JP6413444B2 - Resin sheet, laminated sheet, laminated board, and semiconductor device - Google Patents

Description

  The present invention relates to a resin sheet, a laminated sheet, a laminated plate, and a semiconductor device.

  As a manufacturing technique of a printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers (circuit layers) are alternately stacked is known. In a manufacturing method using a build-up method, the insulating layer is generally formed by curing an insulating resin layer.

  In recent years, miniaturization and thinning of printed wiring boards have been desired, and circuits formed on insulating layers tend to be miniaturized. This is because by miniaturizing the circuit, the density of the circuit formed over the insulating layer can be increased, and the number of stacked layers due to build-up can be reduced.

  In order to achieve further miniaturization and thinning of the printed wiring board, it is conceivable to make the insulating layer thinner. For example, Patent Document 1 discloses a technique for forming a thin insulating layer having excellent mechanical strength using a plurality of resin layers.

International Publication No. 2009/119621

  In reducing the thickness of the insulating layer, it is conceivable to form the insulating layer using a thin insulating resin layer. However, the present inventors have found that when a thin insulating resin layer is used, the formed insulating layer may exhibit high surface roughness after the roughening treatment. As described above, miniaturization of the circuit is desired for downsizing and thinning of the printed wiring board. However, if the roughness of the surface of the insulating layer after the roughening treatment is high, a fine circuit is formed on the insulating layer. It may become an obstacle when forming. The present inventors also have an insulative layer formed by using a thin insulating resin layer, which may swell in the component mounting process by solder reflow, and the conductor layer (circuit layer) may peel off, resulting in poor reflow resistance. I also found that there was a case.

  In the technique described in Patent Document 1, a thin insulating layer having excellent mechanical strength is formed using a resin sheet in which a resin composition layer is further provided on one side of the insulating resin layer. As a result of studying a technique of using the insulating resin layer and the resin composition layer in combination, the inventors of the present invention also exhibit a high surface roughness after the roughening treatment. In some cases, it was found that the reflow resistance may be inferior.

  The present inventors further confirmed that when the resin composition layer used in combination with the insulating resin layer is thinned, pinholes may be formed in the resin composition layer. Thickening the resin composition layer can prevent pinholes to some extent, but it does not contribute to the thinning of the insulating layer, but also has an effect derived from the insulating resin layer used in combination (for example, low thermal expansion coefficient) ).

  The present invention is a resin sheet for circuit formation that is used by being laminated on an insulating resin layer. The surface roughness after the roughening treatment is low, and an insulating layer exhibiting good reflow resistance is provided. It aims at providing the resin sheet provided with the thin resin composition layer by which generation | occurrence | production was suppressed.

  As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by using a resin composition layer containing an epoxy resin and an active ester curing agent, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin sheet for circuit formation used by being laminated on an insulating resin layer,
A support;
A resin composition layer bonded to the support,
The resin composition layer has a thickness of 0.1 μm to 6 μm,
The resin sheet in which the resin composition layer contains (A) an epoxy resin and (B) an active ester curing agent.
[2] The resin sheet according to [1], wherein the resin composition layer further includes (C) an inorganic filler.
[3] The resin sheet according to [2], wherein (C) the inorganic filler is silica.
[4] The content of the inorganic filler (C) in the resin composition is 25% by mass to 65% by mass when the nonvolatile component in the resin composition layer is 100% by mass, [2] or [ 3].
[5] The resin composition layer further includes (D) a polymer component, and (D) the polymer component is selected from the group consisting of an organic filler and a thermoplastic resin. Resin sheet.
[6] The resin sheet according to [5], wherein the polymer component (D) includes one or more selected from the group consisting of an organic filler, a phenoxy resin, and a polyvinyl acetal resin.
[7] The content of the polymer component (D) in the resin composition layer is 0.5% by mass to 23% by mass when the nonvolatile component of the resin composition layer is 100% by mass, [5] or The resin sheet according to [6].
[8] The resin sheet according to any one of [1] to [7], wherein the resin composition layer further includes (E) a curing accelerator.
[9] The content of the (E) curing accelerator in the resin composition layer is 0.1% by mass to 6% by mass when the resin component in the resin composition is 100% by mass. [8] The resin sheet as described in 2.
[10] The resin sheet according to [8] or [9], wherein the (E) curing accelerator includes one or more selected from the group consisting of an imidazole curing accelerator and an amine curing accelerator.
[11] (E) The curing accelerator includes one or more selected from the group consisting of an imidazole-epoxy resin adduct and 4-dimethylaminopyridine, and any of [8] to [10]. Resin sheet.
[12] The resin composition layer further includes (C) an inorganic filler, (D) a polymer component, and (E) a curing accelerator,
(D) the polymer component is selected from the group consisting of organic fillers and thermoplastic resins;
When the non-volatile component in the resin composition layer is 100% by mass, the content of (C) inorganic filler is 25% by mass to 65% by mass, and the content of (D) polymer component is 0.5% by mass to 23%. Mass%,
The resin sheet according to [1], wherein the content of the (E) curing accelerator is 0.1% by mass to 6% by mass when the resin component in the resin composition is 100% by mass.
[13] (C) The inorganic filler is silica,
(D) The polymer component includes one or more selected from the group consisting of an organic filler, a phenoxy resin, and a polyvinyl acetal resin,
(E) The resin sheet according to [12], wherein the curing accelerator includes at least one selected from the group consisting of an imidazole-epoxy resin adduct and 4-dimethylaminopyridine.
[14] The resin according to any one of [1] to [13], wherein the resin composition layer is obtained by drying a resin varnish containing a solvent having a boiling point of 100 ° C. or higher and a solvent having a boiling point of less than 100 ° C. Sheet.
[15] The resin sheet according to [14], wherein the resin composition layer is obtained by drying the resin varnish at a temperature of 150 ° C. or higher.
[16] The resin sheet according to any one of [1] to [15], wherein the support has a thickness of 5 μm to 100 μm.
[17] The resin sheet according to any one of [1] to [16], wherein the support has a thickness of 25 μm to 50 μm.
[18] The resin sheet according to any one of [1] to [17], wherein the arithmetic average roughness (Ra) of the surface in contact with the resin composition layer of the support is less than 200 nm.
[19] The resin sheet according to any one of [1] to [18], wherein the circuit is formed by a plating process.
[20] The resin sheet according to any one of [1] to [19], wherein the insulating resin layer is a prepreg.
[21] A laminated sheet comprising the resin sheet according to any one of [1] to [20] and a prepreg bonded to the resin sheet.
[22] An insulating layer formed by heating the resin sheet according to any one of [1] to [20] and the insulating resin layer in a state where the resin composition layer and the insulating resin layer are joined. Including laminates.
[23] The laminated plate according to [22], including a circuit formed on the surface of the insulating layer.
[24] A semiconductor device including the laminate according to [23].

  According to the present invention, a resin sheet for circuit formation used by being laminated on an insulating resin layer, the surface roughness after roughening treatment is low, and an insulating layer exhibiting good reflow resistance is provided. A resin sheet provided with a thin resin composition layer in which generation of holes is suppressed can be provided.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

[Resin sheet]
The resin sheet of the present invention is a resin sheet for circuit formation used by being laminated on an insulating resin layer. The resin sheet includes a support and a resin composition layer bonded to the support, the thickness of the resin composition layer is 0.1 μm to 6 μm, and the resin composition layer is (A) epoxy. It contains a resin and (B) an active ester curing agent.

  Details of the insulating resin layer used in combination with the resin sheet of the present invention will be described later. In the production of a printed wiring board, the resin sheet of the present invention is laminated on the insulating resin layer so that the resin composition layer and the insulating resin layer are joined. The resin composition layer and the insulating resin layer together form an insulating layer, but a circuit is formed on the surface of the insulating layer derived from the resin composition layer.

<Support>
The support is a structure composed of a plate-like body or a film having two opposing main surfaces, and examples thereof include an organic support and a metal support.

  Examples of the organic support material include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA), polystyrene, cyclic polyolefin, and triacetyl cellulose ( TAC), polyethersulfide (PES), polyetherketone (PEK), polyetheretherketone (PEEK), polyphenylenesulfide (PPS), polyimide, and the like. It is preferable to determine a suitable material according to conditions (details will be described later). For example, when using a vacuum hot press process employing a high temperature condition, the organic support material is preferably a material having a glass transition temperature of 100 ° C. or more from the viewpoint of heat resistance, among which polyethylene naphthalate, polystyrene, polyphenylene Sulfide and polyimide are preferable.

  Examples of the material for the metal support include copper and aluminum, and copper is preferable. As the copper support, a support made of a single metal of copper may be used, and it is made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.). A support may be used.

  The support may be subjected to a mat treatment or a corona treatment on the surface to be joined 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. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resins, olefin resins, urethane resins, and silicone resins. . Commercially available release agents include, for example, “SK-1,” “AL-5,” “AL-7,” Hitachi Chemical Co., Ltd. manufactured by Lintec Corporation, which are alkyd resin release agents. “Tes Fine 303”, “Tes Fine 305”, and the like are available.

  The thickness of the support is not particularly limited as long as the object of the present invention is not impaired, but is preferably 5 μm or more, more preferably 10 μm or more, and further preferably 15 μm or more, 20 μm or more, or 25 μm or more. The upper limit of the thickness of the support is not particularly limited, but is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, even more preferably 55 μm or less, 54 μm or less, 53 μm or less, 52 μm or less, 51 μm or less, Or it is 50 micrometers or less. In addition, when a support body is a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  From the viewpoint of obtaining an insulating layer with low surface roughness, the arithmetic average roughness (Ra) of the surface of the support in contact with the resin composition layer is preferably less than 200 nm, more preferably 180 nm or less, still more preferably 160 nm or less, They are 140 nm or less, 120 nm or less, 110 nm or less, 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, or 60 nm or less. The lower limit of the Ra value is not particularly limited, but can usually be 0.1 nm or more, 1 nm or more, and the like. The arithmetic average roughness (Ra) can be measured using a non-contact type surface roughness meter. As a specific example of the non-contact type surface roughness meter, “WYKO NT3300” manufactured by Becoins Instruments is cited.

  The Ra of the surface of the support that is not in contact with the resin composition layer (that is, the surface opposite to the resin composition layer) is not particularly limited as long as the effect of the present invention is exhibited, and is determined as appropriate. Good.

<Resin composition layer>
In the resin sheet of the present invention, the thickness of the resin composition layer is good in terms of reducing the thickness of the insulating layer, and the effect derived from the insulating resin layer used in combination with the resin sheet of the present invention (for example, low thermal expansion coefficient). From the viewpoint of achieving the above, it is 6 μm or less. When the resin composition layer is thinned, pinholes may be generated in the resin composition layer. Such a resin composition layer having pinholes may become an obstacle to circuit miniaturization when used as an insulating layer of a printed wiring board. Therefore, a technique for suppressing the generation of pinholes is required. In this regard, in the present invention, it is possible to further reduce the thickness of the resin composition layer while suppressing the generation of pinholes. For example, in the resin sheet of the present invention, the resin composition layer may be thinned to 5.5 μm or less, 5 μm or less, 4.5 μm or less, or 4 μm or less. The lower limit of the thickness of the resin composition layer is from the viewpoint of suppressing the generation of pinholes, from the viewpoint of obtaining an insulating layer having a low surface roughness after the roughening treatment, and from the viewpoint of obtaining an insulating layer having good reflow resistance. It is 1 μm or more, preferably 0.2 μm or more, more preferably 0.4 μm or more, further preferably 0.6 μm or more, 0.8 μm or more, or 1 μm or more. The thickness of the resin composition layer can be measured using, for example, a contact-type layer thickness meter. Examples of the contact-type layer thickness meter include “MCD-25MJ” manufactured by Mitutoyo Corporation.

  In the resin sheet of the present invention, the resin composition layer contains (A) an epoxy resin and (B) an active ester curing agent.

-(A) Epoxy resin-
Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak 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, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type Epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing ester Carboxymethyl resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, it has two or more epoxy groups in one molecule, and has a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and three or more epoxy groups in one molecule, It is preferable to contain a solid epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin in combination as an epoxy resin, a resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the cured product of the resin composition is also improved.

  The liquid epoxy resin has a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, and a butadiene structure. Epoxy resins are preferable, and bisphenol A type epoxy resins, bisphenol F type epoxy resins, and naphthalene type epoxy resins are more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032H”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “828US”, “jER828EL” manufactured by Mitsubishi Chemical Corporation. (Bisphenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "ZX1059" (bisphenol A type epoxy resin and bisphenol manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) F-type epoxy resin mixture), “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, “Celoxide 2021P” (manufactured by Daicel Corporation) (alicyclic epoxy resin having an ester skeleton) ), "PB-3600" (pig Epoxy resin) having an end structure. These may be used alone or in combination of two or more.

  Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac 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, and tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferable. Specific examples of the solid epoxy resin include “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” (cresol novolac type epoxy resin) manufactured by DIC Corporation, “ N-695 ”(cresol novolac type epoxy resin),“ HP-7200 ”(dicyclopentadiene type epoxy resin),“ EXA7311 ”,“ EXA7311-G3 ”,“ EXA7311-G4 ”,“ EXA7311-G4S ”,“ HP6000 ” ”(Naphthylene ether type epoxy resin),“ EPPN-502H ”(trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.,“ NC7000L ”(naphthol novolac type epoxy resin),“ NC3000H ”,“ NC3000 ”, “NC3000L”, “NC3100” (biphenyl) Epoxy resin), “ESN475V” (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “ESN485” (naphthol novolac type epoxy resin), “YX4000H”, “YL6121” (biphenyl type) manufactured by Mitsubishi Chemical Corporation Epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., Mitsubishi Chemical Corporation “YL7800” (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. “jER1010” (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “jER1031S” (tetraphenylethane type epoxy resin), and the like.

  When the liquid epoxy resin and the solid epoxy resin are used in combination as the epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1: 6 by mass ratio. preferable. By setting the quantity ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is obtained when used in the form of a resin sheet, ii) when used in the form of a resin sheet Sufficient flexibility is obtained, handling properties are improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii) above, the quantitative ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.3 to 1: 5 by mass ratio. Is more preferable, and the range of 1: 0.6 to 1: 4 is more preferable.

  The content of the epoxy resin in the resin composition layer is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. % Or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 50% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less or 35% by mass. It is as follows.

  In addition, in this invention, content of each component in a resin composition layer is a value when the non-volatile component in a resin composition layer shall be 100 mass% unless there is separate description.

  The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By becoming this range, the crosslinked density of hardened | cured material becomes sufficient and it can bring about an insulating layer with small surface roughness. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  The weight average molecular weight of an epoxy resin becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

-(B) Active ester curing agent-
The active ester curing agent is an active ester compound having one or more active ester groups in one molecule. In the resin sheet for circuit formation used by laminating on the insulating resin layer, the present inventors have a low surface roughness after the roughening treatment by using an active ester curing agent as a curing agent for the epoxy resin. It was also found that a thin insulating layer with good reflow resistance can be realized.

  As the active ester curing agent, an active ester compound having two or more active ester groups in one molecule is preferable. For example, phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds An active ester compound having two or more ester groups with high reaction activity in one molecule is preferably used. An active ester hardening | curing agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  From the viewpoint of improving heat resistance, an active ester compound 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 is preferable. Among them, an active ester compound obtained by reacting a carboxylic acid compound with at least one selected from a phenol compound, a naphthol compound, and a thiol compound is more preferable, and a carboxylic acid compound and an aromatic compound having a phenolic hydroxyl group Aromatic compounds having two or more active ester groups in one molecule, obtained by reacting a carboxylic acid compound having at least two or more carboxy groups in one molecule, and having a phenolic hydroxyl group An aromatic compound obtained by reacting with an aromatic compound, and more preferably an aromatic compound having two or more active ester groups in one molecule. The active ester compound may be linear or branched. Moreover, if the carboxylic acid compound having at least two or more carboxy groups in a molecule is a compound containing an aliphatic chain, the compatibility with the resin composition can be increased, and if it is a compound having an aromatic ring. Heat resistance can be increased.

  Examples of the carboxylic acid compound include an aliphatic carboxylic acid having 1 to 20 carbon atoms (preferably 2 to 10 and more preferably 2 to 8) and an aromatic having 7 to 20 carbon atoms (preferably 7 to 10). Carboxylic acid is mentioned. Examples of the aliphatic carboxylic acid include acetic acid, malonic acid, succinic acid, maleic acid, itaconic acid and the like. Examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Among these, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable from the viewpoint of heat resistance, and isophthalic acid and terephthalic acid are more preferable.

  The thiocarboxylic acid compound is not particularly limited, and examples thereof include thioacetic acid and thiobenzoic acid.

  Examples of the phenol compound include phenol compounds having 6 to 40 carbon atoms (preferably 6 to 30, more preferably 6 to 23, and further preferably 6 to 22). Specific examples include hydroquinone, Resorcin, bisphenol A, bisphenol F, bisphenol S, phenol phthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydroxybenzophenone, tri Examples thereof include hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol and the like. As the phenol compound, a phenol novolak or a phosphorus atom-containing oligomer having a phenolic hydroxyl group described in JP2013-40270A may be used.

  Examples of the naphthol compound include naphthol compounds having 10 to 40 carbon atoms (preferably 10 to 30, more preferably 10 to 20), and specific examples include α-naphthol, β-naphthol, , 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like. A naphthol novolak may also be used as the naphthol compound.

  Among them, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol, phenol novolac, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are preferred, catechol, 1,5 -Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydride Roxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol, phenol novolac, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferable, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 , 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene type diphenol, phenol novolac, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferred, 1,5-dihydroxynaphthalene, 1,6 -Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene diphenol, phenol More preferred are phosphorus, phosphorus atom-containing oligomers having phenolic hydroxyl groups, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type diphenols, phosphorus having phenolic hydroxyl groups Atom-containing oligomers are particularly preferred, and dicyclopentadiene type diphenols are particularly preferred.

  The thiol compound is not particularly limited, and examples thereof include benzene dithiol and triazine dithiol.

  Preferable specific examples of the active ester curing agent include 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 a benzoylated product of phenol novolac. Active ester compounds containing, active ester compounds obtained by reacting aromatic carboxylic acids and phosphorus atom-containing oligomers having phenolic hydroxyl groups, among which active ester compounds containing dicyclopentadiene-type diphenol structures, naphthalene structures More preferred is an active ester compound containing, an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group. In the present invention, the “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.

  As the active ester curing agent, active ester compounds disclosed in JP-A Nos. 2004-277460 and 2013-40270 may be used, and commercially available active ester compounds may also be used. Commercially available active ester compounds include, for example, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T”, “HPC-8000L-65M” (dicyclopentadiene type diacids) manufactured by DIC Corporation. Active ester compound containing a phenol structure), “9416-70BK” (active ester compound containing a naphthalene structure) manufactured by DIC Corporation, “DC808” (active ester compound containing phenol novolac acetylated product) manufactured by Mitsubishi Chemical Corporation Compound), "YLH1026" (active ester compound containing a benzoylated product of phenol novolak) manufactured by Mitsubishi Chemical Corporation, and "EXB9050L-62M" (phosphorus atom-containing active ester compound) manufactured by DIC Corporation.

  From the viewpoint of obtaining a thin insulating layer having a low surface roughness after the roughening treatment, and from the viewpoint of realizing a thin insulating layer exhibiting good reflow resistance, the content of the active ester curing agent in the resin composition is 1 % By mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, more preferably 4% by mass or more, 5% by mass or more, 6% by mass or more, 7% by mass or more, 8% by mass or more, or 10% by mass. The above is even more preferable. The upper limit of the content of the active ester curing agent is not particularly limited, but is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, 18% by mass or less, 16% by mass or less, or 15% by mass. % Is even more preferred.

  Further, when the number of epoxy groups in (A) the epoxy resin is 1, from the viewpoint of obtaining an insulating layer with good mechanical strength, the number of reactive groups in the (B) active ester curing agent is preferably 0.2 to 2, 3-1.5 are more preferable and 0.35-1 are still more preferable. Here, “the number of epoxy groups of the epoxy resin” is a value obtained by totaling the values obtained by dividing the solid mass of each epoxy resin present in the resin composition by the epoxy equivalent for all epoxy resins. The “reactive group” means a functional group capable of reacting with an epoxy group, and the “reactive group number of the active ester compound” means the solid content mass of the active ester compound present in the resin composition. This is the sum of all values divided by reactive group equivalents.

-(C) Inorganic filler-
The resin composition layer may further include an inorganic filler. By including the inorganic filler, the thermal expansion coefficient of the obtained insulating layer can be kept low.

  The material of the inorganic filler is not particularly limited. For example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, 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, and silica is particularly suitable. That. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type. Examples of commercially available spherical fused silica include “SO-C2” and “SO-C1” manufactured by Admatechs.

  The average particle size of the inorganic filler is not particularly limited, but is preferably 4 μm or less, more preferably 3 μm or less, further preferably 2 μm or less, and more preferably 1 μm or less from the viewpoint of obtaining an insulating layer having a low surface roughness after the roughening treatment. 0.7 μm or less, or 0.5 μm or less is even more preferable. On the other hand, from the viewpoint of obtaining a resin varnish having an appropriate viscosity and good handleability when forming the resin varnish, the average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.03 μm or more. 0.05 μm or more, 0.07 μm or more, or 0.1 μm or more is more preferable. The average particle diameter 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 can be created on a volume basis by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction type particle size distribution measuring device, “LA-500”, “LA-750”, “LA-950”, etc. manufactured by Horiba, Ltd. can be used.

  Inorganic fillers are aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents from the viewpoint of improving moisture resistance and dispersibility. It is preferable that it is processed with 1 or more types of surface treating agents. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” (3-mercaptopropyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd.). Silane), Shin-Etsu Chemical "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical "SZ-31" (Hexamethyldisilazane) manufactured by Co., Ltd.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, from the viewpoint of preventing the melt viscosity of the resin varnish and the melt viscosity in the sheet form, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is further included. preferable.

  The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by Horiba, Ltd. can be used.

  From the viewpoint of obtaining an insulating layer having a low coefficient of thermal expansion and obtaining an insulating layer having good reflow resistance, the content of the inorganic filler in the resin composition layer is preferably 25% by mass or more, more preferably 30% by mass. % Or more, more preferably 35% by mass or more, still more preferably 40% by mass or more, 45% by mass or more, or 50% by mass or more. The upper limit of the content of the inorganic filler is preferably 65% by mass or less, more preferably 60% by mass or less, and still more preferably 55% by mass from the viewpoint of suppressing the generation of pinholes and the mechanical strength of the obtained insulating layer. % Or less.

-(D) Polymer component-
The resin composition layer may further include a polymer component selected from the group consisting of (D1) an organic filler and (D2) a thermoplastic resin. By including a polymer component in combination with (A) an epoxy resin and (B) an active ester curing agent, the generation of pinholes can be further suppressed, and a thin insulating layer having a lower surface roughness after roughening treatment Can be formed.

  (D1) As the organic filler, any organic filler that can be used in the production of a printed wiring board may be used. Examples thereof include rubber particles, polyamide fine particles, and silicone particles, and rubber particles are preferable.

  The rubber particle is not particularly limited as long as it is a fine particle of a resin that has been subjected to a chemical crosslinking treatment on a resin exhibiting rubber elasticity and is insoluble and infusible in an organic solvent. For example, acrylonitrile butadiene rubber particles, butadiene rubber particles, Examples include acrylic rubber particles. Examples of commercially available rubber particles include “XER-91” manufactured by Nippon Synthetic Rubber Co., Ltd., “Staffyroid AC3355”, “Staffyroid AC3816”, “Stuffyroid AC3401N”, “Aka Kogyo Co., Ltd.”, “ “Staffyroid AC3816N”, “Stuffyroid AC3832”, “Stuffyroid AC4030”, “Stuffyroid AC3364”, “Stuffyroid IM101”, “Paraloid EXL2655”, “Paraloid EXL2602” manufactured by Kureha Chemical Industry Co., Ltd. .

  The average particle diameter of the organic filler is preferably in the range of 0.005 μm to 1 μm, more preferably in the range of 0.2 μm to 0.6 μm. The average particle diameter 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, etc., and the particle size distribution of the organic filler is measured by mass using a concentrated particle size analyzer (“FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.). It can be measured by creating a standard and setting the median diameter as the average particle diameter.

  (D2) Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, and polycarbonate resin. , Polyether ether ketone resin, and polyester resin. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

  The weight average molecular weight in terms of polystyrene of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C. using chloroform or the like as a mobile phase.

  Examples of the phenoxy resin 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, terpene Examples thereof include phenoxy resins having a skeleton and 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 the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). In addition, “FX280” and “FX293” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “YL7553”, “YL6794”, “YL7213” manufactured by Mitsubishi Chemical Corporation, “YL7290”, “YL7482” and the like can be mentioned.

  Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, “Electrical butyral 4000-2”, “Electrical butyral 5000-A”, “Electrical butyral 6000-C”, and “Electrical butyral 6000-EP” manufactured by Denki Kagaku Kogyo Co., Ltd. Sekisui Chemical Co., Ltd.'s S-REC BH series, BX series, KS series, BL series, BM series and the like.

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (polyimides described in JP-A Nos. 2002-12667 and 2000-319386).

  Specific examples of the polyamide-imide resin include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as “KS9100” and “KS9300” (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Chemical Co., Ltd.

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.

  Among them, from the viewpoint of further suppressing the generation of pinholes in the combination with (A) epoxy resin and (B) active ester curing agent, and from the viewpoint of obtaining a thin insulating layer having a further lower surface roughness after the roughening treatment. The polymer component is preferably an organic filler, a phenoxy resin, or a polyvinyl acetal resin. Therefore, in one suitable embodiment, (D) polymer component contains 1 or more types selected from the group which consists of an organic filler, a phenoxy resin, and a polyvinyl acetal resin.

  The content of the polymer component in the resin composition layer is preferably 0.5% by mass or more from the viewpoint of suppressing the generation of pinholes and obtaining a thin insulating layer having a low surface roughness after the roughening treatment. More preferably, it is 1 mass% or more, More preferably, it is 2 mass% or more, 3 mass% or more, 4 mass% or more, 5 mass% or more, 6 mass% or more, 7 mass% or more, or 8 mass% or more. The upper limit of the content of the polymer component is preferably 23% by mass or less, more preferably 22% by mass or less, still more preferably 21% by mass or less, 20% by mass or less, 19% by mass or less, 18% by mass or less, and 17% by mass. Hereinafter, it is 16 mass% or less, or 15 mass% or less.

-(E) Curing accelerator-
The resin composition layer may further contain a curing accelerator. By including a curing accelerator, the roughness of the surface of the insulating layer after the roughening treatment can be further reduced, and the reflow resistance can be further improved.

  Although it does not specifically limit as a hardening accelerator, For example, an imidazole type hardening accelerator, an amine type hardening accelerator, a phosphorus type hardening accelerator, a guanidine type hardening accelerator etc. are mentioned. A hardening accelerator may be used individually by 1 type, or may be used in combination of 2 or more type.

  Among them, from the viewpoint of obtaining an insulating layer having a particularly low surface roughness after the roughening treatment in a combination with (A) an epoxy resin and (B) an active ester curing agent, particularly from a viewpoint of obtaining an insulating layer having good reflow resistance. The curing accelerator preferably contains one or more selected from the group consisting of an imidazole curing accelerator and an amine curing accelerator.

  Examples of the imidazole curing accelerator 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'-undecylimidazolyl- (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 isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl Examples include imidazole compounds such as -3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins (also referred to as “adducts of imidazole-epoxy resins”), and imidazoles. -Adducts of epoxy resin are preferred. Specific examples of the imidazole-epoxy resin adduct include “P200H50” manufactured by Mitsubishi Chemical Corporation.

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

  Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

  Examples of the guanidine curing accelerator include 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] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  Among these, in combination with (A) epoxy resin and (B) active ester curing agent, from the viewpoint of realizing an insulating layer having particularly low reflow resistance and particularly low surface roughness after roughening treatment, As the curing accelerator, an imidazole-epoxy resin adduct and 4-dimethylaminopyridine are preferable. Accordingly, in a preferred embodiment, the curing accelerator includes at least one selected from the group consisting of an imidazole-epoxy resin adduct and 4-dimethylaminopyridine.

  From the viewpoint of obtaining an insulating layer having a low surface roughness after the roughening treatment, and from the viewpoint of obtaining an insulating layer having good reflow resistance, the content of the curing accelerator in the resin composition layer is the resin in the resin composition layer. When the component is 100% by mass, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, 0.3% by mass or more, 0.4% by mass or more, or 0.5% by mass or more. is there. The upper limit of the content is preferably 6% by mass or less, more preferably 5.5% by mass or less, still more preferably 5% by mass or less, 4.5% by mass or less, or 4% by mass or less. In addition, the “resin component” referred to regarding the content of the curing accelerator refers to a component excluding the inorganic filler among the non-volatile components constituting the resin composition layer.

  From the viewpoint of realizing an insulating layer having a particularly low surface roughness after the roughening treatment and having particularly good reflow resistance, the content of the curing accelerator in the resin composition is (B) in the resin composition layer. When the active ester curing agent is 100% by mass, the content of the curing accelerator is preferably 0.5% by mass or more, more preferably 0.75% by mass or more, further preferably 1% by mass or more, and 2% by mass. Or 3% by mass or more. The upper limit of the content is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, 30% by mass or less, or 25% by mass or less.

In a preferred embodiment, the resin composition layer further comprises (C) an inorganic filler, (D) a polymer component, and (E) a curing accelerator in addition to (A) the epoxy resin and (B) the active ester curing agent. And (D) the polymer component is selected from the group consisting of organic fillers and thermoplastic resins,
When the non-volatile component in the resin composition layer is 100% by mass, the content of (C) inorganic filler is 25% by mass to 65% by mass, and the content of (D) polymer component is 0.5% by mass to 23%. Mass%,
When the resin component in a resin composition is 100 mass%, content of (E) hardening accelerator is 0.1 mass%-6 mass%.

  According to such an embodiment, it is possible to provide an insulating layer having a low surface roughness after the roughening treatment, exhibiting good reflow resistance, and realizing a thin resin composition layer in which the occurrence of pinholes is suppressed. can do.

  Among such embodiments, (C) the inorganic filler is silica, and (D) the polymer component includes one or more selected from the group consisting of organic fillers, phenoxy resins, and polyvinyl acetal resins, (E ) An embodiment in which the curing accelerator includes at least one selected from the group consisting of an adduct of imidazole-epoxy resin and 4-dimethylaminopyridine is effective in suppressing surface roughness, reflow resistance, and pinhole generation. All show particularly good performance.

-(F) Curing agents other than active ester curing agents-
The resin composition layer may further contain a curing agent other than the active ester curing agent.

  The curing agent other than the active ester curing agent is not particularly limited as long as it has a function of curing an epoxy resin. For example, a phenol-based curing agent, a naphthol-based curing agent, a cyanate ester-based curing agent, a benzoxazine-based curing agent, and a carbodiimide. System curing agent and the like. These curing agents may be used alone or in combination of two or more.

  Among them, from the viewpoint of obtaining an insulating layer having a particularly low surface roughness after the roughening treatment in a combination with (A) an epoxy resin and (B) an active ester curing agent, particularly from a viewpoint of obtaining an insulating layer having good reflow resistance. As the curing agent other than the active ester curing agent, one or more selected from the group consisting of a phenolic curing agent, a naphthol curing agent and a cyanate ester curing agent is preferable.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of obtaining an insulating layer having excellent adhesion strength with the conductor layer, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. preferable. Among these, a triazine skeleton-containing phenol novolac resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion strength with the conductor layer. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "SN-495", "SN-375", "SN-395", "LA-7052," "LA-7054," "LA-3018," "LA-1356," "TD2090" manufactured by DIC Corporation Or the like.

  Although it does not specifically limit as a cyanate ester type hardening | curing agent, For example, novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening agent, dicyclopentadiene type cyanate ester type hardening agent, bisphenol type (bisphenol A type, And bisphenol F type, bisphenol S type, and the like) and cyanate ester-based curing agents, and prepolymers in which these are partially triazines. Specific examples include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4′-ethylidene diphenyl. Dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, Bifunctional cyanate resins such as 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol novolac and cresol novolac Invite from etc. Polyfunctional cyanate resin is, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (both phenol novolak polyfunctional cyanate ester resins) and “BA230” (part or all of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. And the like, and the like, and the like.

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Specific examples of the carbodiimide curing agent include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.

  When a curing agent other than the active ester curing agent is used, the content of the curing agent in the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 1.5% by mass. % Or more, or 2 mass% or more. The upper limit of the content is preferably 20% by mass or less, more preferably 15% by mass or less, 14% by mass or less, 13% by mass or less, or 12% by mass or less.

-(G) Flame retardant-
The resin composition layer may further contain a flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may be used in combination of 2 or more type. Although content of the flame retardant in a resin composition layer is not specifically limited, Preferably it is 0.5 mass%-10 mass%, More preferably, it is 1 mass%-9 mass%.

-Other additives-
The resin composition layer may further contain other components as necessary. Examples of such other components include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, and resins such as thickeners, antifoaming agents, leveling agents, adhesion promoters, and colorants. An additive etc. are mentioned.

  Although mentioned later for details, in the resin sheet of this invention, it is preferable that a resin composition layer is obtained by drying the resin varnish containing a solvent with a boiling point of 100 degreeC or more and a solvent with a boiling point of less than 100 degreeC. Thereby, generation | occurrence | production of a pinhole can be suppressed further and the insulating layer which has much better reflow tolerance is realizable. Especially, it is preferable that a resin composition layer is obtained by drying a resin varnish at the temperature of 150 degreeC or more.

  In the resin sheet of the present invention, a protective film according to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). Although the thickness of a protective film is not specifically limited, For example, it can be set as 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The resin sheet can be wound and stored in a roll shape, and can be used by removing the protective film when forming an insulating layer in the production of a printed wiring board.

  The resin sheet of the present invention is a resin sheet for circuit formation used by being laminated on an insulating resin layer. In the production of printed wiring boards, by using the resin sheet of the present invention in combination with an insulating resin layer, it is possible to realize a thin insulating layer having low surface roughness after roughening treatment and good reflow resistance. it can. Especially, the resin sheet of this invention can be used especially suitably as a resin sheet (resin sheet for circuit formation by a plating process) for performing circuit formation by a plating process.

[Production method of resin sheet]
The resin sheet of the present invention can be produced by providing a resin composition layer having a thickness of 0.1 μm to 6 μm so as to be bonded to a support.

In one embodiment, the resin sheet of the present invention can be produced by a method including the following (i), (ii) and (iii).
(I) (A) An epoxy resin and (B) a resin composition containing an active ester curing agent is dissolved in a solvent to prepare a resin varnish (ii) a resin varnish is coated on a support (iii) a resin Drying the varnish to form a resin composition layer having a thickness of 0.1 μm to 6 μm

  In (i), a resin varnish is prepared by dissolving a resin composition containing (A) an epoxy resin and (B) an active ester curing agent in a solvent. Details of each component (that is, (C) to (G) component and other additives) that can be used for forming the resin composition layer, including (A) epoxy resin and (B) active ester curing agent, As described in the above <Resin composition layer>.

  Solvents used for preparing the resin varnish include, for example, ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, ethers such as cellosolve, butyl carbitol, propylene glycol monomethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, Examples thereof include acetates such as propylene glycol monomethyl ether acetate and carbitol acetate, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. A solvent may be used individually by 1 type or may be used in combination of 2 or more type.

  From the viewpoint of suppressing the occurrence of pinholes in the resin composition layer and obtaining an insulating layer having good reflow resistance, the solvent has a boiling point of 100 ° C. or higher (preferably 105 ° C. or higher, more preferably 110 ° C. or higher. , 115 ° C or higher, or 120 ° C or higher) and a solvent having a boiling point of less than 100 ° C (preferably 95 ° C or lower, more preferably 90 ° C or lower, 85 ° C or lower, or 80 ° C or lower). Is preferred. Accordingly, in a preferred embodiment, a mixed solvent of a solvent having a boiling point of 100 ° C. or higher and a solvent having a boiling point of less than 100 ° C. is used as the solvent.

  The mass ratio of the solvent having a boiling point of 100 ° C. or higher and the solvent having a boiling point of lower than 100 ° C. [(solvent having a boiling point of 100 ° C. or higher) / (solvent having a boiling point of lower than 100 ° C.)] is preferably 2/8 to 8/2. More preferably, it is 3/7 to 7/3, more preferably 4/6 to 6/4, and still more preferably 4.5 / 5.5 to 5.5 / 4.5.

  The resin varnish is preferably prepared so that the content of nonvolatile components in the resin varnish is preferably in the range of 30% by mass to 70% by mass, more preferably 40% by mass to 70% by mass.

  In (ii), a resin varnish is applied on the support. The details of the support are as described above in <Support>.

  The application of the resin varnish may be performed by any conventionally known method as long as a coating film having a uniform thickness can be formed. For example, the resin varnish can be coated on the support using a coating device such as a die coater, a comma coater, a gravure coater, or a bar coater.

  From the viewpoint of obtaining an insulating layer having a low surface roughness, the arithmetic average roughness (Ra) of the surface of the support to which the resin varnish is applied is preferably less than 200 nm. The preferred range of Ra is as described above in <Support>.

  In (iii), the resin varnish is dried to form a resin composition layer having a thickness of 0.1 μm to 6 μm. The preferred range of the thickness of the resin composition layer is as described above in <Resin composition layer>.

  The resin varnish may be dried by a known drying method such as heating or hot air blowing. The drying conditions may be determined according to the boiling point of the solvent contained in the resin varnish.

  The drying process may be performed only once or a plurality of times. When the drying treatment is performed a plurality of times, the respective drying conditions may be the same or different.

  When the drying treatment is performed only once, for example, 50 to 200 ° C. (preferably 80 to 200 ° C., more preferably 90 to 200 ° C.) for 1 to 30 minutes (preferably 1 to 20 minutes, More preferably, the resin composition layer may be formed by drying the resin varnish for 1 minute to 15 minutes. From the viewpoint of obtaining an insulating layer having good reflow resistance, and when using a prepreg as the insulating resin layer, from the viewpoint of reducing the problem that the sheet-like fiber substrate is exposed in the insulating layer after the roughening treatment, 150 ° C. or higher ( It is preferable to dry the resin varnish at a temperature of preferably 160 ° C. or higher, 170 ° C. or higher, or 180 ° C. or higher.

  When the drying process is performed a plurality of times, for example, the second and subsequent drying processes may be performed at a higher temperature than the first drying process. Thereby, even when the above mixed solvent is used, the organic solvent having a low boiling point is volatilized by the first drying treatment, and the organic solvent having a high boiling point is efficiently volatilized by the second and subsequent drying treatments. Can do. For example, the first drying process is performed at a temperature of 50 ° C. or higher and lower than 150 ° C. (preferably 70 ° C. or higher and 140 ° C. or lower, more preferably 80 ° C. or higher and 130 ° C. or lower, or 90 ° C. or higher and 120 ° C. or lower). The second and subsequent drying treatments may be performed at a temperature of 200 ° C. or lower (preferably 160 ° C. or higher and 200 ° C. or lower, 170 ° C. or higher and 200 ° C. or lower, or 180 ° C. or higher and 200 ° C. or lower). When the drying treatment is performed a plurality of times, each drying treatment time is, for example, 1 minute to 30 minutes (preferably 1 minute to 20 minutes, more preferably 1 minute to 15 minutes, or 1 minute to 10 minutes). Good.

  In (iii), it is not always necessary to completely remove the solvent. When the content of the non-volatile component in the resin composition layer is 100% by mass, the content of the solvent is preferably 5% by mass or less, more preferably 3% by mass or less, 2% by mass or less, or 1% by mass or less. It may be.

  The method for producing a resin sheet may further include (iv) providing a protective film so as to be joined to the resin composition layer after (iii). The protective film is as described in the above [Resin sheet].

  In (iv), it is preferable that the protective film is laminated on the resin composition layer by a roll, press-bonding or the like. Lamination treatment can be performed using a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nichigo Morton, and the like.

[Laminated sheet]
The resin sheet of the present invention is excellent in adhesiveness, and can easily form a laminated sheet with various films including an insulating resin layer.

  In one embodiment, the laminated sheet of the present invention includes the resin sheet of the present invention and an insulating resin layer bonded to the resin composition layer of the resin sheet.

  As the insulating resin layer, a conventionally known insulating resin layer can be used when forming the insulating layer of the printed wiring board. The thickness of the insulating resin layer is preferably 70 μm or less, more preferably 60 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, or 20 μm or less from the viewpoint of reducing the thickness of the insulating layer. Although the minimum of the thickness of an insulating resin layer is not specifically limited, Usually, 1 micrometer or more, 5 micrometers or more, 10 micrometers or more etc. can be used.

  From the viewpoint of obtaining a thin insulating layer having excellent mechanical strength, the insulating resin layer is preferably a prepreg, but a thermosetting resin composition layer (hereinafter simply referred to as “thermosetting resin composition” not containing a sheet-like fiber base material). May be used). The thermosetting resin composition layer is not particularly limited as long as it exhibits sufficient hardness and insulation after curing, but generally contains an epoxy resin and a curing agent. The kind and content of the epoxy resin are as described for the (A) epoxy resin in the above <resin composition layer>. As the curing agent, a curing agent other than (B) active ester curing agent and (F) active ester curing agent in the above <resin composition layer>, that is, an active ester curing agent, a phenol curing agent, a naphthol curing agent, One or more selected from the group consisting of a cyanate ester-based curing agent and a benzoxazine-based curing agent may be used. At this time, the amount ratio between the epoxy resin and the curing agent is [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the curing agent] from the viewpoint of improving the mechanical strength and water resistance of the obtained insulating layer. ], Preferably 1: 0.2 to 1: 2, more preferably 1: 0.3 to 1: 1.5, and still more preferably 1: 0.4 to 1: 1. 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 the curing agent. From the viewpoint of reducing the coefficient of thermal expansion of the resulting insulating layer and preventing the occurrence of cracks and circuit distortion due to the difference in thermal expansion between the insulating layer and the conductor layer, the thermosetting resin composition layer contains an inorganic filler. Furthermore, it is preferable to include. As the inorganic filler, the (C) inorganic filler in the above <resin composition layer> may be used. The content of the inorganic filler in the thermosetting resin composition layer is, from the viewpoint of reducing the coefficient of thermal expansion of the resulting insulating layer, when the nonvolatile component in the thermosetting resin composition layer is 100% by mass, Preferably they are 50 mass% or more, More preferably, they are 55 mass% or more, More preferably, they are 60 mass% or more, 65 mass% or more, 70 mass% or more, or 75 mass% or more. The upper limit of the content of the inorganic filler is preferably 95% by mass or less, more preferably 90% by mass or less or 85% by mass or less, from the viewpoint of mechanical strength of the obtained insulating layer. Examples of other components that can be contained in the thermosetting resin composition layer include (D) the polymer component, (E) the curing accelerator, and “other additives” described in the above <Resin composition layer>. Is mentioned.

  In a preferred embodiment, the laminated sheet of the present invention includes the resin sheet of the present invention and a prepreg bonded to the resin composition layer of the resin sheet.

  A prepreg is formed by impregnating a thermosetting resin composition in a sheet-like fiber base material.

  The thermosetting resin composition used for the prepreg is not particularly limited as long as the cured product has sufficient hardness and insulation, and a conventionally known thermosetting resin composition used for forming an insulating layer of a printed wiring board. May be used. For example, you may use the resin composition used for formation of said thermosetting resin composition layer. Alternatively, the thermosetting resin composition used for the prepreg may be the same as the resin composition used for forming the resin composition layer in the resin sheet of the present invention.

The sheet-like fiber base material used for a prepreg is not specifically limited, What is used normally as base materials for prepregs, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of reducing the thickness of the insulating layer, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, 25 μm or less, or 20 μm or less. Although the minimum of the thickness of a sheet-like fiber base material is not specifically limited, Usually, you may be 5 micrometers or more, 10 micrometers or more. Specific examples of the glass cloth base material used as the sheet-like fiber base material include “Style 1027MS” (warp density 75/25 mm, weft density 75/25 mm, fabric weight 20 g / m ² ) manufactured by Asahi Schwer Corporation. , Thickness 19 μm), “Style 1037MS” manufactured by Asahi Schubel Co., Ltd. (warp density 70/25 mm, weft density 73/25 mm, fabric weight 24 g / m ² , thickness 28 μm), manufactured by Arisawa Manufacturing Co., Ltd. "1078" (warp density 54 / 25mm, weft density 54 / 25mm, fabric weight 48g / m ² , thickness 43μm), "1037NS" manufactured by Arizawa Seisakusho (warp density 72 / 25mm, weft Density 69 pieces / 25 mm, fabric weight 23 g / m ² , thickness 21 μm) “1027NS” manufactured by Arisawa Manufacturing Co., Ltd. (warp density 75 pieces / 25 mm, weft density 75 Book / 25 mm, cloth weight 19.5 g / m ² , thickness 16 μm), “1015NS” manufactured by Arisawa Manufacturing Co., Ltd. (warp density 95/25 mm, weft density 95/25 mm, cloth weight 17.5 g / m ² , 15 μm thick), “1000NS” manufactured by Arisawa Manufacturing Co., Ltd. (warp density 85/25 mm, weft density 85/25 mm, fabric weight 11 g / m ² , thickness 10 μm), and the like. Specific examples of the liquid crystal polymer nonwoven fabric include “Veculus” (weight per unit area: 6 to 15 g / m ² ) and “Vectran” manufactured by Kuraray Co., Ltd., which are produced by the melt blow method of an aromatic polyester nonwoven fabric.

  The prepreg can be produced by a known method such as a hot melt method or a solvent method.

  When using a thin prepreg, the sheet-like fiber base material may be exposed in the insulating layer after the roughening treatment. The exposure of such a sheet-like fiber base material becomes an obstacle in forming a fine circuit in the production of a printed wiring board. In this regard, according to the laminated sheet of the present invention in which the resin composition layer containing (A) the epoxy resin and (B) the active ester curing agent is bonded to the prepreg, the thin prepreg is used. Moreover, exposure of the sheet-like fiber base material in the insulating layer after the roughening treatment can be advantageously suppressed. For example, the thickness of the prepreg may be reduced to 70 μm or less, 60 μm or less, 50 μm or less, 40 μm or less, or 30 μm or less. Although the minimum of the thickness of a prepreg is not specifically limited, Usually, it may be 10 micrometers or more, 12 micrometers or more, etc. The thickness of the prepreg can be easily changed by adjusting the amount of impregnation of the thermosetting resin composition.

  The laminated sheet of the present invention is produced by laminating the resin sheet of the present invention and the insulating resin layer so that the resin composition layer of the resin sheet of the present invention and the insulating resin layer (preferably prepreg) are joined. be able to. For example, the laminated sheet of the present invention can be produced by laminating the resin sheet of the present invention on an insulating resin layer such that the resin composition layer of the resin sheet is bonded to the insulating resin layer.

  Since the lamination of the resin sheet and the insulating resin layer of the present invention has good workability and a uniform contact state is easily obtained, the resin sheet of the present invention can be applied to the insulating resin layer by roll crimping or press crimping. Lamination is preferable. Lamination can be performed using a commercially available vacuum laminator. The commercially available vacuum laminator is as described above.

  In the production of the laminated sheet, the insulating resin layer may be used in the form of an adhesive sheet including a support and an insulating resin layer bonded to the support. As the support, the same support as described for the resin sheet may be used.

  When the insulating resin layer is used in the form of an adhesive sheet, a protective film according to the support is further provided on the surface of the insulating resin layer that is not joined to the support (that is, the surface opposite to the support). Can be stacked. As a protective film, you may use the same thing as the protective film demonstrated about the said resin sheet. The adhesive sheet can be wound and stored in a roll shape, and can be used by peeling off the protective film when producing a laminated sheet.

  The laminated sheet of the present invention can be used as a laminated sheet for forming an insulating layer of a printed wiring board (a laminated sheet for an insulating layer of a printed wiring board). The method for producing a printed wiring board using the laminated sheet of the present invention will be described later. By forming an insulating layer of the printed wiring board using the laminated sheet of the present invention, the surface roughening after the roughening treatment is performed. A thin insulating layer having a low degree and good reflow resistance can be realized. Above all, in the production of printed wiring boards by the build-up method, it can be suitably used as a laminated sheet for forming an insulating layer (a laminated sheet for a build-up insulating layer of a printed wiring board), and on top of that by a plating process It can be more suitably used as a laminated sheet for forming an insulating layer on which a circuit is formed (a laminated sheet for a build-up insulating layer of a printed wiring board on which a circuit is formed by a plating process).

  When the insulating resin layer is used in the form of the adhesive sheet in the production of the laminated sheet, the obtained laminated sheet is a surface of the insulating resin layer that is not bonded to the resin sheet of the present invention (that is, the resin of the present invention). A support derived from an adhesive sheet is provided on the surface opposite to the sheet. When manufacturing a laminated board and a printed wiring board, it becomes useable by peeling the support body derived from such an adhesive sheet.

[Laminated board]
The laminated board of this invention contains the insulating layer formed by heating the resin sheet of this invention, and the insulating resin layer in the state which the resin composition layer and the insulating resin layer joined.

In one embodiment, the laminate of the present invention can be produced by a method including the following step (I-1) using the resin sheet and the insulating resin layer of the present invention (hereinafter referred to as “first embodiment”). Also called.).
(I-1) One or more insulating resin layers are arranged between two resin sheets arranged so that the resin composition layers face each other, and heated and pressurized at 200 ° C. or higher under reduced pressure. Integrated molding process

  The resin sheet and insulating resin layer used in the first embodiment are as described above. In the first embodiment, the insulating resin layer is preferably a prepreg.

  Step (I-1) can be performed, for example, using a vacuum hot press apparatus according to the following procedure.

First, a laminated structure in which one or more insulating resin layers are arranged between two resin sheets arranged so that the resin composition layers face each other is set in a vacuum hot press apparatus.
The laminated structure is preferably set in a vacuum hot press apparatus via a cushion sheet, a metal plate such as a stainless plate (SUS plate), a release film, or the like. The laminated structure is, for example, cushion paper / metal plate / release film / laminated structure (for example, resin sheet / insulating resin layer / resin sheet) / release film / SUS plate / cushion paper in this order and vacuum hot press apparatus Set to
Here, the symbol “/” means that the components shown so as to sandwich this are arranged so as to contact each other (the same applies to the description of the laminated structure and the like hereinafter).

  Next, a vacuum hot press process is performed in which the laminated structure is thermocompression bonded under reduced pressure conditions.

  The vacuum hot press treatment can be performed using a conventionally known vacuum hot press apparatus that presses the laminated structure from both sides thereof with a heated metal plate such as an SUS plate. Examples of commercially available vacuum heat press apparatuses include “MNPC-V-750-5-200” manufactured by Meiki Seisakusho, “VH1-1603” manufactured by Kitagawa Seiki Co., Ltd., and the like.

  The vacuum hot press treatment may be performed only once or may be repeated twice or more.

In the vacuum hot press treatment, the pressure bonding pressure (pressing force) is preferably 5 kgf / cm ^{2 to} 80 kgf / cm ² (0.49 MPa to 7.9 MPa), more preferably 10 kgf / cm ^{2 to} 60 kgf / cm ² (0. 98 MPa to 5.9 MPa).

In the vacuum hot press treatment, the pressure of the atmosphere, that is, the pressure at the time of depressurization in the chamber in which the laminated structure to be treated is stored is preferably 3 × 10 ⁻² MPa or less, more preferably 1 × 10 ⁻² MPa or less. It is.

  In the vacuum hot press treatment, the heating temperature (T) is 200 ° C. or higher, preferably 210 ° C. or higher, more preferably 220 ° C. or higher. Although the upper limit of heating temperature (T) is not specifically limited, Usually, it can be 240 degrees C or less.

  In the vacuum hot press treatment, from the viewpoint of obtaining an insulating layer having a low surface roughness after the roughening treatment, the temperature is raised stepwise or continuously and / or the temperature is lowered stepwise or continuously. However, it is preferable to implement. In such a case, it is preferable that the highest temperature reaches the desired temperature condition.

Vacuum hot pressing process, for example, the temperature was raised at a heating rate S ₁ from room temperature to the heating temperature (T), after holding for a predetermined time at heating temperature (T), the heating temperature (T) at a cooling rate S ₂ You may implement on the heating conditions which fall to normal temperature. Heating rate _{S 1} and cooling rate _{S 2} is generally 0.5 ° C. / min to 30 ° C. / min, preferably 1 ° C. / minute to 10 ° C. / min, more preferably at 2 ° C. / min to 8 ° C. / min is there. The time for holding at the heating temperature (T) is not particularly limited as long as the effect of the present invention is exhibited, but is usually 1 minute to 180 minutes, preferably 5 minutes to 150 minutes, more preferably 10 minutes to 120 minutes. is there.

  The step (I-1) may be performed by using two or more insulating resin layers and further disposing an inner layer substrate between the insulating resin layers. Two or more insulating resin layers may be the same or different.

  In the present invention, the “inner layer substrate” is mainly a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or a pattern process on one or both sides of the substrate. A circuit board on which a conductive layer (circuit) is formed. Further, when the printed wiring board is manufactured, an inner layer circuit board of an intermediate product in which an insulating layer and / or a conductor layer is further formed is also included in the “inner layer board” in the present invention.

  By the step (I-1), the resin composition layer of the resin sheet and the insulating resin layer are integrated to form an insulating layer.

In another embodiment, the laminate of the present invention can be produced by a method including the following steps (II-1) and (II-2) using the laminate sheet of the present invention (hereinafter, “second” Also referred to as “embodiment”).
(II-1) A step of laminating the laminated sheet on the inner layer substrate so that the insulating resin layer is in contact with the inner layer substrate (II-2) A step of thermosetting the laminated sheet to form an insulating layer

  The laminated sheet and inner layer substrate used in the second embodiment are as described above.

  In step (II-1), the laminated sheet of the present invention is laminated on the inner layer substrate so that the insulating resin layer is in contact with the inner layer substrate.

  Lamination of the laminated sheet and the inner layer substrate in the step (II-1) can be performed, for example, by thermocompression bonding the laminated sheet to the inner layer substrate from the support side. Examples of the member that heat-presses the laminated sheet to the inner layer substrate (hereinafter also referred to as “heat-pressing member”) include a heated metal plate (SUS end plate, etc.) or a metal roll (SUS roll). In addition, it is preferable not to press the thermocompression bonding member directly on the laminated sheet but to press the laminated sheet through an elastic material such as heat-resistant rubber so that the laminated sheet sufficiently follows the surface irregularities of the inner layer substrate.

The lamination of the laminated sheet and the inner layer substrate may be performed by a vacuum laminating method. In the vacuum laminating method, the heating temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably in the range of 80 ° C. to 140 ° C., and the pressure bonding pressure is preferably 1 kgf / cm ^{2 to} 18 kgf / cm ² (0.098 MPa to 1.77MPa), more preferably in the range of ^{3kgf / cm 2 ~15kgf / cm 2} (0.29MPa~1.47MPa), bonding time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 The range of seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

  In step (II-1), the laminated sheet may be laminated on one side of the inner layer substrate, or may be laminated on both sides of the inner layer substrate.

  Lamination | stacking of a lamination sheet and an inner layer board | substrate can be performed with a commercially available vacuum laminator. The commercially available vacuum laminator is as described above.

  After the lamination, the laminated sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment may be the same conditions as the thermocompression bonding conditions for the laminate. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination | stacking and a smoothing process continuously using said commercially available vacuum laminator.

  In step (II-2), the laminated sheet is thermally cured to form an insulating layer.

  The conditions for thermosetting are not particularly limited, and the conditions normally employed when forming the insulating layer of the printed wiring board may be used.

  For example, although the thermosetting conditions of the laminated sheet vary depending on the composition of the resin composition layer and the insulating resin layer, the curing temperature is in the range of 120 ° C. to 240 ° C. (preferably in the range of 150 ° C. to 210 ° C., more preferably 170. C. to 190.degree. C.), and the curing time may be in the range of 5 to 90 minutes (preferably 10 to 75 minutes, more preferably 15 to 60 minutes).

  Prior to thermosetting the laminated sheet, the laminated sheet may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the laminated sheet, the laminated sheet is kept at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower) for 5 minutes or longer ( (Preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

  By the step (II-2), both the resin composition layer and the insulating resin layer in the laminated sheet are thermally cured to form an integrated insulating layer.

  The insulating layer formed according to the present invention can exhibit the effects derived from the insulating resin layer satisfactorily. The insulating resin layer is usually designed to provide an insulating layer with a low coefficient of thermal expansion, and according to the present invention, it is possible to form an insulating layer that exhibits the effect of such a low coefficient of thermal expansion. In one embodiment, the insulating layer contained in the laminate of the present invention can exhibit a linear thermal expansion coefficient of preferably 15 ppm / ° C. or lower, 14 ppm / ° C. or lower, or 13 ppm / ° C. or lower. The lower limit of the coefficient of linear thermal expansion of the insulating layer is not particularly limited, but is usually 1 ppm or more. The linear thermal expansion coefficient of the insulating layer can be measured by a known method such as thermomechanical analysis. Examples of the thermomechanical analyzer include “Thermo Plus TMA8310” manufactured by Rigaku Corporation. In this invention, the linear thermal expansion coefficient of an insulating layer is an average linear thermal expansion coefficient in the range of 25 degreeC-150 degreeC of a plane direction at the time of performing a thermomechanical analysis by the tension | pulling load method (JIS K7197).

  Regardless of whether the first embodiment or the second embodiment is different, (III) a step of drilling the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a circuit on the surface of the insulating layer. May be further implemented. Therefore, in one embodiment, the laminate of the present invention includes a circuit formed on the surface of the insulating layer.

  In addition, what is necessary is just to remove a support body before forming a circuit in the surface of an insulating layer irrespective of the difference of 1st Embodiment and 2nd Embodiment. In detail, in 1st Embodiment, a support body is between process (I-1) and process (III), between process (III) and process (IV), or process (IV) and process ( V) may be removed. In 2nd Embodiment, a support body is between process (II-1) and process (II-2), between process (II-2) and process (III), process (III) and process (IV). ) Or between step (IV) and step (V). When an organic support is used as the support, the organic support can be peeled off. When a metal support is used as the support, the metal support can be removed by etching.

  Step (III) is a step of making a hole 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, a laser, plasma, or the like depending on the resin composition layer used for forming the insulating layer, the composition of the insulating resin layer, and the like. 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 for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board 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 neutralization treatment with a neutralizing liquid in this order. Although it does not specifically limit as a swelling liquid, An alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution, As this alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan Co., Ltd. Although the swelling process by a swelling liquid is not specifically limited, For example, it can carry out by immersing an insulating layer for 1 minute-20 minutes in 30-90 degreeC swelling liquid. Although it does not specifically limit as an oxidizing agent, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan Co., Ltd. The neutralizing solution is preferably an acidic aqueous solution. Examples of commercially available products include “Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes.

  As described above, when a thin insulating layer is formed using a thin insulating resin layer, the formed insulating layer may exhibit a high surface roughness after the roughening treatment. On the other hand, according to the present invention, it is possible to advantageously form an insulating layer that is thin but has a low surface roughness after the roughening treatment. In one embodiment, the arithmetic average roughness (Ra) of the insulating layer surface after the roughening treatment is preferably 250 nm or less, more preferably 240 nm or less, still more preferably 220 nm or less, even more preferably 200 nm or less, 190 nm or less, It is 180 nm or less, 170 nm or less, 160 nm or less, or 150 nm or less. Although the lower limit of Ra value is not specifically limited, 0.5 nm or more is preferable and 1 nm or more is more preferable. The arithmetic average roughness (Ra) of the insulating layer surface can be measured using a non-contact type surface roughness meter. As a specific example of the non-contact type surface roughness meter, “WYKO NT3300” manufactured by Becoins Instruments is cited.

  Step (V) is a step of forming a circuit (conductor layer) on the surface of the insulating layer.

  The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is 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. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel / chromium alloy, copper / An alloy layer of nickel alloy or copper / titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel / chromium alloy is more preferable, and a single layer of copper is preferable. A metal layer is more preferred.

  The conductor layer may have a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types 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.

  Although the thickness of a conductor layer is based on the design of a desired printed wiring board, it is 3 micrometers-50 micrometers normally, Preferably it is 5 micrometers-30 micrometers.

  The conductor layer can be formed by a plating process. For example, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. Hereinafter, an example in which the conductor layer is formed by a semi-additive method will be described.

  First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. A metal layer is formed by electrolytic plating on the exposed plating seed layer, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

  The insulating layer and the conductor layer are required to exhibit sufficient peel strength (adhesion strength), and in general, such adhesion is obtained by an anchor effect caused by irregularities on the surface of the insulating layer. However, if the irregularities on the surface of the insulating layer are large, it is difficult to remove the seed layer of the anchor portion when removing the unnecessary plating seed layer by etching when forming the wiring pattern, and the conditions under which the plating seed layer of the anchor portion can be sufficiently removed. In the case of the etching, the dissolution of the wiring pattern becomes remarkable, which hinders circuit miniaturization. On the other hand, according to the present invention, even when a thin insulating layer is formed, the surface roughness after the roughening treatment is low while maintaining sufficient peel strength between the insulating layer and the conductor layer. An insulating layer can be advantageously obtained. Therefore, the present invention significantly contributes to both circuit miniaturization and thinning of the insulating layer. For example, the ratio (L / S) of the conductor circuit width (line; L) to the width (space; S) between the conductor circuits is preferably 35/35 μm or less, more preferably 30/30 μm or less, and even more preferably 25/25 μm. Hereinafter, a fine circuit of 20/20 μm or less, 15/15 μm or less, or 10/10 μm or less can be formed with high yield.

  The laminated board of the present invention is used for various applications depending on its production method and structure (for example, the presence or absence of the use of the inner layer substrate in the first embodiment, the presence or absence of the circuit in the first and second embodiments, etc.). obtain. For example, it may be used as an inner layer substrate such as an insulating core substrate or an inner layer circuit substrate used for manufacturing a printed wiring board, or may be used as a printed wiring board.

[Semiconductor device]
A semiconductor device can be manufactured using a printed wiring board made of the laminated board of the present invention or using a printed wiring board manufactured using the laminated board of the present invention. Use of the laminate of the present invention advantageously suppresses separation between the insulating layer and the conductor layer (circuit) due to swelling of the insulating layer, etc., in a mounting process employing a high solder reflow temperature with a peak temperature of 260 ° C. And high reflow reliability can be realized.

  Examples of the semiconductor device include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

  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. The “conduction location” is a “location where an electrical signal is transmitted on a printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, “a mounting method using a build-up layer without a bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. It is.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, “parts” means “parts by mass” unless otherwise specified.

<Measurement method / Evaluation method>
First, various measurement methods and evaluation methods will be described.

[Preparation of evaluation substrate]
(1) Base treatment of inner layer circuit board Etching on both sides of glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18μm, substrate thickness 0.8mm, Matsushita Electric Works “R5715ES”) Thus, a circuit pattern was formed to produce an inner layer circuit board. The copper circuit of the obtained inner layer circuit board was roughened with a microetching agent (“CZ8100” manufactured by Mec Co., Ltd.).

(2) Production of Laminate Board Using the resin sheet produced in Examples and Comparative Examples, the insulating resin layer, and the inner layer circuit board obtained in (1) above, the support / insulating layer / inner layer circuit board / insulation A laminate having a layer configuration of layer / support was prepared. A prepreg (“GEA-800G” manufactured by Hitachi Chemical Co., Ltd., thickness 0.06 mm) was used as the insulating resin layer.

  The laminated board was produced using the vacuum heat press apparatus ("VH1-1603" by Kitagawa Seiki Co., Ltd.). In detail, the following structure was made into 1 set, and it implemented by carrying out the vacuum hot press process in the state which piled up this 3 sets.

  Structure: cushion paper / SUS board / release film / resin sheet (support / resin composition layer) / insulating resin layer / inner circuit board / insulating resin layer / resin sheet (resin composition layer / support) / release Film / SUS board / cushion paper

  “AACP-9N” (800 μm thickness) manufactured by Awa Paper Co., Ltd. was used as the cushion paper, and “Aflex 50N NT” (50 μm thickness) manufactured by Asahi Glass Co., Ltd. was used as the release film. The thickness of the SUS plate was 1 μm.

The conditions for the vacuum hot press treatment are as follows.
Temperature: The temperature was raised from room temperature (room temperature) to 220 ° C. at a rate of temperature rise of 5 ° C./min, held at 220 ° C. for 90 minutes, and then the temperature drop pressure from 220 ° C. to room temperature at a temperature drop rate of 5 ° C./min ( (Pressing force): The pressing force is set to 50 kgf / cm ² (4.9 MPa) at the start of temperature rise from room temperature, and this is maintained until the temperature is lowered. Pressure of the holding atmosphere: 70 mmHg to 74 mmHg (9.3 × 10 ⁻³ MPa to 9.MPa). 9 × 10 ⁻³ MPa)

(3) Removal of support When the support was an organic support, it was peeled off. When the support was a metal support, the laminate was immersed in a ferric chloride aqueous solution at 25 ° C. for 10 minutes and removed by etching.

(4) Roughening treatment After removing the support, the laminate was placed in a swelling liquid (“Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd.) at 60 ° C. for 5 minutes, and then an oxidizing agent (Atotech Japan Co., Ltd.). “Concentrate Compact CP”, an aqueous solution of potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) at 80 ° C. for 20 minutes, and finally a neutralization solution (“Reduction Solution” manufactured by Atotech Japan Co., Ltd.) -It immersed in securigant P ") for 5 minutes at 40 degreeC. The obtained substrate is referred to as “evaluation substrate 1”.

(5) Formation of conductor layer Thereafter, a conductor layer was formed on the surface of the insulating layer by a plating process according to a semi-additive method. Specifically, a 1 μm thick copper layer was formed by electroless copper plating. Thereafter, electrolytic copper plating was performed to form a conductor layer (copper layer) having a total thickness of 30 μm. The obtained substrate is referred to as “evaluation substrate 2”.

<Evaluation of appearance of resin composition layer surface>
The resin sheets produced in the examples and comparative examples were cut into 100 mm × 100 mm test pieces, and the surface state of the resin composition layer was observed using a microscope (a microscope “VH-5500” manufactured by KEYENCE Co., Ltd.). Based on the following criteria, the appearance of the resin composition layer surface in the resin sheet was evaluated.
Evaluation criteria:
○: 2 or less pinholes ×: 3 or more pinholes

<Measurement of linear thermal expansion coefficient of insulating layer>
The resin sheets prepared in Examples and Comparative Examples and the insulating resin layer are arranged so that the resin composition layer and the insulating resin layer are bonded, and according to the thermocompression bonding conditions described in [Preparation of evaluation substrate] above. Under such conditions, the resin composition layer and the insulating resin layer were cured to obtain a cured product film. A prepreg (“GEA-800G” manufactured by Hitachi Chemical Co., Ltd., thickness 0.06 mm) was used as the insulating resin layer. The support was removed from the resulting cured film and cut into test pieces having a width of about 5 mm and a length of about 15 mm. The test piece was subjected to thermomechanical analysis by a tensile load method (JIS K7197) using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Corporation). Specifically, after mounting the test piece on the thermomechanical analyzer, the test piece was measured twice continuously under the measurement conditions of a load of 1 g, a heating rate of 5 ° C./min, and a temperature range of 25 ° C. to 250 ° C. In the second measurement, the average linear thermal expansion coefficient (ppm / ° C.) in the range from 25 ° C. to 150 ° C. was calculated. And based on the following reference | standard, the linear thermal expansion coefficient of the insulating layer was evaluated.
Evaluation criteria:
○: Average linear thermal expansion coefficient is 15 ppm / ° C or less ×: Average linear thermal expansion coefficient is greater than 15 ppm / ° C

<Evaluation of the appearance of the insulating layer surface>
The evaluation board | substrate 1 was cut | disconnected to the test piece of 100 mm x 100 mm, and the surface state was observed using the microscope (KEYENCE Corporation | KK microscope "VH-5500"). The appearance of the insulating layer surface was evaluated based on the following criteria.
Evaluation criteria:
○: No exposure of sheet-like fiber base material (0 locations)
X: Sheet-like fiber substrate is exposed (one or more locations)

<Measurement of arithmetic average roughness (Ra) of insulating layer surface>
With respect to the evaluation substrate 1, using a non-contact type surface roughness meter ("WYKO NT3300" manufactured by BEIKO INSTRUMENTS), Ra value was obtained by a numerical value obtained with a measurement range of 121 μm × 92 μm by a VSI contact mode and a 50 × lens. . The average value of 10 points selected at random was obtained, and the arithmetic average roughness (Ra) was evaluated according to the following criteria.
Evaluation criteria:
○: The average value of Ra is 250 nm or less ×: The average value of Ra is larger than 250 nm

<Evaluation of reflow resistance>
The evaluation substrate 2 was cut into a 100 mm × 100 mm test piece. About the obtained test piece, IPC / JEDEC J-STD-020C ("Moisture / Refractive Sensitivity For Non-Harmetic Solid State 4th month, 7th year," HAS6116 "manufactured by Antom Co., Ltd.) The simulated reflow process was repeated 20 times with the reflow temperature profile described in (1) (profile for lead-free assembly; peak temperature 260 ° C.). And reflow tolerance was evaluated according to the following evaluation criteria.
Evaluation criteria:
○: Separation between insulating layer and conductor layer is 2 or less ×: Separation between insulation layer and conductor layer is 3 or more

<Preparation Example 1> Preparation of Support 1 Alkyd resin ("Tesfine 303" manufactured by Hitachi Chemical Polymer Co., Ltd.), 48% by mass of solid content, mixed solution of solvent containing toluene and isopropyl alcohol in a ratio of 4: 1 ) 100 parts, and p-toluenesulfonic acid solution (“Dryer 900” manufactured by Hitachi Chemical Co., Ltd., solid content 50% by mass, mixed solution of solvent containing toluene and isopropyl alcohol in a ratio of 4: 1) 5 parts was mixed with a solvent containing toluene and isopropyl alcohol at a ratio of 4: 1 to prepare a release agent solution having a solid content concentration of 1.5% by mass. The release agent solution is applied to one side of a PPS film (“Torelina 25-3030” manufactured by Toray Industries, Inc., thickness 25 μm) so that the thickness of the release layer after drying is 0.1 μm. Drying was performed at a temperature of 1 minute to prepare a support 1 (an organic support with a release layer). Ra of the surface of the release layer of the support 1 was 110 nm, and Ra on the surface opposite to the release layer was 110 nm.

<Production Example 2> Production of support 2 Polystyrene film ("Oydis CA-F" manufactured by Kurashiki Spinning Co., Ltd.), thickness instead of PPS film ("Torelina 25-3030" manufactured by Toray Industries, Inc., thickness 25 [mu] m) A support 2 (an organic support with a release layer) was prepared in the same manner as in Production Example 1, except that 50 μm) was used. Ra of the release layer surface of the support 2 was 60 nm, and Ra on the surface opposite to the release layer was 60 nm.

<Preparation Example 1> Preparation of resin varnish 1 Liquid bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent 169) 15 parts, 40 parts of biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 280), phenoxy resin (“YX6954BH30” manufactured by Mitsubishi Chemical Corporation), 30% by mass of non-volatile components, MEK and cyclohexanone 25 parts of a mixed solution with a solvent contained at a ratio of 1: 1) was dissolved in a mixed solvent of 40 parts of MEK and 40 parts of toluene while stirring. There, 12.5 parts of a triazine skeleton-containing phenol novolac-based curing agent (“LA-7054” manufactured by DIC Corporation, a hydroxyl group equivalent of 125, a MEK solution containing 60% by mass of nonvolatile components), an active ester curing agent (DIC Corporation) "HPC8000-65T" manufactured, 35 parts by weight of an active group equivalent of about 223, 65% by mass of a non-volatile component, imidazole curing accelerator ("P200H50" manufactured by Mitsubishi Chemical Corporation), imidazole-epoxy resin adduct, non-volatile 5 parts of a solution prepared by adjusting a component of 50% by mass of propylene glycol monomethyl ether) to 25% by mass of non-volatile components with cyclohexanone, polyvinyl butyral resin (“BX-5Z” manufactured by Sekisui Chemical Co., Ltd.), 10% by mass of non-volatile components, MEK And a mixture of a solvent containing cyclohexanone in a ratio of 1: 1) 50 parts, amino Spherical silica (“SO-C1” manufactured by Admatechs Co., Ltd.), surface treated with a run coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0.5 μm, carbon amount per unit surface area Resin varnish 1 was prepared by mixing 80 parts of 0.39 mg / m ² ) and 3 parts of rubber particles (“STAPHYLOID AC3401N” manufactured by Aika Industry Co., Ltd.) and uniformly dispersing with a high-speed rotary mixer.

<Preparation Example 2> Preparation of Resin Varnish 2 Active ester curing agent instead of 35 parts active ester curing agent ("HPC8000-65T" manufactured by DIC Corporation, toluene solution with active group equivalent of about 223, non-volatile component 65 mass%) Resin varnish 2 was prepared in the same manner as in Preparation Example 1, except that 35 parts of the agent ("HPC8000L-65M" manufactured by DIC Corporation, MEK solution having an active group equivalent of about 220 and a nonvolatile component of 65% by mass) was used. .

<Preparation Example 3> Preparation of Resin Varnish 3 1) Mixing with polyvinyl butyral resin ("BX-5Z" manufactured by Sekisui Chemical Co., Ltd.), 10% by mass of nonvolatile components, and a solvent containing MEK and cyclohexanone in a ratio of 1: 1. 2) Mixing with phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Corporation), 30% by mass of non-volatile components, and a solvent containing MEK and cyclohexanone in a ratio of 1: 1. Resin varnish 3 was prepared in the same manner as in Preparation Example 1, except that the amount of (Liquid) was changed to 10 parts.

<Preparation Example 4> Preparation of Resin Varnish 4 The blending amount of phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Corporation, 30% by mass of a non-volatile component, a mixture of MEK and a solvent containing cyclohexanone at a ratio of 1: 1) Resin varnish 4 was prepared in the same manner as in Preparation Example 1, except that the amount was changed to 120 parts.

<Preparation Example 5> Preparation of Resin Varnish 5 Spherical silica ("SO-C1" manufactured by Admatechs Co., Ltd.), average particle diameter, surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) Resin varnish 5 was prepared in the same manner as in Preparation Example 1, except that the blending amount of 0.5 μm and the carbon amount per unit surface area of 0.39 mg / m ² ) was changed to 45 parts.

<Preparation Example 6> Preparation of Resin Varnish 6 Spherical silica ("SO-C1" manufactured by Admatechs Co., Ltd.), average particle diameter, surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) Resin varnish 6 was prepared in the same manner as in Preparation Example 1, except that the blending amount of 0.5 μm and the carbon amount per unit surface area of 0.39 mg / m ² ) was changed to 150 parts.

<Preparation Example 7> Preparation of resin varnish 7 Imidazole-based curing accelerator ("P200H50" manufactured by Mitsubishi Chemical Corporation, adduct body of imidazole-epoxy resin, propylene glycol monomethyl ether solution of 50 mass% nonvolatile component) is nonvolatile with cyclohexanone Resin varnish 7 was prepared in the same manner as in Preparation Example 1, except that the amount of the solution adjusted to 25% by mass of the component was changed to 0.8 part.

<Preparation Example 8> Preparation of resin varnish 8 Imidazole-based curing accelerator ("P200H50" manufactured by Mitsubishi Chemical Corporation, adduct body of imidazole-epoxy resin, propylene glycol monomethyl ether solution of 50 mass% nonvolatile component) is nonvolatile with cyclohexanone Resin varnish 8 was prepared in the same manner as in Preparation Example 1, except that the amount of the solution adjusted to 25% by mass of the component was changed to 21 parts.

<Preparation Example 9> Preparation of Resin Varnish 9 1) Add 20 parts of active ester curing agent (“HPC8000-65T” manufactured by DIC Corporation, active group equivalent of about 223, 65% by mass non-volatile component toluene solution) Changed point and 2) 10 parts of cyanate ester-based curing agent ("BA230-75M" manufactured by Lonza Japan Co., Ltd., cyanate equivalent of about 232, prepolymer of bisphenol A dicyanate, MEK solution with a non-volatile component of 75% by mass) A resin varnish 9 was prepared in the same manner as in Preparation Example 1, except for the added point.

<Preparation Example 10> Preparation of Resin Varnish 10 Resin varnish 10 is prepared in the same manner as Preparation Example 1, except that the amount of rubber particles ("STAPHYLOID AC3401N" manufactured by Aika Industry Co., Ltd.) is changed to 7 parts. did.

<Preparation Example 11> Preparation of Resin Varnish 11 1) The amount of rubber particles ("STAPHYLOID AC3401N" manufactured by Aika Kogyo Co., Ltd.) was changed to 7 parts, 2) Imidazole-based curing accelerator (Mitsubishi Chemical Corporation) ) “P200H50”, adduct body of imidazole-epoxy resin, propylene glycol monomethyl ether solution of 50% by mass of non-volatile component) is replaced with 5 parts of a solution prepared by cyclohexanone to 25% by mass of non-volatile component, and an amine curing accelerator ( Resin varnish 11 was prepared in the same manner as in Preparation Example 1, except that 10 parts of 4-dimethylaminopyridine (DMAP) and an MEK solution having a solid content of 5% by mass were used.

<Preparation example 12> Preparation of resin varnish 12 1) Compounding amount of active ester curing agent ("HPC8000-65T" manufactured by DIC Corporation, active group equivalent of about 223, toluene solution of 65% by mass of non-volatile component) to 20 parts The same as in Preparation Example 1 except that 10 parts of the changed point and 2) carbodiimide-based curing agent (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., toluene solution of 50% by mass of nonvolatile components) were further added. Resin varnish 12 was prepared.

<Preparation Example 13> Preparation of resin varnish 13 Instead of 35 parts active ester curing agent ("HPC8000-65T" manufactured by DIC Corporation, toluene solution with an active group equivalent of about 223 and 65 mass% non-volatile component), naphthol-based curing Resin varnish 13 was prepared in the same manner as in Preparation Example 1, except that 38 parts of an agent (“SN485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., MEK solution having a hydroxyl group equivalent of 215 and a nonvolatile component of 60 mass%) was used.

<Preparation Example 14> Preparation of resin varnish 14 Instead of 35 parts active ester curing agent ("HPC8000-65T" manufactured by DIC Corporation, toluene solution with an active group equivalent of about 223 and 65% by mass of non-volatile components), cyanate ester type Except for using 30 parts of a curing agent ("BA230-75M" manufactured by Lonza Japan Co., Ltd., cyanate equivalent of about 232, prepolymer of bisphenol A dicyanate, MEK solution with a non-volatile component of 75% by mass), the same as in Preparation Example 1 Resin varnish 14 was prepared.

  The compositions of resin varnishes 1 to 14 are shown in Table 1.

<Example 1>
The resin varnish 1 is uniformly applied to the surface of the release layer of the support 1 and dried at 60 ° C. to 120 ° C. (average 90 ° C.) for 3 minutes, and further dried at 180 ° C. for 4 minutes to obtain a resin composition. A resin sheet having a layer thickness of 4 μm was produced. In addition, the thickness of the resin composition layer was measured using a contact-type layer thickness meter (“MCD-25MJ” manufactured by Mitutoyo Corporation).

  Each evaluation was implemented about the produced resin sheet according to said <measurement method and evaluation method>. The same applies to the following examples and comparative examples unless otherwise specified.

<Example 2>
A resin sheet was prepared in the same manner as in Example 1 except that the resin varnish 2 was used instead of the resin varnish 1.

<Example 3>
A resin sheet was produced in the same manner as in Example 1 except that the support 3 (metal support) was used instead of the support 1. As the support 3, copper foil (“HLP” manufactured by JX Nippon Mining & Metals Co., Ltd., thickness 18 μm, Ra of smooth surface is 160 nm, Ra of rough surface is 450 nm) is used. Resin varnish 1 was applied to the surface.

<Example 4>
A resin sheet was produced in the same manner as in Example 1 except that the support 2 was used in place of the support 1.

<Example 5>
A resin sheet was produced in the same manner as in Example 1 except that the resin varnish 3 was used instead of the resin varnish 1.

<Example 6>
A resin sheet was produced in the same manner as in Example 1 except that the resin varnish 4 was used instead of the resin varnish 1.

<Example 7>
A resin sheet was produced in the same manner as in Example 1 except that the resin varnish 5 was used instead of the resin varnish 1.

<Example 8>
A resin sheet was prepared in the same manner as in Example 1 except that the resin varnish 6 was used instead of the resin varnish 1.

<Example 9>
A resin sheet was produced in the same manner as in Example 1 except that the resin varnish 7 was used instead of the resin varnish 1.

<Example 10>
A resin sheet was prepared in the same manner as in Example 1 except that the resin varnish 8 was used instead of the resin varnish 1.

<Example 11>
A resin sheet was produced in the same manner as in Example 1 except that the resin varnish 9 was used instead of the resin varnish 1.

<Example 12>
A resin sheet was produced in the same manner as in Example 1 except that the resin varnish 10 was used instead of the resin varnish 1.

<Example 13>
A resin sheet was produced in the same manner as in Example 1 except that the resin varnish 11 was used instead of the resin varnish 1.

<Example 14>
A resin sheet was produced in the same manner as in Example 1 except that the resin varnish 12 was used instead of the resin varnish 1.

<Comparative Example 1>
In Comparative Example 1, each evaluation was performed without using a resin sheet. That is, in the above <Measurement method / Evaluation method>, each evaluation was performed without using a resin sheet.

<Comparative example 2>
A resin sheet was produced in the same manner as in Example 1 except that the thickness of the resin composition layer was changed to 8 μm.

<Comparative Example 3>
A resin sheet was produced in the same manner as in Example 1 except that the resin varnish 13 was used instead of the resin varnish 1.

<Comparative example 4>
A resin sheet was produced in the same manner as in Example 1 except that the resin varnish 14 was used instead of the resin varnish 1.

Claims (25)

A resin sheet for circuit formation used by being laminated on an insulating resin layer,
A support;
A resin composition layer bonded to the support,
The resin composition layer has a thickness of 0.1 μm to 6 μm,
The resin sheet in which the resin composition layer contains (A) an epoxy resin and (B) an active ester curing agent.   The resin sheet according to claim 1, wherein the resin composition layer further comprises (C) an inorganic filler.   (C) The resin sheet according to claim 2, wherein the inorganic filler is silica. The content of the resin composition layer (C) inorganic filler, when the non-volatile components of the resin composition layer is 100 mass%, 25 mass% to 65 mass%, according to claim 2 or 3 Resin sheet. The resin sheet according to claim 4 , wherein the content of the inorganic filler (C) in the resin composition layer is 59.5% by mass or less when the nonvolatile component in the resin composition layer is 100% by mass. . The resin sheet according to any one of claims 1 to 5 , wherein the resin composition layer further comprises (D) a polymer component, and (D) the polymer component is selected from the group consisting of an organic filler and a thermoplastic resin. . (D) The resin sheet of Claim 6 in which a polymer component contains 1 or more types selected from the group which consists of an organic filler, a phenoxy resin, and a polyvinyl acetal resin. The content of (D) a polymer component of the resin composition layer is, when the non-volatile components of the resin composition layer is 100 mass%, 0.5 mass% to 23 mass%, according to claim 6 or 7 Resin sheet. The resin sheet according to any one of claims 1 to 8 , wherein the resin composition layer further comprises (E) a curing accelerator. The content of the resin composition layer (E) a curing accelerator, when the resin component of the resin composition is 100 mass%, 0.1 mass% to 6 mass%, according to claim 9 Resin sheet. (E) The resin sheet of Claim 9 or 10 in which a hardening accelerator contains 1 or more types selected from the group which consists of an imidazole type hardening accelerator and an amine type hardening accelerator. (E) The resin sheet of any one of Claims 9-11 in which a hardening accelerator contains 1 or more types selected from the group which consists of the adduct body of imidazole-epoxy resin, and 4-dimethylaminopyridine. . The resin composition layer further includes (C) an inorganic filler, (D) a polymer component, and (E) a curing accelerator,
(D) the polymer component is selected from the group consisting of organic fillers and thermoplastic resins;
When the non-volatile component in the resin composition layer is 100% by mass, the content of (C) inorganic filler is 25% by mass to 65% by mass, and the content of (D) polymer component is 0.5% by mass to 23%. Mass%,
The resin sheet of Claim 1 whose content of (E) hardening accelerator is 0.1 mass%-6 mass% when the resin component in a resin composition is 100 mass%. (C) the inorganic filler is silica;
(D) The polymer component includes one or more selected from the group consisting of an organic filler, a phenoxy resin, and a polyvinyl acetal resin,
(E) The resin sheet of Claim 13 in which a hardening accelerator contains 1 or more types selected from the group which consists of the adduct body of an imidazole-epoxy resin, and 4-dimethylamino pyridine. The resin sheet according to any one of claims 1 to 14 , wherein the resin composition layer is obtained by drying a resin varnish containing a solvent having a boiling point of 100 ° C or higher and a solvent having a boiling point of less than 100 ° C. The resin sheet according to claim 15 , wherein the resin composition layer is obtained by drying the resin varnish at a temperature of 150 ° C. or higher. The thickness of the support is 5 m to 100 m, the resin sheet according to any one of claims 1-16. The thickness of the support is 25Myuemu～55myuemu, the resin sheet according to any one of claims 1 to 17. The resin sheet according to any one of claims 1 to 18 , wherein an arithmetic average roughness (Ra) of a surface in contact with the resin composition layer of the support is less than 200 nm. Circuit formation is performed by plating process, the resin sheet according to any one of claims 1 to 19. The resin sheet according to any one of claims 1 to 20 , wherein the insulating resin layer is a prepreg. Laminate sheet including a resin sheet according to any one of claims 1 to 21 and a prepreg bonded to the resin composition layer of the resin sheet. An insulating layer formed by heating the resin sheet according to any one of claims 1 to 21 and the insulating resin layer in a state where the resin composition layer and the insulating resin layer are joined, Laminated board. The laminated board of Claim 23 containing the circuit formed in the surface of an insulating layer. A semiconductor device comprising the laminate according to claim 24 .