the present invention is particularly useful when its cured product has a low tensile modulus. For example, the tensile modulus at 23° C. measured according to JIS K7127 of the cured product obtained by thermally curing the resin composition of the present invention at 180° C. for 1 hour is preferably 10 GPa or less, more preferably. is 5 GPa or less, more preferably 2 GPa or less, and particularly preferably 1 GPa or less.

The effect of suppressing the haloing phenomenon will be described below with reference to the drawings.

FIG. 2 is a cross-sectional view schematically showing an insulating layer 100 obtained by curing the resin composition of the present invention into a sheet, together with an inner layer substrate 200. As shown in FIG. 2 shows a cross section of the insulating layer 100 taken along a plane passing through the center 120C of the bottom 120 of the via hole 110 and parallel to the thickness direction of the insulating layer 100. FIG.

As shown in FIG. 2, the insulating layer 100 is a layer obtained by curing a resin composition formed on an inner layer substrate 200 including a conductor layer 210, and is made of a cured product of the resin composition. A via hole 110 is formed in the insulating layer 100 . Via hole 110 generally has a larger diameter closer to surface 100U of insulating layer 100 opposite conductor layer 210 and a smaller diameter closer to conductor layer 210. Ideally, via hole 110 is formed in a forward tapered shape. It is formed in a columnar shape having a constant diameter in the thickness direction of 100 . The via hole 110 is usually formed by irradiating the surface 100U of the insulating layer 100 opposite to the conductor layer 210 with a laser beam to partially remove the insulating layer 100 .

The bottom of the via hole 110 on the side of the conductor layer 210 is appropriately called a “via bottom” and denoted by reference numeral 120 . The diameter of the via bottom 120 is called a bottom diameter _Lb. An opening formed on the side of the via hole 110 opposite to the conductor layer 210 is appropriately called a “via top” and denoted by reference numeral 130 . The diameter of the via top 130 is called a top diameter _Lt. Generally, the via bottom 120 and the via top 130 are circular when viewed in the thickness direction of the insulating layer 100, but they may be oval. When the planar shapes of the via bottom 120 and the via top 130 are elliptical, the bottom diameter _Lb and the top diameter _Lt respectively represent the longer diameters of the elliptical shapes.

FIG. 3 is a plan view schematically showing a surface 100U of the insulating layer 100 obtained by curing the resin composition of the present invention into a sheet, opposite to the conductor layer 210 (not shown in FIG. 3). is.

As shown in FIG. 3 , looking at the insulating layer 100 with the via hole 110 formed therein, the insulating layer 100 extends from the edge 180 of the via top 130 to the edge 190 on the outer peripheral side of the discolored portion 140 around the via hole 110 . A discolored portion 140 may be observed. This discolored portion 140 may be formed by deterioration of the resin during formation of the via hole 110 , and is normally formed continuously from the via hole 110 . Moreover, in many cases, the discolored portion 140 is a whitened portion.

FIG. 4 is a cross-sectional view schematically showing the insulating layer 100 after roughening treatment, which is obtained by curing the resin composition of the present invention into a sheet, together with the inner layer substrate 200 . 4 shows a cross section of insulating layer 100 cut along a plane passing through center 120C of via bottom 120 of via hole 110 and parallel to the thickness direction of insulating layer 100. FIG.

As shown in FIG. 4, when the insulating layer 100 having the via hole 110 formed therein is roughened, a haloing phenomenon occurs, the insulating layer 100 at the discolored portion 140 is separated from the conductive layer 210, and the edge of the via bottom 120 is peeled off. A gap 160 continuous from 150 may be formed.

By using the resin composition of the present invention, the haloing phenomenon can be suppressed. Therefore, the separation of the insulating layer 100 from the conductor layer 210 can be suppressed, so that the size of the gap 160 can be reduced.

The edge 150 of the via bottom 120 corresponds to the inner edge of the gap 160 . Therefore, the distance Wb from the edge 150 of the via bottom 120 to the edge 170 on the outer peripheral side of the gap 160 (that is, the edge on the far side from the center 120C of the via bottom 120) is the size of the gap 160 in the in-plane direction. Equivalent to. Here, the in-plane direction means a direction perpendicular to the thickness direction of the insulating layer 100 . Further, in the following description, the distance Wb may be referred to as a haloing distance Wb of the via hole 110 from the edge 150 of the via bottom 120 . The degree of suppression of the haloing phenomenon can be evaluated by the haloing distance Wb from the edge 150 of the via bottom 120 . Specifically, it can be evaluated that the smaller the haloing distance Wb from the edge 150 of the via bottom 120 is, the more effectively the haloing phenomenon can be suppressed.

For example, a resin composition layer containing a resin composition formed on a copper foil is heated at 100° C. for 30 minutes and then cured by heating _at 180° C. for 30 minutes. Light is applied to form a via hole 110 having a top diameter _Lt of about 50 μm. After that, it is immersed in a swelling liquid at 60° C. for 5 minutes, then in an oxidizing agent solution at 80° C. for 15 minutes, then in a neutralizing liquid at 40° C. for 5 minutes, and then dried at 80° C. for 15 minutes. When the resin composition of the present invention is used, the haloing distance Wb from the edge 150 of the via bottom 120 of the via hole 110 of the insulating layer 100 thus obtained is preferably 10 μm or less, more preferably 8 μm or less, and even more preferably 8 μm or less. can be 6 μm or less, particularly preferably 4 μm or less.

The haloing distance Wb from the edge 150 of the via bottom 120 is measured by using an FIB (focused ion beam) to cut the insulating layer 100 so that a cross section parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the via bottom 120 appears. It can be measured by observing the cross section with an electron microscope after shaving it out.

Moreover, by using the resin composition of the present invention, even when the reflow resistance is evaluated, almost no abnormality such as blistering is observed in the plated conductor layer. Reflow resistance evaluation can be performed, for example, as follows. A resin composition layer containing a resin composition formed on a PET film is cured by heating at 180° C. for 30 minutes to form an insulating layer. Thereafter, it is immersed in a swelling liquid at 60°C for 5 minutes, then in a roughening liquid at 80°C for 15 minutes, then in a neutralizing liquid at 40°C for 5 minutes, and then dried at 80°C for 15 minutes. It is then immersed in an electroless plating solution containing PdCl ₂ and then in an electroless copper plating solution. Then, after annealing by heating at 150° C. for 30 minutes, an etching resist is formed, and after pattern formation by etching, copper sulfate electroplating is performed to form a conductor layer with a thickness of 30±5 μm. , Annealing treatment is performed at 180° C. for 60 minutes. After that, it is cut into small pieces of 100 mm × 50 mm and passed through a reflow device (“HAS-6116” manufactured by Nippon Antom Co., Ltd.) that reproduces a solder reflow temperature with a peak temperature of 260 ° C. (reflow temperature profile is IPC / JEDEC J-STD) 5 times. -020C). At that time, even when visually observed, almost no abnormalities such as blisters are observed in the conductor layer. For example, out of 5 small pieces, preferably 2 or less, more preferably 1 or less, and particularly preferably 0, are abnormal.

<Application of resin composition>
The resin composition of the present invention can provide a cured product that can suppress the haloing phenomenon. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulation. Specifically, a resin composition for forming an insulating layer for forming a conductor layer (including a rewiring layer) formed on an insulating layer (resin for forming an insulating layer for forming a conductor layer composition), and can be used more preferably for forming an insulating layer for forming a conductor layer after roughening treatment. In addition, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board), and a resin for forming an interlayer insulating layer of a printed wiring board It can be used more preferably as a composition (a resin composition for an interlayer insulation layer of a printed wiring board). Moreover, since the resin composition of the present invention provides an insulating layer with low elasticity, it can be suitably used for forming an insulating layer of a flexible wiring board.

Further, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention is used as an insulating layer for forming a rewiring layer. (a resin composition for forming a rewiring layer) and a resin composition for sealing a semiconductor chip (a resin composition for semiconductor chip sealing). A rewiring layer may be further formed on the encapsulation layer when the semiconductor chip package is manufactured.
(1) a step of laminating a temporary fixing film on a substrate;
(2) temporarily fixing the semiconductor chip on the temporary fixing film;
(3) forming a sealing layer on the semiconductor chip;
(4) a step of peeling the base material and the temporary fixing film from the semiconductor chip;
(5) forming a rewiring layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been removed; and (6) forming a rewiring layer as a conductor layer on the rewiring layer. forming process

<Resin sheet>
The resin sheet of the present invention includes a support and a resin composition layer formed of the resin composition of the present invention provided on the support.

The thickness of the resin composition layer is preferably 15 μm or less, more preferably 13 μm or less, and even more preferably 13 μm or less, from the viewpoint of thinning the printed wiring board and providing a cured product having excellent insulation even if it is a thin film. It is 10 μm or less, or 8 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can be usually 1 μm or more, 1.5 μm or more, or 2 μm or more.

Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketones, polyimides, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.

The support may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface to be bonded to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used, for example, "SK-1" manufactured by Lintec Co., Ltd., "SK-1", " AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel".

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range.

In one embodiment, the resin sheet may further contain other layers as necessary. Such other layers include, for example, a protective film conforming to the support provided on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). be done. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, the surface of the resin composition layer can be prevented from being dusted or scratched.

For the resin sheet, for example, a resin varnish is prepared by dissolving a resin composition in an organic solvent, the resin varnish is applied onto a support using a die coater or the like, and dried to form a resin composition layer. It can be manufactured by

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol; carbitols; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, drying at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes The resin composition layer can be formed.

The resin sheet can be wound into a roll and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

The resin sheet of the present invention provides an insulating layer (cured product of a resin composition layer) that can maintain thin-film insulation properties and adhesion to a conductor layer after an environmental test in a high-temperature and high-humidity environment, even if it is thin. . Therefore, the resin sheet of the present invention can be suitably used as a resin sheet for forming an insulating layer of a printed wiring board (for forming an insulating layer of a printed wiring board), and forming an interlayer insulating layer of a printed wiring board. It can be more suitably used as a resin sheet (resin sheet for an interlayer insulation layer of a printed wiring board) for the purpose. Further, for example, in a printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer, the By forming the insulating layer with a resin sheet, the distance between the first and second conductor layers (the thickness of the insulating layer between the first and second conductor layers) is 6 μm or less (preferably 5.5 μm or less, more preferably 5.5 μm or less). is 5 μm or less), and excellent thin film insulation can be obtained.

<Printed wiring board>
The printed wiring board of the present invention includes an insulating layer, a first conductor layer, and a second conductor layer formed from the cured resin composition of the present invention. The insulating layer is provided between the first conductor layer and the second conductor layer, and insulates the first conductor layer from the second conductor layer (the conductor layer is sometimes called a wiring layer). be).

Since the insulating layer is formed from the cured product of the resin composition of the present invention, it has excellent thin film insulating properties. Therefore, the thickness of the insulating layer between the first and second conductor layers is preferably 6 μm or less, more preferably 5.5 μm or less, even more preferably 5 μm or less. Although the lower limit is not particularly limited, it may be 0.1 μm or more. The distance between the first conductor layer and the second conductor layer (the thickness of the insulating layer between the first and second conductor layers) is, as shown in FIG. 11 and the thickness t1 of the insulating layer 3 between the main surface 21 of the second conductor layer 2 . The first and second conductor layers are conductor layers adjacent to each other with an insulating layer interposed therebetween, and the main surfaces 11 and 21 face each other.

The thickness t2 of the entire insulating layer is preferably 15 μm or less, more preferably 13 μm or less, and even more preferably 10 μm or less. Although the lower limit is not particularly limited, it can be usually 1 μm or more, 1.5 μm or more, 2 μm or more, or the like.

A printed wiring board can be manufactured using the resin sheet described above by a method including the following steps (I) and (II).
(I) Step of laminating the resin composition layer of the resin sheet on the inner layer substrate such that the resin composition layer is bonded to the inner layer substrate (II) Step of thermally curing the resin composition layer to form an insulating layer

The "inner layer substrate" used in step (I) is a member that serves as a printed wiring board substrate, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc. The substrate may also have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having conductor layers (circuits) formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board." Further, an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing a printed wiring board is also included in the "inner layer substrate" as used in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components can be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls). Instead of pressing the thermocompression member directly onto the resin sheet, it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the uneven surface of the inner layer substrate.

Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60° C. to 160° C., more preferably 80° C. to 140° C., and the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. .29 MPa to 1.47 MPa, and the heat pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

Lamination can be done with a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch vacuum pressurized laminator, and the like.

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above. Smoothing treatment can be performed with a commercially available laminator. Lamination and smoothing may be performed continuously using the above-mentioned commercially available vacuum laminator.

The support may be removed between steps (I) and (II) or after step (II).

In step (II), the resin composition layer is thermally cured to form an insulating layer.

The thermosetting conditions for the resin composition layer are not particularly limited, and conditions that are commonly used for forming insulating layers of printed wiring boards may be used.

For example, although the thermosetting conditions for the resin composition layer vary depending on the type of resin composition, etc., the curing temperature is preferably 120° C. to 240° C., more preferably 150° C. to 220° C., and still more preferably 170° C. to 200° C. °C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, even more preferably 15 minutes to 90 minutes.

Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is cured at a temperature of 50° C. or higher and less than 120° C. (preferably 60° C. or higher and 115° C. or lower, more preferably 70° C. or higher and 110° C. or lower). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes).

When manufacturing a printed wiring board, (III) the step of drilling holes in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or step ( It may be carried out between IV) and step (V). If necessary, the steps (II) to (V) of forming the insulating layer and the conductor layer may be repeated to form a multilayer wiring board. In this case, the thickness of the insulating layer between the conductor layers (t1 in FIG. 1) is preferably within the above range.

Step (III) is a step of making holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, laser, plasma, or the like, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are commonly used in forming insulating layers of printed wiring boards can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order. The swelling liquid used in the roughening treatment is not particularly limited, but examples thereof include alkaline solutions, surfactant solutions, etc., preferably alkaline solutions, more preferably sodium hydroxide solutions and potassium hydroxide solutions. preferable. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30.degree. C. to 90.degree. C. for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 80° C. for 10 to 30 minutes. Further, the permanganate concentration in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan. Moreover, as a neutralization liquid used for the roughening treatment, an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd. can be mentioned. The treatment with the neutralizing solution can be carried out by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method of immersing an object roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less. Although the lower limit is not particularly limited, it is preferably 0.5 nm or more, more preferably 1 nm or more. The root mean square roughness (Rq) of the surface of the insulating layer after roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less. Although the lower limit is not particularly limited, it is preferably 0.5 nm or more, more preferably 1 nm or more. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer. When no conductor layer is formed on the inner layer substrate, the step (V) is a step of forming a first conductor layer, and when a conductor layer is formed on the inner layer substrate, the conductor layer becomes the first conductor layer. and step (V) is a step of forming a second conductor layer.

The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper- nickel alloys and copper-titanium alloys). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, nickel-chromium alloys, copper- Nickel alloys and copper/titanium alloy alloy layers are preferred, and single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium alloy alloy layers are more preferred, and copper single metal layers are preferred. A metal layer is more preferred.

The conductor layer may have a single layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

The thickness of the conductor layer is generally between 3 μm and 35 μm, preferably between 5 μm and 30 μm, depending on the desired printed wiring board design.

In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating the surface of an insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. It is preferably formed by a method. An example of forming a conductor layer by a semi-additive method is shown below.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electroplating, the mask pattern is removed. After that, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

Since the resin sheet of the present invention provides an insulating layer having good component embedding properties, it can be suitably used even when the printed wiring board is a component-embedded circuit board. A circuit board with a built-in component can be manufactured by a known manufacturing method.

A printed wiring board manufactured using the resin sheet of the present invention is provided with an insulating layer that is a cured product of the resin composition layer of the resin sheet, and an embedded wiring layer embedded in the insulating layer. good too.

<Semiconductor device>
A semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. A "conducting part" is a "part where an electric signal is transmitted on a printed wiring board", and the place may be a surface or an embedded part. Also, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. (BBUL) mounting method, anisotropic conductive film (ACF) mounting method, non-conductive film (NCF) mounting method, and the like. Here, the ``mounting method using a build-up layer without bumps'' is a ``mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board and the semiconductor chip is connected to wiring on the printed wiring board.''

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. The invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Synthesis Example 1: Synthesis of Elastomer>
In a reaction vessel, 69 g of bifunctional hydroxy group-terminated polybutadiene ("G-3000" manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3000, hydroxy group equivalent = 1800 g / eq.), and an aromatic hydrocarbon-based mixed solvent (Idemitsu Oil 40 g of "Ipsol 150" manufactured by Kagaku Co., Ltd.) and 0.005 g of dibutyltin laurate were added and mixed to dissolve uniformly. When the mixture became uniform, the temperature was raised to 60° C., and 8 g of isophorone diisocyanate (“IPDI” manufactured by Evonik Degussa Japan, isocyanate group equivalent=113 g/eq.) was added while stirring, and the reaction was carried out for about 3 hours.

Next, 23 g of a cresol novolac resin ("KA-1160" manufactured by DIC, hydroxyl equivalent=117 g/eq.) and 60 g of ethyl diglycol acetate (manufactured by Daicel) were added to the reactant and heated to 150° C. while stirring. The temperature was raised and the reaction was carried out for about 10 hours. The disappearance of the NCO peak at 2250 cm ⁻¹ was confirmed by FT-IR. Confirmation of the disappearance of the NCO peak was regarded as the end of the reaction, and the reaction mixture was allowed to cool to room temperature. Then, the reaction product was filtered through a 100-mesh filter cloth to obtain an elastomer having a butadiene structure and phenolic hydroxyl groups (phenolic hydroxyl group-containing butadiene resin: 50% by mass of non-volatile components). The elastomer had a number average molecular weight of 5900 and a glass transition temperature of -7°C.

<Example 1>
Biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent about 269) 10 parts, bisphenol AF type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX7760", epoxy equivalent about 235) 10 parts, bisphenol A type epoxy resin (“828EL” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 180) 5 parts, 40 parts of the elastomer obtained in Synthesis Example 1, active ester compound (“HPC-8000-65T” manufactured by DIC Corporation, active Group equivalent of about 223, non-volatile component of 65 mass% toluene solution) 5 parts, triazine skeleton-containing phenolic curing agent (DIC Corporation "LA-3018-50P", hydroxyl equivalent of about 151, solid content of 50% 2- Methoxypropanol solution) 5 parts, phosphazene compound (manufactured by Otsuka Chemical Co., Ltd., "SPS-100" solid content 50% cyclohexanone solution) 10 parts, curing accelerator (4-dimethylaminopyridine (DMAP), solid content 5 mass% MEK solution) 4 parts, spherical silica (average particle diameter 0.5 μm, specific surface area 4 to 7 m ² /g, Co., Ltd.) surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 30 parts of "SO-C2" manufactured by Admatechs) and 25 parts of methyl ethyl ketone were mixed and uniformly dispersed in a high-speed rotating mixer to prepare a resin varnish.

<Example 2>
Spherical silica (average particle diameter 0.5 μm, specific surface area 4 to 7 m ² /g, Admatechs Co., Ltd. “SO- C2”) was added to 30 parts of spherical silica (average particle diameter 0.08 μm, specific surface area 30.7 m ² /g, Denka A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that 30 parts of "UFP-30" manufactured by Co., Ltd. was used.

<Example 3>
A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that 10 parts of a phosphazene compound (manufactured by Otsuka Chemical Co., Ltd., "SPS-100" solid content 50% cyclohexanone solution) was changed to 2 parts.

<Example 4>
10 parts of a phosphazene compound (manufactured by Otsuka Chemical Co., Ltd., "SPS-100" solid content 50% cyclohexanone solution), 5 parts of a phosphazene compound (manufactured by Otsuka Chemical Co., Ltd., "SPS-100" solid content 50% cyclohexanone solution) and phosphazene A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that the compound (manufactured by Otsuka Chemical Co., Ltd., "SPH-100" solid content 50% cyclohexanone solution) was changed to 5 parts.

<Example 5>
10 parts of a phosphazene compound (manufactured by Otsuka Chemical Co., Ltd., "SPS-100" solid content 50% cyclohexanone solution), 5 parts of a phosphazene compound (manufactured by Otsuka Chemical Co., Ltd., "SPS-100" solid content 50% cyclohexanone solution) and phosphazene Phosphorus-based flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide)2. A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that the amount was changed to 5 parts.

<Example 6>
Example 1 except that 40 parts of the elastomer obtained in Synthesis Example 1 was changed to 65 parts of a phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone having a solid content of 30% by mass). A resin varnish and an adhesive film were prepared in the same manner as above.

<Example 7>
Spherical silica (average particle diameter 0.5 μm, specific surface area 4 to 7 m ² /g, Admatechs Co., Ltd. “SO- A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that 30 parts of C2") was not used.

<Example 8>
A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that 2 parts of rubber particles (PARALOID EXL2655, manufactured by Dow Chemical Japan Co., Ltd.) were additionally used.

<Example 9>
Spherical silica (average particle diameter 0.5 μm, specific surface area 4 to 7 m ² /g, Admatechs Co., Ltd. “SO- C2") was added to 30 parts of spherical alumina (average particle diameter 1.5 μm, specific surface area 1.0 m ² /g, Denka ( A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that 30 parts of "DAW-01" (manufactured by Co., Ltd.) was used.

<Example 10>
A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that 10 parts of a phosphazene compound (manufactured by Otsuka Chemical Co., Ltd., "SPS-100" solid content 50% cyclohexanone solution) was changed to 1 part.

<Example 11>
A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that 10 parts of a phosphazene compound (manufactured by Otsuka Chemical Co., Ltd., "SPS-100" solid content 50% cyclohexanone solution) was changed to 30 parts.

<Example 12>
10 parts of a phosphazene compound (manufactured by Otsuka Chemical Co., Ltd., "SPS-100" solid content 50% cyclohexanone solution) was changed to 10 parts of a phosphazene compound (manufactured by Otsuka Chemical Co., Ltd. "SPH-100" solid content 50% cyclohexanone solution). A resin varnish and an adhesive film were produced in the same manner as in Example 1 except for the above.

<Example 13>
Except for changing 5 parts of bisphenol A type epoxy resin ("828EL" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 180) to 4 parts of naphthalene type epoxy resin ("HP4032SS" manufactured by DIC Corporation, epoxy equivalent of about 144) , a resin varnish and an adhesive film were prepared in the same manner as in Example 1.

<Example 14>
Biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent about 269) 10 parts xylene type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX7700", epoxy equivalent 270) Except for changing 10 parts , a resin varnish and an adhesive film were prepared in the same manner as in Example 1.

<Example 15>
Change 10 parts of biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269) to 10 parts of naphthylene ether type epoxy resin ("HP-6000" manufactured by DIC Corporation, epoxy equivalent of 250) A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that

<Example 16>
5 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, an active group equivalent of about 223, a toluene solution of 65% by mass of non-volatile components), a triazine skeleton-containing phenolic curing agent (manufactured by DIC Corporation "LA -3018-50P", hydroxyl equivalent of about 151, 2-methoxypropanol solution with a solid content of 50%) 5 parts of phenol novolac resin (manufactured by DIC Corporation "TD-2090-60M", hydroxyl equivalent of about 105, non-volatile component 60 A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that the content was changed to 4 parts of a methyl ethyl ketone solution (% by mass).

<Example 17>
Curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5% by mass) 4 parts of curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., "2-phenyl-4-methylimidazole (2P4MZ), solid A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that the content was changed to 4 parts.

<Example 18>
Resin varnish and adhesive were prepared in the same manner as in Example 1, except that 40 parts of the elastomer obtained in Synthesis Example 1 was changed to 30 parts and 5 parts of hydrogenated styrene-butadiene resin ("H1041" manufactured by Asahi Kasei Co., Ltd.) was used. A film was produced.

<Comparative Example 1>
Spherical silica (average particle diameter 0.5 μm, specific surface area 4 to 7 m ² /g, Admatechs Co., Ltd. “SO- C2") 30 parts of spherical silica not surface-treated with a silane coupling agent (average particle size 0.5 μm, specific surface area 4 to 7 m ² /g, Admatechs Co., Ltd. “SO-C2”) 30 parts A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that the

<Comparative Example 2>
A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that 10 parts of a phosphazene compound (manufactured by Otsuka Chemical Co., Ltd., "SPS-100" solid content 50% cyclohexanone solution) was not used.

<Test Example 1: Measurement of tensile modulus>
(1) Preparation of cured product for evaluation On the release agent-untreated surface of a release agent-treated PET film (“501010” manufactured by Lintec Co., Ltd., thickness 38 μm, 240 mm square), glass cloth base epoxy resin double-sided copper-clad lamination A plate (“R5715ES” manufactured by Panasonic Corporation, thickness 0.7 mm, 255 mm square) was overlapped and its four sides were fixed with a polyimide adhesive tape (width 10 mm) (hereinafter sometimes referred to as “fixed PET film”).

The resin varnishes prepared in Examples and Comparative Examples were applied on the release-treated surface of the "fixed PET film" with a die coater so that the thickness of the resin composition layer after drying was 40 μm, and the temperature was set at 80 ° C. It was dried at 120°C (100°C on average) for 10 minutes to obtain a resin sheet.

Then, the resin composition layer was heat-cured under curing conditions for 90 minutes after being placed in an oven at 180°C.

After thermal curing, the polyimide adhesive tape was peeled off, the cured product was removed from the glass cloth-based epoxy resin double-sided copper-clad laminate, and the PET film ("501010" manufactured by Lintec Co., Ltd.) was also peeled off to obtain a sheet-like cured product. rice field. The resulting cured product is referred to as "evaluation cured product".

(2) Measurement of tensile modulus The cured product for evaluation was cut into dumbbell-shaped No. 1 specimens to obtain test pieces. The tensile strength of the test piece was measured using a tensile tester "RTC-1250A" manufactured by Orientec Co., Ltd. to obtain the tensile modulus at 23°C. The measurement was carried out according to JIS K7127. This operation was performed 3 times. The average value of 3 times is shown in the following table.

<Test Example 2: Evaluation of reflow resistance>
(1) Lamination of resin sheets The resin varnishes prepared in Examples and Comparative Examples were released using a PET film ("Lumirror R80" manufactured by Toray Industries, Inc.) with an alkyd resin release agent ("AL-5" manufactured by Lintec). , Thickness 38 μm, softening point 130° C., hereinafter sometimes referred to as “release PET”). It was dried at 120°C (100°C on average) for 10 minutes to obtain a resin sheet. This resin sheet was laminated using a batch-type vacuum pressure laminator (MVLP-500, manufactured by Meiki Co., Ltd.) so that the resin composition layers were in contact with both sides of the laminate. Lamination was performed by reducing the pressure for 30 seconds to an air pressure of 13 hPa or less, and then pressing for 30 seconds at 100° C. and a pressure of 0.74 MPa.

(2) Curing of Resin Composition Layer The release PET was peeled off from the laminated resin sheet, and the resin composition layer was cured under curing conditions of 180° C. for 30 minutes to form an insulating layer. This is called substrate A.

(3) Roughening Treatment The surface of the insulating layer of the prepared substrate A is immersed in a swelling liquid, Swelling Dip Securigand P containing diethylene glycol monobutyl ether manufactured by Atotech Japan Co., Ltd., at 60° C. for 5 minutes, and then roughened. As a liquid, it is immersed in Concentrate Compact P (KMnO4: 60 g / L, NaOH: 40 g / L aqueous solution) manufactured by Atotech Japan Co., Ltd. for 15 minutes at 80 ° C. Finally, as a neutralization liquid, Reduction manufactured by Atotech Japan Co., Ltd. It was immersed in Shoryusin Securigant P at 40° C. for 5 minutes. This substrate was used as substrate B for evaluation.

(4) Plating by semi-additive method In order to form a circuit on the insulating layer surface, the substrate for evaluation B was immersed in an electroless plating solution containing PdCl ₂ and then in an electroless copper plating solution. After annealing by heating at 150° C. for 30 minutes, an etching resist was formed, and after pattern formation by etching, copper sulfate electroplating was performed to form a conductor layer with a thickness of 30±5 μm. Annealing was then performed at 180° C. for 60 minutes. This circuit board was used as a board C for evaluation.

(5) Blistering evaluation in the reflow process Cut the evaluation substrate C into small pieces of 100 mm × 50 mm, and repeat the solder reflow temperature with a peak temperature of 260°C. (Reflow temperature profile conforms to IPC/JEDEC J-STD-020C).

Evaluation was performed on 5 small pieces, and three or more small pieces with abnormalities such as swelling in the conductor layer were judged to be "x", and 1 to 2 small pieces with abnormalities such as swelling in the plated conductor layer was judged as "Δ", and those with no abnormality at all were judged as "◯". The results are shown in the table below.

<Test Example 3: Evaluation of haloing>
(1) Preparation of resin sheet The resin varnishes prepared in Examples and Comparative Examples are applied on release PET with a die coater so that the thickness of the resin composition layer after drying is 30 μm, and the temperature is from 80 ° C. Each resin sheet was obtained by drying at 120° C. (average 100° C.) for 10 minutes.

(2) Preparation of inner layer substrate As an inner layer substrate, a glass cloth-based epoxy resin double-sided copper-clad laminate having copper foil layers on both sides (copper foil thickness 18 μm, substrate thickness 0.4 mm, manufactured by Panasonic Corporation) “R1515A”) was etched by 1 μm with “CZ8101” manufactured by MEC Co., Ltd. to roughen the copper surface.

(3) Lamination of resin sheet The protective film was peeled off from the resin sheet to expose the resin composition layer. Both surfaces of the inner layer substrate were laminated so that the resin composition layer was in contact with the inner layer substrate using a batch-type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., 2-stage build-up laminator "CVP700"). Lamination was carried out by pressure bonding for 30 seconds at 130° C. and pressure of 0.74 MPa after reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less. Then, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 60 seconds.

(4) Thermal Curing of Resin Composition Layer After that, the inner layer substrate laminated with the resin sheet was placed in an oven at 100° C. and heated for 30 minutes. Then, it was transferred to an oven at 180° C. and heated for 30 minutes to thermally cure the resin composition layer to form an insulating layer. After that, the support was peeled off to obtain a cured substrate A having an insulating layer, an inner layer substrate and an insulating layer in this order.

(5) Laser via processing Using a CO ₂ laser processing machine (“605GTWIII (-P)” manufactured by Mitsubishi Electric), the insulating layer is irradiated with a laser beam, and the top diameter (diameter) of the insulating layer is about A plurality of via holes of 50 μm were formed. The irradiation conditions of the laser light were mask diameter 1.6 mm, pulse width 27 μs, energy 1.34 W/shot, number of shots 2, and burst mode. The cured substrate A in which via holes are formed in the insulating layer in this way is called a via-processed substrate A. As shown in FIG.

(6) Roughening Treatment The via-processed substrate A was subjected to a desmearing treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was performed.

(Wet desmear treatment)
The surface of the insulating layer of the via-processed substrate A is immersed in a swelling liquid (“Swelling Dip Securigant P” manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60° C. for 5 minutes, followed by an oxidizing agent. Immersed in a solution ("Concentrate Compact CP" manufactured by Atotech Japan, an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) at 80 ° C. for 10 minutes, and then a neutralizing solution (Atotech Japan "Reduction Solution Securigant P" manufactured by Co., Ltd., sulfuric acid aqueous solution) at 40° C. for 5 minutes, and then dried at 80° C. for 15 minutes. The via-processed substrate A subjected to this wet desmearing process is called a roughened substrate A. As shown in FIG.

(7) Measurement of Dimensions of Via Holes and Haloing Distance after Roughening Treatment The cross-section of the roughened substrate A was observed using an FIB-SEM composite device ("SMI3050SE" manufactured by SII Nanotechnology). Specifically, an FIB (focused ion beam) was used to shave the insulating layer so that a cross section parallel to the thickness direction of the insulating layer and passing through the center of the via bottom of the via hole appeared. This cross section was observed by SEM. In the observed image, a gap formed by peeling the insulating layer from the copper foil layer of the inner layer substrate continuously from the edge of the via bottom was observed. Therefore, the distance from the edge of the via bottom to the outer edge of the gap was measured as the haloing distance.

(Evaluation criteria for haloing)
If the haloing distance was 6 μm or less, it was judged as “◯”; The results are shown in the table below.

As shown in Table 1, (A) an epoxy resin, (B) a curing agent, and (C) a phosphazene compound, and further (D) an inorganic filler surface-treated with a silane coupling agent and (D') a silane coupling agent. The haloing distance was 10 μm or less when the total content of inorganic fillers not surface-treated with an agent was 50% by mass or less and the content of component (D′) was 4% by mass or less. On the other hand, when the component (D) is not included and the component (D') is more than 4% by mass (Comparative Example 1), and when the phosphazene compound is not included (Comparative Example 2), the haloing distance is greater than 10 μm. became. From the above results, if the total content of the components (A) to (C) is included, the total content of the components (D) and (D') is 50% by mass or less, and the component (D) is not included, It can be seen that a cured product capable of suppressing the haloing phenomenon can be obtained by using a resin composition in which the content of component (D') is 4% by mass or less.

REFERENCE SIGNS LIST 1 first conductor layer 11 principal surface of first conductor layer 2 second conductor layer 21 principal surface of second conductor layer 3 insulation layer 100 insulation layer 100U surface of insulation layer opposite to conductor layer 110 via hole 120 via bottom 120C center of via bottom 130 via top 140 discolored portion 150 edge of via bottom of via hole 160 gap portion 170 end portion of gap portion on outer peripheral side 180 edge of via top 190 edge portion on outer peripheral side of discolored portion 200 inner layer substrate 210 conductor layer t1 Distance between first conductor layer and second conductor layer (thickness of insulating layer between first and second conductor layers)
t2 Overall thickness of insulating layer Lb Bottom diameter of via hole Lt Top diameter of via hole Wb Haloing distance from edge of via bottom

Claims (19)

(A) an epoxy resin, (B) a curing agent, and (C) a phosphazene compound,
Further (D) contains an inorganic filler surface-treated with a silane coupling agent,
Further (D') contains or does not contain an inorganic filler that is not surface-treated with a silane coupling agent,
The total content of component (D) and component (D') is 50% by mass or less when the non-volatile component in the resin composition is 100% by mass,
A resin composition in which the content of the component (D) is 10% by mass or more when the non-volatile component in the resin composition is taken as 100 % by mass (however, a resin containing both a cyanate compound and a metal soap compositions; resin compositions containing both cyanate compounds and silicone polymers; and resin compositions containing both elastomers containing phosphorus atoms and phenolic hydroxyl groups, and metal hydrates.). (A) epoxy resin, (B) curing agent, (C) phosphazene compound, and (E) polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkyleneoxy structure, polyisoprene in the molecule a resin elastomer having one or more structures selected from a structure, a polyisobutylene structure, and a polycarbonate structure;
Further (D) contains an inorganic filler surface-treated with a silane coupling agent,
Further (D') contains or does not contain an inorganic filler that is not surface-treated with a silane coupling agent,
The total content of component (D) and component (D') is 50% by mass or less when the non-volatile component in the resin composition is 100% by mass,
A resin composition in which the content of component (D) is 10% by mass or more when the non-volatile component in the resin composition is 100% by mass (however, a resin composition containing both a cyanate compound and a silicone polymer and elastomers containing phosphorus atoms and phenolic hydroxyl groups, and resin compositions containing both metal hydrates). (A) an epoxy resin, (B) a curing agent, and (C) a phosphazene compound,
Further (D) contains an inorganic filler surface-treated with a silane coupling agent,
Further (D') contains or does not contain an inorganic filler that is not surface-treated with a silane coupling agent,
the silane coupling agent is a silane coupling agent selected from the group consisting of aminosilane coupling agents, epoxysilane coupling agents, and methacrylsilane coupling agents;
The total content of component (D) and component (D') is 50% by mass or less when the non-volatile component in the resin composition is 100% by mass,
A resin composition in which the content of component (D) is 10% by mass or more when the non-volatile component in the resin composition is taken as 100% by mass (however, a resin composition containing both a cyanate compound and a metal soap and elastomers containing phosphorus atoms and phenolic hydroxyl groups, and resin compositions containing both metal hydrates). (A) epoxy resin, (B) curing agent, (C) phosphazene compound, and (E) polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkyleneoxy structure, polyisoprene in the molecule a resin elastomer having one or more structures selected from a structure, a polyisobutylene structure, and a polycarbonate structure;
Further (D) contains an inorganic filler surface-treated with a silane coupling agent,
Further (D') contains or does not contain an inorganic filler that is not surface-treated with a silane coupling agent,
the silane coupling agent is a silane coupling agent selected from the group consisting of aminosilane coupling agents, epoxysilane coupling agents, and methacrylsilane coupling agents;
The total content of component (D) and component (D') is 50% by mass or less when the non-volatile component in the resin composition is 100% by mass,
A resin composition in which the content of component (D) is 10% by mass or more when the non-volatile component in the resin composition is 100% by mass (however, an elastomer containing a phosphorus atom and a phenolic hydroxyl group, and a metal excluding resin compositions containing both hydrates). The resin composition according to any one of claims 1 to 4, comprising 90% by mass or more of the component (D) when the total of the components (D) and (D') is 100% by mass. The resin composition according to any one of claims 1 to 5 , which does not contain component (D'). The resin composition according to any one of claims 1 to 6 , wherein the content of component (C) is 1 to 15 mass% when the non-volatile component in the resin composition is 100 mass%. The resin composition according to any one of claims 1 to 7 , wherein the specific surface area of component (D) and component (D') is 0.5 to 50 m ² /g. The resin composition according to any one of claims 1 to 8, further comprising ( F) a thermoplastic resin . Component (C) has the following formula (1):

[In the formula, R ¹ and R ² each independently represent an optionally substituted aryl group, and n represents an integer of 1-23. ]
The resin composition according to any one of claims 1 to 9, which is a compound represented by R ¹ and R ² are each independently an alkyl group, an alkoxy group, a cyano group, a halogen atom, and -X-R ³ (X is a single bond, -(alkylene group)-, -O-, -S -, -CO-, -SO ₂ -, -NHCO-, -CONH-, -OCO- or -COO-, and R ³ is selected from the group consisting of an alkyl group, an alkoxy group, a cyano group and a halogen atom An aryl group optionally having 1 to 3 substituents selected from the group consisting of groups represented by The resin composition according to claim 10, wherein The resin composition according to any one of claims 1 to 11, wherein the cured product obtained by heat curing at 180°C for 1 hour has a tensile modulus at 23°C of 5 GPa or less measured according to JIS K7127. thing. 13. The resin composition according to claim 12, wherein the tensile modulus is 2 GPa or less. The resin composition according to any one of claims 1 to 13, which is used for forming an insulating layer for forming a conductor layer. 15. The resin composition according to claim 14, which is used for forming an insulating layer for forming a conductor layer after roughening treatment. A cured product of the resin composition according to any one of claims 1 to 15. A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of claims 1 to 13 provided on the support. A printed wiring board comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,
A printed wiring board, wherein the insulating layer is a cured product of the resin composition according to any one of claims 1 to 13. 19. The printed wiring board according to claim 18, wherein said insulating layer has via holes.

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