KR102387485B1 - Resin sheet - Google Patents

Abstract

[Project] To provide a resin sheet (metal foil with resin) capable of suppressing a decrease in the peel strength of the insulating layer and circuit in a high-temperature, high-humidity environment by HAST even when a metal foil having a low roughness surface is used.
[Solutions] A resin sheet for circuit formation by a subtractive method or a modified semi-additive method, comprising a metal foil having first and second main surfaces, and a resin layer bonded to the first main surface of the metal foil, , the arithmetic mean roughness (Ra) of the first main surface of the metal foil is 300 nm or less, the thickness of the resin layer is 8 to 400 μm, the resin layer is (a) an epoxy resin, (b) an active ester-based curing agent and a triazine structure A resin sheet comprising at least one curing agent selected from the group consisting of a phenol-based curing agent.

Description

Resin sheet {RESIN SHEET}

The present invention relates to a resin sheet. Moreover, it relates to the laminated board and semiconductor device obtained using the said resin sheet.

As a manufacturing technique of a printed wiring board, the manufacturing method by the buildup system which laminates|stacks an insulating layer and a conductor layer (circuit layer) alternately is known. In the manufacturing method by a build-up system, in general, an insulating layer is formed by laminating|stacking a resin layer on a circuit board using the resin sheet etc. containing a resin layer, and hardening the said resin layer. For example, Patent Document 1 discloses a resin sheet including a metal foil and a resin layer formed on the metal foil.

Japanese Patent Laid-Open No. 2007-22091

In the manufacturing method by a build-up system, a circuit is formed on the said insulating layer after insulating layer formation. When using the resin sheet in which the resin layer was formed on the metal foil, it is possible to form a circuit by the subtractive method or a modified semiadditive method using the said metal foil. In this case, when forming a fine circuit, it is suitable that the interface roughness of an insulating layer and metal foil is low.

However, in order to reduce the interface roughness between the insulating layer and the metal foil, when a resin sheet formed by forming a resin layer on a metal foil having a low roughness surface is used, the obtained insulating layer and the adhesion strength (peel strength) of the circuit ) may be lowered. In particular, the present inventors discovered that the adhesive strength of an insulating layer and a circuit tended to fall remarkably in the high-temperature, high-humidity environment by HAST (Highly Accelerated temperature and humidity Stress Test).

The present invention provides a resin sheet (metal foil with resin) capable of suppressing a decrease in the peel strength of the insulating layer and circuit in a high-temperature, high-humidity environment by HAST even when a metal foil having a low roughness surface is used. make it a task

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the said subject, the present inventors discovered that the said subject was solvable by using the resin layer containing an epoxy resin and a specific hardening|curing agent, and came to complete this invention.

That is, the present invention includes the following contents.

[1] A resin sheet for circuit formation by a subtractive method or a modified semi-additive method, comprising:

a metal foil having first and second main surfaces;

The resin layer joined to the first main surface of the metal foil

including,

The arithmetic mean roughness (Ra) of the first main surface of the metal foil is 300 nm or less,

The thickness of the resin layer is 8 to 400 μm,

A resin sheet, wherein the resin layer contains at least one curing agent selected from the group consisting of (a) an epoxy resin, (b) an active ester curing agent and a triazine structure-containing phenol curing agent.

[2] The resin sheet according to [1], wherein the resin layer further contains (c) an inorganic filler.

[3] (c) The resin sheet according to [2], wherein the inorganic filler is silica.

[4] The resin sheet according to [2] or [3], wherein the content of the (c) inorganic filler in the resin layer is 40 to 85 mass% when the nonvolatile component in the resin layer is 100 mass%.

[5] The resin sheet according to any one of [1] to [4], wherein the resin layer further contains (d) a polymer component, and (d) the polymer component is selected from the group consisting of an organic filler and a thermoplastic resin.

[6] The resin sheet according to [5], wherein (d) the polymer component contains at least one selected from the group consisting of an organic filler, a phenoxy resin, and a polyvinyl acetal resin.

[7] The resin sheet according to [5] or [6], wherein the content of the polymer component (d) in the resin layer is 0.5 to 10 mass% when the nonvolatile component in the resin layer is 100 mass%.

[8] The resin sheet according to any one of [1] to [7], wherein the resin layer further contains (e) a curing accelerator.

[9] The resin sheet according to [8], wherein the content of the (e) curing accelerator in the resin layer is 0.03 to 4 mass% when the resin component in the resin layer is 100 mass%.

[10] The resin sheet according to [8], wherein the content of the (e) curing accelerator in the resin layer is 0.3 to 3% by mass when the resin component in the resin layer is 100% by mass.

[11] (e) The resin sheet according to any one of [8] to [10], wherein the curing accelerator contains at least one selected from the group consisting of an imidazole-based curing accelerator and an amine-based curing accelerator.

[12] (e) in any one of [8] to [11], wherein the curing accelerator contains at least one selected from the group consisting of an adduct of imidazole-epoxy resin and 4-dimethylaminopyridine. The resin sheet described.

[13] the resin layer further contains (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 nonvolatile component in the resin layer is 100% by mass, (c) the content of the inorganic filler is 40 to 85% by mass, (d) the content of the polymer component is 0.5 to 10% by mass,

The resin sheet as described in [1] whose content of (e) hardening accelerator is 0.03-4 mass % when the resin component of a resin layer is 100 mass %.

[14] (c) the inorganic filler is silica,

(d) the polymer component contains at least one selected from the group consisting of organic fillers, phenoxy resins and polyvinyl acetal resins,

(e) The resin sheet according to [13], wherein the curing accelerator contains at least one selected from the group consisting of an imidazole-epoxy resin adduct and 4-dimethylaminopyridine.

[15] The resin sheet according to any one of [1] to [14], wherein the minimum melt viscosity of the resin layer is 8000 to 40000 poise.

[16] The resin sheet according to any one of [1] to [14], wherein the minimum melt viscosity of the resin layer is 300 to 12000 poise.

[17] After curing the resin layer to form an insulating layer, and forming a circuit by a subtractive method or a modified semi-additive method, the peel strength of the insulating layer and the circuit is 0.5 kgf/cm or more,

The insulating layer and the circuit after curing the resin layer to form an insulating layer, forming a circuit by a subtractive method or a modified semi-additive method, and lapse of 100 hours under the conditions of 130°C and 85%RH The resin sheet according to any one of [1] to [16], wherein the peeling strength is 0.3 kgf/cm or more.

[18] The resin sheet according to any one of [1] to [17], wherein the metal foil has a thickness of 1 to 40 µm.

[19] The resin sheet according to any one of [1] to [18], wherein the arithmetic mean roughness (Ra) of the first main surface of the metal foil is 250 nm or less.

[20] The resin sheet according to any one of [1] to [19], wherein the arithmetic mean roughness (Ra) of the second main surface of the metal foil is 300 nm or more.

[21] The inner layer substrate is disposed between the two resin sheets according to any one of [1] to [20] so that the resin layer and the inner layer substrate are bonded, and collectively formed by vacuum hot press treatment or vacuum lamination treatment. obtained, a laminate.

[22] The laminate according to [21], comprising a circuit formed by a subtractive method or a modified semiadditive method.

[23] The laminate according to [22], including a circuit having a wiring pitch of 50 µm or less.

[24] A semiconductor device obtained by using the laminate according to any one of [21] to [23].

According to the present invention, even when a metal foil having a low roughness surface is used, a resin sheet (metal foil with resin) capable of suppressing a decrease in the peel strength of the insulating layer and circuit in a high-temperature, high-humidity environment by HAST. can

ADVANTAGE OF THE INVENTION According to the resin sheet of this invention, the reliable printed wiring board which has a fine circuit can be implement|achieved.

Hereinafter, the present invention will be described in detail based on preferred embodiments thereof.

[Resin Sheet]

The resin sheet of the present invention is a resin sheet (metal foil with resin) for circuit formation by a subtractive method or a modified semi-additive method. The resin sheet includes a metal foil having first and second main surfaces, and a resin layer joined to the first main surface of the metal foil, wherein the arithmetic mean roughness (Ra) of the first main surface of the metal foil is 300 nm or less; The base layer has a thickness of 8 to 40 μm, and the resin layer contains at least one curing agent selected from the group consisting of (a) an epoxy resin, (b) an active ester curing agent, and a triazine structure-containing phenol curing agent. do it with

The resin sheet of this invention can form an insulating layer by hardening a resin layer at the time of manufacture of a printed wiring board. In addition, a circuit can be formed by a subtractive method or a modified semi-additive method using metal foil. By using the resin sheet of this invention, while being able to form a fine circuit, the highly reliable printed wiring board which can suppress the fall of the peeling strength of the insulating layer in the high-temperature, high-humidity environment by HAST and a circuit is realizable. .

<Metal foil>

Metal foil has 1st and 2nd main surface. In the resin sheet of this invention, the 1st main surface of metal foil will join a resin layer.

From a viewpoint of being able to form a fine circuit, the 1st main surface of metal foil is not substantially roughened, and arithmetic mean roughness Ra is 300 nm or less. From a viewpoint of being able to form a fine circuit, Ra of the 1st main surface of metal foil becomes like this. Preferably it is 280 nm or less, More preferably, it is 260 nm or less, More preferably, it is 250 nm or less. As described above, when a resin sheet obtained by forming a resin layer on a metal foil having a low surface roughness is used, the obtained insulating layer and the peel strength of the circuit may decrease. In particular, the present inventors are discovering that there exists a tendency for the adhesive strength of an insulating layer and a circuit to fall remarkably in the high-temperature, high-humidity environment by HAST. On the other hand, according to the resin sheet of this invention which uses the resin layer containing an epoxy resin and a specific hardening|curing agent, it is possible to use the metal foil which has a surface of lower roughness without lowering in peeling strength. In this invention, 240 nm or less, 220 nm or less, 200 nm or less, 180 nm or less, or 160 nm or less may be sufficient as Ra of the 1st main surface of metal foil, for example. Although the lower limit of Ra of the 1st main surface of metal foil is not specifically limited, From a viewpoint of stabilizing the peeling strength of the insulating layer and circuit obtained, it can be normally set as 1 nm or more, 5 nm or more, 10 nm or more.

Although Ra of the 2nd main surface of metal foil is not specifically limited, From a viewpoint of improving the drilling processability by a laser at the time of manufacture of a printed wiring board, Preferably it is 300 nm or more, More preferably, it is 320 nm or more, More preferably, it is 340 nm or more. , 360 nm or more, 380 nm or more, or 400 nm or more. Although the upper limit of Ra of the 2nd main surface of metal foil is not specifically limited, Usually, it can be 1000 nm or less, 900 nm or less, 800 nm or less, etc.

The arithmetic mean roughness (Ra) of the surface of metal foil can be measured using a non-contact type surface roughness meter. As a non-contact type surface roughness machine, "WYKO NT3300" by a BCoin Instruments company is mentioned, for example.

As a material of metal foil, copper, aluminum, etc. are mentioned, for example, Copper is preferable. As the copper foil, a foil made of a single metal of copper may be used, or a foil made of an alloy of copper and another metal (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. good.

The metal foil 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 metal foil has a multilayer structure, the layer in contact with the resin layer is preferably a single metal layer of nickel, tin, chromium, zinc, molybdenum, cobalt or titanium, or an alloy layer thereof.

Although the thickness of the metal foil is not particularly limited, from the viewpoint of forming a fine circuit by the subtractive method, and from the viewpoint of smoothly forming the circuit by the modified semi-additive method, preferably 40 µm or less, more Preferably it is 35 micrometers or less, More preferably, it is 30 micrometers or less, 28 micrometers or less, 26 micrometers or less, 24 micrometers or less, 22 micrometers or less, or 20 micrometers or less. The lower limit of the thickness of the metal foil is not particularly limited, and may be determined according to the method used for circuit formation, the design of the desired printed wiring board, and the like. The lower limit of the thickness of metal foil can be 1 micrometer or more, 2 micrometers or more, 3 micrometers or more, 5 micrometers or more, 10 micrometers or more normally. Moreover, when metal foil has a multilayer structure, it is preferable that the thickness of the whole metal foil is such a range.

The manufacturing method of metal foil is not specifically limited as long as the metal foil which has desired surface roughness is obtained. Metal foil can be manufactured by well-known methods, such as an electrolysis method and a rolling method, for example. When the metal foil is manufactured using the electrolytic method, the Ra value can be changed by controlling the smoothness of the drum surface at the time of manufacturing the metal foil, the current density, the plating bath temperature, and the like.

Metal foil may use a commercial item. As a commercial item of metal foil, HLP foil by JX Nikko Nippon-Kinzoku Co., Ltd., TP-III foil by Mitsui Kinzoku Kosan Co., Ltd. etc. are mentioned, for example.

<Resin Layer>

In the resin sheet of the present invention, the thickness of the resin layer may be determined according to the desired design of the printed wiring board, but from the viewpoint of reducing the thickness of the printed wiring board, it is 400 µm or less, preferably 350 µm or less, more preferably 300 µm or less, more preferably 250 µm or less, 200 µm or less, 180 µm or less, 160 µm or less, 140 µm or less, 120 µm or less, 100 µm or less, 80 µm or less, 60 µm or less, or 40 µm or less. The lower limit of the thickness of the resin layer is 8 µm or more, preferably 10 µm or more, 15 µm or more, or 20 µm or more.

In the resin sheet of the present invention, the resin layer contains at least one curing agent selected from the group consisting of (a) an epoxy resin, (b) an active ester curing agent and a triazine structure-containing phenol curing agent.

-(a) Epoxy resin-

Examples of the epoxy resin include bisphenol A 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 novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, Cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, butadiene structure epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, naph A thylene ether type epoxy resin, a trimethylol type epoxy resin, a tetraphenylethane type epoxy resin, etc. are mentioned. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable that an epoxy resin contains the epoxy resin which has two or more epoxy groups in 1 molecule. When the nonvolatile component of the epoxy resin is 100 mass %, it is preferable that at least 50 mass % or more is an epoxy resin which has two or more epoxy groups in 1 molecule. Among them, an epoxy resin having two or more epoxy groups in one molecule and liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resin"), and two or more (preferably 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. As the epoxy resin, a resin layer having excellent flexibility is obtained by using a liquid epoxy resin and a solid epoxy resin together. Further, the breaking strength of the obtained insulating layer is also improved.

As a liquid epoxy resin, 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 novolak type epoxy resin, an alicyclic epoxy resin having an ester skeleton, and a butadiene structure The epoxy resin which has is preferable, and a bisphenol A epoxy resin, a bisphenol F type epoxy resin, and a naphthalene type epoxy resin 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 Co., Ltd. (Bisphenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "ZX1059" (bisphenol A type epoxy resin) manufactured by Shin-Nittetsu Chemical Co., Ltd. and bisphenol F-type epoxy resin), “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Co., Ltd., and “Ceroxide 2021P” manufactured by Daicel Corporation (ester skeletonized alicyclic epoxy resin having) and "PB-3600" (epoxy resin having a butadiene structure). These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the solid-state epoxy resin include naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, and naphthylene ether-type epoxy resins. , anthracene type epoxy resin, bisphenol A type epoxy resin, tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, dicyclopentadiene type epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more desirable. 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 novolak epoxy resin), "HP7200", "HP7200HH" (dicyclopentadiene epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nihon Kayaku Co., Ltd., "NC7000L" (naphthol novolak type epoxy resin), "NC3000H", " NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthol type epoxy resin) manufactured by Shin-Nittetsu Chemical Co., Ltd., "ESN485" (naphthol novolak type epoxy resin), "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. Osaka Chemical Co., Ltd. “PG-100” and “CG-500” manufactured by Mitsubishi Chemical Co., Ltd. “YL7800” (fluorene type epoxy resin), “jER1010” manufactured by Mitsubishi Chemical Co., Ltd. (solid bisphenol A type epoxy) resin), "jER1031S" (tetraphenylethane type epoxy resin), etc. are mentioned.

As an epoxy resin, when using a liquid epoxy resin and a solid epoxy resin together, these ratios (liquid epoxy resin: solid epoxy resin) are mass ratio, and the range of 1:0.1 - 1:6 is preferable. By setting the ratio of the liquid epoxy resin and the solid epoxy resin to such a range, i) suitable adhesiveness is obtained when used in the form of a resin sheet, ii) sufficient flexibility is obtained when used in the form of a resin sheet, The handleability is improved, and effects such as iii) being able to obtain an insulating layer having sufficient breaking strength are obtained. From the viewpoint of the effects of i) to iii) above, the amount ratio of the liquid epoxy resin and the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is, in terms of mass ratio, more preferably in the range of 1:0.3 to 1:5, 1 The range of :0.6 to 1:4 is more preferable.

The content of the epoxy resin in the resin layer is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. am. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention appears, Preferably it is 50 mass % or less, More preferably, 45 mass % or less, More preferably, it is 40 mass % or less or 35 mass %. % or less.

In addition, in this invention, unless otherwise indicated, content of each component in a resin layer is a value when the non-volatile component in a resin layer is 100 mass %.

The epoxy equivalent of an epoxy resin becomes like this. Preferably it is 50-5000, More preferably, it is 50-3000, More preferably, it is 80-2000, More preferably, it is 110-1000. By being in this range, the crosslinking density of hardened|cured material becomes sufficient and it can lead to the insulating layer with small surface roughness. In addition, an epoxy equivalent can be measured according to JISK7236, and is the mass of 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 an epoxy resin is a weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) method.

-(b) Active ester-based curing agent and/or triazine structure-containing phenol-based curing agent-

The component (b) is at least one curing agent selected from the group consisting of (b1) an active ester curing agent and (b2) a triazine structure-containing phenol curing agent. The present inventors, in a resin sheet (metal foil with a resin) for circuit formation by a subtractive method or a modified semi-additive method, by using this specific curing agent as a curing agent for an epoxy resin, under a high-temperature, high-humidity environment by HAST It discovered that the fall in the peeling strength of the insulating layer in and a circuit could be suppressed.

(b1) The active ester curing agent is an active ester compound having one or more active ester groups in one molecule. 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, heterocyclic hydroxy compounds An active ester compound having two or more ester groups having high reactive activity such as esters in one molecule is preferably used. An active ester type hardening|curing agent may be used individually by 1 type, and may be used in combination of 2 or more type.

From a viewpoint of suppressing the fall of the peeling strength of the insulating layer and circuit in a high-temperature, high-humidity environment by HAST, and a viewpoint of heat resistance, to the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound, and a hydroxy compound and/or a thiol compound An active ester compound obtained by Among these, 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 obtained by reacting an aromatic compound having a phenolic hydroxyl group , more preferably an aromatic compound having two or more active ester groups in one molecule, and an aromatic compound obtained by reacting a carboxylic acid compound having at least two or more carboxy groups in one molecule with an aromatic compound having a phenolic hydroxyl group, wherein one molecule An aromatic compound having two or more active ester groups in it is still more preferable. The active ester compound may be linear or branched may be sufficient as it. In addition, if the carboxylic acid compound having at least two or more carboxyl groups in one molecule is a compound containing an aliphatic chain, compatibility with other resin components constituting the resin layer can be increased, and if it is a compound having an aromatic ring, heat resistance can be increased can

As the carboxylic acid compound, for example, an aliphatic carboxylic acid having 1 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 8), an aromatic carboxylic acid having 7 to 20 carbon atoms (preferably 7 to 10). and carboxylic acids. Examples of the aliphatic carboxylic acid include acetic acid, malonic acid, succinic acid, maleic acid, and itaconic acid. Examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Among these, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable from the viewpoint of suppressing the decrease in the peel strength of the insulating layer and circuit in a high-temperature, high-humidity environment by HAST, and from the viewpoint of heat resistance, Isophthalic acid and terephthalic acid are more preferable.

Although there is no restriction|limiting in particular as a thiocarboxylic acid compound, For example, thioacetic acid, thiobenzoic acid, etc. are mentioned.

Examples of the phenol compound include a phenol compound having 6 to 40 carbon atoms (preferably 6 to 30, more preferably 6 to 23, still more preferably 6 to 22), and suitable specific examples include: Hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydro and hydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzenetriol, and dicyclopentadiene type diphenol. As a phenol compound, you may use the phosphorus atom containing oligomer which has a phenolic hydroxyl group further described in phenol novolak, cresol novolak, and Unexamined-Japanese-Patent No. 2013-40270.

Examples of the naphthol compound include naphthol compounds having 10 to 40 carbon atoms (preferably 10 to 30, more preferably 10 to 20), and suitable specific examples include α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, etc. are mentioned. As the naphthol compound, naphthol novolac may also be used.

Among these, 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-dihydr Roxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadiene diphenol, phenol novolac , cresol novolac, naphthol novolac, phosphorus atom-containing oligomers having a phenolic hydroxyl group are preferable, and catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxy Naphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadiene diphenol, phenol novolac, cresol novolac, naphthol novolac, phenol A phosphorus atom-containing oligomer having a hydroxyl group is more preferable, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzo Phenone, tetrahydroxybenzophenone, dicyclopentadiene type diphenol, phenol novolac, cresol novolak, naphthol novolak, and phosphorus atom-containing oligomers having a phenolic hydroxyl group are more preferable, and 1,5-dihydroxynaphthalene , 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenol, phenol novolac, cresol novolak, naphthol novolac, phosphorus atom-containing oligomers having a phenolic hydroxyl group are further More preferably, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenol, and phosphorus atom-containing oligomers having phenolic hydroxyl groups are particularly More preferably, dicyclopentadiene type diphenol is particularly preferable.

Although there is no restriction|limiting in particular as a thiol compound, For example, benzene dithiol, triazine dithiol, etc. are mentioned.

Suitable 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 phenol novolac an active ester compound containing a benzoylate, an active ester compound obtained by reacting an aromatic carboxylic acid with an oligomer containing a phosphorus atom having a phenolic hydroxyl group; among them, an active ester compound containing a dicyclopentadiene type diphenol structure , an active ester compound having a naphthalene structure, or an active ester compound obtained by reacting an aromatic carboxylic acid with an oligomer containing a phosphorus atom having a phenolic hydroxyl group is more preferable. In addition, in this invention, "dicyclopentadiene type diphenol structure" represents the divalent structural unit which consists of phenylene-dicyclopentylene-phenylene.

As an active ester type hardening|curing agent, the active ester compound disclosed by Unexamined-Japanese-Patent No. 2004-277460 and Unexamined-Japanese-Patent No. 2013-40270 may be used, and also a commercially available active ester compound can also be used. As a commercial item of an active ester compound, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000L-65M" (dicyclopentadiene type) manufactured by DIC Corporation are, for example, Active ester compound containing a diphenol structure), "9416-70BK" manufactured by DIC Corporation (active ester compound containing a naphthalene structure), "DC808" manufactured by Mitsubishi Chemical Co., Ltd. (Acetyl of phenol novolac) Active ester compound containing a compound), "YLH1026" manufactured by Mitsubishi Chemical Co., Ltd. (active ester compound containing a benzoyl compound of phenol novolac), "EXB9050L-62M" manufactured by DIC Corporation (containing phosphorus atom) active ester compounds).

(b2) The triazine structure-containing phenolic curing agent is a phenolic curing agent having both a triazine structure and a phenolic hydroxyl group in one molecule. The triazine structure-containing phenolic curing agent preferably contains two or more, three or more, or four or more triazine structures in one molecule, and preferably two or more, three or more in one molecule. , or those containing 4 or more phenolic hydroxyl groups are suitable. A triazine structure containing phenol type hardening|curing agent may be used individually by 1 type, and may be used in combination of 2 or more type.

The triazine structure-containing phenolic curing agent is obtained, for example, by reacting at least one selected from the group consisting of a phenol compound and a naphthol compound, a triazine ring-containing compound, and formaldehyde.

Suitable examples of the phenol compound and the naphthol compound are as described for the active ester curing agent (b1). Among them, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, resorcin, hydroquinone, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadiene type Diphenol, phenol novolac, cresol novolac and naphthol novolac are preferable.

As a triazine ring containing compound, a melamine, benzoguanamine, acetoguanamine etc. are mentioned, for example, A melamine and benzoguanamine are preferable.

From a viewpoint of suppressing the fall of the peeling strength of the insulating layer and circuit in a high-temperature, high-humidity environment by HAST, and a viewpoint of heat resistance, as a triazine structure containing phenol type hardening|curing agent, a triazine structure containing phenol novolak type hardening|curing agent, a triazine structure A cresol novolak type curing agent containing a triazine structure and a naphthol novolak type curing agent containing a triazine structure are preferable, and a phenol novolak type curing agent containing a triazine structure and a cresol novolak type curing agent containing a triazine structure are more preferable.

As a commercial item of a phenolic hardening|curing agent containing a triazine structure, For example, "LA-3018" (a cresol novolak type hardener containing a triazine structure) manufactured by DIC Co., Ltd., "LA-7052" manufactured by DIC Corporation, "LA-7054", "LA-1356" (triazine structure containing phenol novolak type hardening|curing agent), etc. are mentioned.

1 mass % or more is preferable, and, as for content of (b) component in a resin layer, from a viewpoint of suppressing the fall of the peeling strength of the insulating layer and circuit in high temperature, high humidity environment by HAST, 2 mass % or more is more preferable and 3 mass % or more, 4 mass % or more, or 5 mass % or more is more preferable. (b) Although the upper limit of content of a component is not specifically limited, 30 mass % or less is preferable, 25 mass % or less is more preferable, 20 mass % or less is still more preferable, 18 mass % or less, 16 mass % or less, or 15 mass % is still more preferable.

In addition, when the number of epoxy groups in component (a) is 1, from the viewpoint of obtaining an insulating layer with good mechanical strength, the number of reactors in component (b) is preferably 0.2 to 2, more preferably 0.3 to 1.5, , 0.35 to 1 are more preferable. Here, "the number of epoxy groups of component (a)" is a value obtained by dividing the solid content mass of each epoxy resin corresponding to component (a) present in the resin layer by the epoxy equivalent, and is a value summed for all epoxy resins. In addition, the "reactive group" referred to in the component (b) means an active ester group and a phenolic hydroxyl group, and "the number of reactive groups of the component (b)" refers to each curing agent corresponding to the component (b) present in the resin layer. It is the sum of all the values obtained by dividing the solid mass by the reactor equivalent.

-(c) inorganic fillers-

The resin layer may further contain an inorganic filler. By containing an inorganic filler, the thermal expansion coefficient of the insulating layer obtained can be suppressed low.

Although 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, Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate , barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, and silica is particularly suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as a 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. As commercially available spherical fused silica, "SO-C2", "SO-C1" manufactured by Adomatex Corporation, "IMSIL A-8" manufactured by Unimin, "IMSIL A-10", etc. are mentioned.

The average particle diameter of the inorganic filler is preferably 4 µm or less, more preferably 3 µm or less, still more preferably 2.5 µm or less, still more preferably 2 µm or less, particularly preferably 1 µm or less, 0.7 µm or less. or less, or 0.5 µm or less. The minimum of the average particle diameter of an inorganic filler becomes like this. Preferably it is 0.01 micrometer or more, More preferably, it is 0.03 micrometer or more, More preferably, it is 0.05 micrometer or more, 0.07 micrometer or more, or 0.1 micrometer or more. The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, it can measure by creating the particle size distribution of an inorganic filler on a volume basis with a laser diffraction type particle size distribution measuring apparatus, and making the median diameter into an average particle diameter. As a measurement sample, what disperse|distributed the inorganic filler in water by ultrasonic wave can be used preferably. As a laser diffraction type particle size distribution measuring apparatus, "LA-500", "LA-750", "LA-950" manufactured by Horiba Corporation, "LA-950", etc. can be used.

From the viewpoint of improving moisture resistance and dispersibility, inorganic fillers include aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, organosilazane compounds, titanate-based coupling agents, and the like. It is preferably treated with one or more surface treatment agents. As a commercial item of a surface treatment agent, For example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyl trimethoxysilane), Shin-Etsu Chemical Co., Ltd. product "KBM803" (3-mercapto) Propyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltri methoxysilane), Shin-Etsu Chemical Co., Ltd. product "SZ-31" (hexamethyldisilazane), etc. are mentioned.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and still more preferably 0.2 mg/m 2 or more. On the other hand, from the viewpoint of preventing an increase in melt viscosity of the resin varnish or melt viscosity in 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 still more preferable.

The amount of carbon per unit surface area of an inorganic filler can be measured, after washing-processing the inorganic filler after surface treatment 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 a surface treatment agent, followed by ultrasonic cleaning at 25° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horibase Corporation, etc. can be used.

From the viewpoint of obtaining an insulating layer having a low coefficient of thermal expansion, the content of the inorganic filler in the resin layer is preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, 55% by mass or more. or more, or 60 mass % or more. The upper limit of the content of the inorganic filler is preferably 85% by mass or less, more preferably 80% by mass or less from the viewpoint of the mechanical strength of the obtained insulating layer.

-(d) polymer component-

The resin layer may further contain a polymer component selected from the group consisting of (d1) an organic filler and (d2) a thermoplastic resin. (a) By containing a polymer component in combination with an epoxy resin and (b) a specific hardening|curing agent, the fall of the peeling strength of the insulating layer in the high-temperature, high-humidity environment by HAST and a circuit can further be suppressed.

(d1) As the organic filler, any organic filler that can be used in the production of printed wiring boards may be used, and examples thereof include rubber particles, polyamide fine particles, silicon particles, and the like, and rubber particles are preferable.

The rubber particles are not particularly limited as long as they are fine particles of a resin that is chemically crosslinked to a resin exhibiting rubber elasticity and made insoluble or infusible in an organic solvent, for example, acrylonitrile butadiene rubber particles, butadiene rubber particles, acrylic a rubber particle etc. are mentioned. As commercially available rubber particles, for example, "XER-91" manufactured by Nippon Kosei Rubber Co., Ltd., "Staphyloid AC3355", "Staphyloid AC3816", and "Staphyloid AC3401N" by Aika Kogyo Co., Ltd. ”, “Staphyloid AC3816N”, “Staphyloid AC3832”, “Staphyloid AC4030”, “Staphyloid AC3364”, “Staphyloid IM101”, Kureha Chemical Co., Ltd.’s “Pararoid EXL2655” ', "Pararoid EXL2602", etc. are mentioned.

The average particle diameter of the organic filler is preferably in the range of 0.005 to 1 µm, more preferably in the range of 0.2 to 0.6 µm. The average particle diameter of an organic filler can be measured using a dynamic light scattering method. For example, the organic filler is uniformly dispersed in a suitable organic solvent by ultrasonic waves or the like, and the particle size of the organic filler is obtained using a thick particle size analyzer ("FPAR-1000" manufactured by Otsuka Denshi Co., Ltd.). It can measure by creating a distribution on a mass basis, and making the median diameter into an 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, polycarbonate resin, polyether ether ketone resin, and polyester resin are mentioned. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

The range of 8,000-70,000 is preferable, as for the polystyrene conversion weight average molecular weight of a thermoplastic resin, the range of 10,000-60,000 is more preferable, The range of 20,000-60,000 is still more preferable. The weight average molecular weight of a thermoplastic resin in terms of polystyrene is measured by a gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight in terms of polystyrene 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 Corporation as a column. -804L/K-804L can be calculated by using chloroform or the like as a mobile phase, measuring the column temperature at 40°C, and using a standard polystyrene calibration curve.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetphenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene. and phenoxy resins having at least one skeleton selected from the group consisting of skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. Any functional group, such as a phenolic hydroxyl group and an epoxy group, may be sufficient as the terminal of a phenoxy resin. 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 resins) manufactured by Mitsubishi Chemical Co., Ltd., "YX8100" (phenoxy resin containing a bisphenol S skeleton), and "YX6954" (Bisphenol acetphenone skeleton-containing phenoxy resin), in addition, "FX280" and "FX293" manufactured by Shin-Nittetsu Chemical Co., Ltd., "YL7553" and "YL6794" manufactured by Mitsubishi Chemical Co., Ltd. ', "YL7213", "YL7290" and "YL7482".

As polyvinyl acetal resin, polyvinyl formal resin and polyvinyl butyral resin are mentioned, for example, Polyvinyl butyral resin is preferable. As a specific example of polyvinyl acetal resin, "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", and "Denka Butyral 4000-2" manufactured by Denki Chemical Co., Ltd. are, for example, examples of polyvinyl acetal resin. Butyral 6000-EP", Sekisui Chemical Co., Ltd. S-Rec BH series, BX series, KS series, BL series, BM series, etc. are mentioned.

As a specific example of polyimide resin, "Ricacoat SN20" and "Ricacoat PN20" by Shin-Nippon Rica Co., Ltd. are mentioned. As a specific example of the polyimide resin, furthermore, a linear polyimide obtained by reacting a difunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (a polyimide described in Japanese Patent Application Laid-Open No. 2006-37083); Modified polyimides, such as polysiloxane skeleton containing polyimide (the polyimide of Unexamined-Japanese-Patent No. 2002-12667 and Unexamined-Japanese-Patent No. 2000-319386), are mentioned.

Specific examples of the polyamideimide resin include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyoho Seki Co., Ltd. Specific examples of the polyamideimide resin include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing polysiloxane skeleton) manufactured by Nippon Kasei Kogyo Co., Ltd.

As a specific example of polyether sulfone resin, Sumitomo Chemical Co., Ltd. product "PES5003P" etc. are mentioned.

As a specific example of polysulfone resin, Solvay Advanced Polymers Co., Ltd. product polysulfone "P1700", "P3500", etc. are mentioned.

Among these, (a) epoxy resin and (b) combination with a specific curing agent WHEREIN: From a viewpoint which can further suppress the fall of the peeling strength of the insulating layer in the high temperature, high humidity environment by HAST, and a circuit, as a polymer component , organic fillers, phenoxy resins, and polyvinyl acetal resins are preferred. Accordingly, in one suitable embodiment, the polymer component (d) contains at least one selected from the group consisting of an organic filler, a phenoxy resin, and a polyvinyl acetal resin.

Content of the polymer component in a resin layer, from a viewpoint of suppressing generation|occurrence|production of a pinhole, from a viewpoint of suppressing the fall of the peeling strength of an insulating layer and a circuit, Preferably it is 0.5 mass % or more, More preferably, it is 1 mass % or more, More Preferably it is 1.5 mass % or more, or 2 mass % or more. The upper limit of the content of the polymer component is preferably 10% by mass or less, more preferably 9% by mass or less, still more preferably 8% by mass or less, 7% by mass or less, 6% by mass or less, or 5% by mass or less. .

-(e) curing accelerator-

The resin layer may further contain a curing accelerator.

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, a metal 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 these, (a) epoxy resin and (b) combination with a specific curing agent. , it is preferable to contain at least one selected from the group consisting of imidazole-based curing accelerators and amine-based curing accelerators.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl Imidazolyl (1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-tri azine, 2,4-diamino-6-[2'-methylimidazolyl-(1')-ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a ]Imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins Sieves (also referred to as "adduct body of imidazole-epoxy resin".) are mentioned, and the adduct body of imidazole-epoxy resin is preferable. As a specific example of the adduct body of imidazole-epoxy resin, "P200H50" by Mitsubishi Chemical Co., Ltd. is mentioned.

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

Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphoniumdecanoate, (4-methylphenyl)triphenyl Phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc. are mentioned, Triphenyl phosphine and tetrabutyl phosphonium decanoate are preferable.

Examples of the guanidine-based 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]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc. are mentioned, dicyandiamide, 1,5,7-triazabicyclo[4.4.0]deca-5-ene is preferred.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese and tin. Specific examples of the organometallic complex include organocobalt complexes such as cobalt(II)acetylacetonate and cobalt(III)acetylacetonate, organocopper complexes such as copper(II)acetylacetonate, zinc(II)acetylacetonate, and the like. organic zinc complexes, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Specific examples of the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Among these, (a) the epoxy resin and (b) the combination of the specific curing agent WHEREIN: From a viewpoint which can further suppress the fall of the peeling strength of the insulating layer and circuit in the high-temperature, high-humidity environment by HAST, as a hardening accelerator, The adduct body of imidazole-epoxy resin, 4-dimethylaminopyridine is preferable. Accordingly, in one suitable embodiment, the curing accelerator contains at least one selected from the group consisting of an adduct of imidazole-epoxy resin, and 4-dimethylaminopyridine.

From a viewpoint which can further suppress the fall of the peeling strength of the insulating layer and circuit in high-temperature, high-humidity environment by HAST, when content of the hardening accelerator in a resin layer makes the resin component in a resin layer 100 mass %, it is preferable Preferably it is 0.03 mass % or more, More preferably, it is 0.05 mass % or more, 0.1 mass % or more, 0.15 mass % or more, or 0.2 mass % or more. In the case of manufacturing a printed wiring board, when the resin sheet and the inner layer substrate are collectively molded by vacuum hot press processing, the content of the curing accelerator in the resin layer is preferably higher, and the resin component in the resin layer is 100% by mass. Preferably, it is 0.3 mass % or more, 0.5 mass % or more, 0.6 mass % or more, 0.8 mass % or more, or 1 mass % or more. The upper limit of content of a hardening accelerator becomes like this. Preferably it is 4 mass % or less, More preferably, it is 3.5 mass % or less, 3 mass % or less, or 2.5 mass % or less. In addition, the "resin component" talking about content of a hardening accelerator means the component except an inorganic filler among the nonvolatile components which comprise a resin layer.

In addition, when using a metallic hardening accelerator as a hardening accelerator, content of the metallic hardening accelerator in a resin layer may be lower than said range. For example, when the content of the metal-based curing accelerator in the resin layer is 100% by mass of the resin component in the resin layer, the amount of the metal derived from the metal-based curing accelerator is preferably 25 to 1000 ppm, more preferably 40 to Even 500ppm is fine.

In a suitable embodiment, the resin layer further contains, in addition to (a) an epoxy resin and (b) a specific curing agent, (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 nonvolatile component in the resin layer is 100% by mass, (c) the content of the inorganic filler is 40 to 85% by mass, (d) the content of the polymer component is 0.5 to 10% by mass,

When the resin component in a resin layer is 100 mass %, content of (e) hardening accelerator is 0.03-4 mass %.

According to this embodiment, even if it is a case of using the metal foil which has a low roughness surface, the resin sheet (metal foil with resin) which can suppress further the fall of the peeling strength of the insulating layer and circuit in the high-temperature, high-humidity environment by HAST. can be realized

Among these embodiments, (c) the inorganic filler is silica, (d) the polymer component contains at least one selected from the group consisting of an organic filler, a phenoxy resin, and a polyvinyl acetal resin, and (e) a curing accelerator In the embodiment containing at least one selected from the group consisting of a, imidazole-epoxy resin adduct and 4-dimethylaminopyridine, the peel strength of the insulating layer and circuit under a high-temperature, high-humidity environment by HAST It is particularly excellent in the performance of suppressing the deterioration of

-(f) curing agents other than active ester curing agents and phenolic curing agents containing triazine structures-

The resin layer may further contain a curing agent other than the component (b), that is, a curing agent other than the active ester curing agent and the triazine structure-containing phenol curing agent.

(b) The curing agent other than the component is not particularly limited as long as it has a function of curing the epoxy resin, for example, a phenol-based curing agent (excluding a phenol-based curing agent containing a triazine structure), a cyanate ester-based curing agent, and benzo and an oxazine-based curing agent, a carbodiimide-based curing agent, and an acid anhydride-based curing agent. These hardening|curing agents may be used individually by 1 type, or may be used in combination of 2 or more type.

Although it does not specifically limit as a phenolic hardening|curing agent (except a triazine structure containing phenolic hardening|curing agent), For example, a biphenyl-type hardening|curing agent, a naphthalene-type hardening|curing agent, a phenol novolak-type hardening|curing agent, a naphthylene ether type hardening|curing agent, etc. are mentioned there is. As a specific example, "MEH-7700", "MEH-7810", "MEH-7851" (biphenyl type hardening|curing agent) manufactured by Meiwa Kasei Co., Ltd., "NHN", "CBN" manufactured by Nihon Kayaku Co., Ltd. ”, “GPH” (naphthalene-type hardener), manufactured by Shin-Nittetsu Chemical Co., Ltd. “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN375”, “ SN395" (naphthalene type curing agent), "TD-2090" (phenol novolak type curing agent) manufactured by DIC Corporation, "EXB-6000" manufactured by DIC Corporation (naphthylene ether type curing agent), etc. are mentioned. .

Although it does not specifically limit as a cyanate ester type hardening|curing agent, For example, a novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening|curing agent, a dicyclopentadiene type cyanate ester type hardening|curing agent, bisphenol type (bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate ester curing agent, and a prepolymer in which these are partially triazined, and the like. Specific examples include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis (2,6-dimethylphenyl cyanate), 4 ,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene)benzene, bis(4-cyanatephenyl)thioether, and bis bifunctional cyanate resins such as (4-cyanate phenyl) ether, polyfunctional cyanate resins derived from phenol novolac and cresol novolak, etc., and prepolymers in which these cyanate resins are partially triazined, and the like. As a specific example of a nate ester type hardening|curing agent, "PT30", "PT30S" and "PT60" (all are phenol novolak type polyfunctional cyanate ester resin), "BADcy" (bisphenol A dicyanate) manufactured by Ron Japan Co., Ltd. , "BA230" (a prepolymer in which a part or all of bisphenol A dicyanate was triazineized to become a trimer), etc. are mentioned.

As a specific example of a benzoxazine type hardening|curing agent, "HFB2006M" by Showa Kofunshi Co., Ltd., "P-d", and "F-a" by Shikoku Kasei Kogyo Co., Ltd. are mentioned.

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

Although it does not specifically limit as an acid anhydride type hardening|curing agent, For example, For example, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride , trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, anhydride Trimellitic acid, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl)-naphtho [1,2-C] furan-1, polymer-type acid anhydrides, such as 3-dione, ethylene glycol bis (anhydro trimellitate), and styrene maleic acid resin which copolymerized styrene and maleic acid, etc. are mentioned. Specific examples of the acid anhydride curing agent include "SMA EF30" manufactured by Cray Valley HSC.

(b) When using a curing agent other than the component, the content of the curing agent in the resin layer is preferably 0.5 mass % or more, more preferably 1 mass % or more, still more preferably 1.5 mass % or more, or 2 mass % or more. % or more The upper limit of the said content becomes like this. Preferably it is 20 mass % or less, More preferably, it is 15 mass % or less, or 10 mass % or less.

-(g) flame retardant-

The resin 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 layer is not specifically limited, Preferably it is 0.5-10 mass %, More preferably, it is 1-9 mass %.

-Other additives-

The resin layer may further contain other components as needed. Examples of such other components include organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds, and resin additives such as thickeners, defoamers, leveling agents, adhesion imparting agents, and colorants.

What is necessary is just to determine the minimum melt viscosity of a resin layer according to the method of collectively molding a resin sheet and an inner-layer board|substrate at the time of manufacture of a printed wiring board.

When the resin sheet and the inner layer substrate are collectively molded by vacuum hot press processing, the minimum melt viscosity of the resin layer is preferably 8000 poise or more, more preferably 8500 poise or more, from the viewpoint of suppressing the seeping of the resin, Or more than 9000 poise. The upper limit of the minimum melt viscosity of the resin layer is preferably 40000 poise or less, more preferably 38000 poise or less, 36000 poise or less, 34000 poise or less, or 32000 poise or less, from the viewpoint of achieving good lamination property (circuit embedding property). is below.

When the resin sheet and the inner layer substrate are collectively molded by vacuum lamination, the minimum melt viscosity of the resin layer is preferably 300 poise or more, more preferably 500 poise or more, 700 from the viewpoint of suppressing the resin seeping out. Poise or more, 900 poise or more, or 1000 poise or more. The upper limit of the minimum melt viscosity of the resin layer is preferably 12,000 poise or less, more preferably 10000 poise or less, still more preferably 8000 poise or less, 7000 poise or less from the viewpoint of achieving good lamination property (circuit embedding property). , 6000 poise or less, 5000 poise or less, or 4000 poise or less.

In addition, the "minimum melt viscosity" of a resin layer means the minimum viscosity which a resin layer shows when resin of a resin layer melt|dissolves. Specifically, when the resin layer is heated at a constant temperature increase rate to melt the resin, in the initial stage, the melt viscosity decreases as the temperature rises, and then, when the temperature exceeds a certain temperature, the melt viscosity increases with the temperature rise. "Minimum melt viscosity" means such a minimum melt viscosity. The minimum melt viscosity of the resin layer can be measured by a dynamic viscoelasticity method, for example, according to the method described in <Measurement of the minimum melt viscosity of the resin layer> described later.

The minimum melt viscosity of a resin layer can be adjusted by changing content of (e) component, drying conditions of the resin varnish mentioned later, etc., for example.

The resin sheet of this invention can bring about a printed wiring board with high peeling strength of an insulating layer and a circuit. Specifically, the peeling strength (S1) of the insulating layer and the circuit after forming the insulating layer by curing the resin layer and forming the circuit by the subtractive method or the modified semi-additive method is preferably 0.5 kgf/cm or more, more preferably 0.52 kgf/cm or more, still more preferably 0.54 kgf/cm or more, 0.56 kgf/cm or more, 0.58 kgf/cm or more, or 0.6 kgf/cm or more. Although the upper limit of the said peeling strength S1 is not specifically limited, Usually, it can be set as 1.2 kgf/cm or less, etc.

The resin sheet of this invention can bring about the highly reliable printed wiring board which can suppress the fall of the peeling strength of the insulating layer in high-temperature, high-humidity environment by HAST, and a circuit. Specifically, the resin layer is cured to form an insulating layer, a circuit is formed by a subtractive method or a modified semi-additive method, and after 100 hours have elapsed under the conditions of 130° C. and 85% RH, The peeling strength (S2) of an insulating layer and a circuit becomes like this. Preferably it is 0.3 kgf/cm or more, More preferably, it is 0.32 kgf/cm or more, More preferably, it is 0.34 kgf/cm or more, 0.36 kgf/cm or more, 0.38 kgf/ cm or more or 0.4 kgf/cm or more. Although the upper limit of the said peeling strength S2 is not specifically limited, Usually, it can be set as 1.2 kgf/cm or less, etc.

The measurement of the peeling strength of an insulating layer and a circuit can be performed based on JISC6481, For example, it can measure according to the method as described in <Measurement of the peeling strength of an insulating layer and a circuit> mentioned later.

The resin sheet of this invention WHEREIN: A protective film can further be laminated|stacked on the surface (namely, the surface on the opposite side to the metal foil) of the resin layer which is not joined to the metal foil. Accordingly, in one embodiment, the resin sheet of the present invention includes a metal foil having first and second main surfaces, a resin layer bonded to the first main surface of the metal foil, and a protective film bonded to the resin layer. do. As the protective film, a film made of a plastic material is preferably used. Here, as the plastic material, for example, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic such as polycarbonate (PC) and polymethyl methacrylate (PMMA), polystyrene, and cyclic polyolefin , triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone (PEK), polyether ether ketone (PEEK), polyphenylene sulfide (PPS), polyimide, and the like. By laminating|stacking a protective film, adhesion of dust, etc. to the surface of a resin layer, and a flaw can be prevented. A resin sheet can be wound up and stored in roll shape, and in the case of manufacture of a printed wiring board, it becomes usable by peeling a protective film.

The resin sheet of this invention can be produced by providing a resin layer so that it may join with the 1st main surface of metal foil.

The resin layer can be provided by a known method. For example, a resin varnish in which a resin composition is dissolved in a solvent is prepared, this resin varnish is applied to the first main surface of metal foil using a coating device such as a die coater, and the resin varnish is dried to provide a resin layer. there is.

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

What is necessary is just to dry the resin varnish by well-known drying methods, such as a heating and hot air spraying. When a large amount of solvent remains in the resin layer, since it causes swelling after curing, the amount of residual solvent in the resin layer is usually 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, It is dried so that it may become 2 mass % or less, or 1 mass % or less. Although it also changes depending on the boiling point of the solvent in the resin varnish, for example, when using a resin varnish containing 30 to 60 mass % of a solvent, by drying at 50 to 150° C. for 3 to 10 minutes, a resin layer can be formed. there is.

When providing a protective film, it is preferable to laminate a protective film to a resin layer by a roll, press crimping|compression-bonding, etc.. A lamination process can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, the vacuum pressurization type laminator by the Meiki Sesakusho Co., Ltd. product, the vacuum applicator by the Nichigo Morton Co., Ltd. product, etc. are mentioned, for example.

Alternatively, using an adhesive film including a resin layer, the resin layer may be provided to be bonded to the first main surface of the metal foil. In such a form, the adhesive film containing a support body and the resin layer joined with the said support body is laminated|stacked on metal foil so that a resin layer may join with the 1st main surface of metal foil. Thereby, even when using thin metal foil with difficult application|coating of a resin varnish, a resin layer can be provided easily. What is necessary is just to make the material of a support body similar to said protective film, and in this form, it is possible for a support body to also serve as said protective film.

The adhesive film can be prepared by, for example, preparing a resin varnish in which a resin composition is dissolved in a solvent, applying this resin varnish on a support using a die coater or the like, and drying the resin varnish to form a resin layer. there is. What is necessary is just to use the solvent similar to the above.

Since lamination of the adhesive film and the metal foil has good workability and a constant state of contact is easily obtained, it is preferable to laminate the adhesive film to the metal foil by roll crimping, press crimping, or the like. Among these, the vacuum lamination method of laminating under reduced pressure is more preferable. A lamination process can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators are as described above.

The resin sheet produced using the adhesive film becomes usable by removing the support body derived from an adhesive film, when manufacturing a printed wiring board.

[Laminate]

A laminated board can be manufactured using the resin sheet of this invention.

In a preferred embodiment, the laminate of the present invention is formed by placing the inner layer substrate between two resin sheets of the present invention so that the resin layer and the inner layer substrate are bonded, and collectively molding by vacuum hot press treatment or vacuum lamination treatment. is obtained.

In the present invention, the "inner layer substrate" mainly refers to a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or one or both sides of the substrate Refers to a circuit board on which a patterned conductor layer (circuit) is formed. In addition, when manufacturing a printed wiring board, an inner-layer circuit board of an intermediate product on which an insulating layer and/or a conductor layer must be additionally formed is also included in the "inner-layer board" referred to in the present invention.

Hereinafter, the embodiment to be collectively molded by vacuum hot press processing is referred to as “first embodiment”, and the embodiment to be collectively molded by vacuum lamination processing is referred to as “second embodiment”.

-First embodiment-

In 1st Embodiment, it is suitable to manufacture the laminated board of this invention by the following procedure using a vacuum hot press apparatus.

First, a laminated structure in which an inner layer substrate is disposed so that the resin layer and the inner layer substrate are bonded between two resin sheets of the present invention is prepared, and the laminated structure is set in a vacuum hot press apparatus.

It is preferable to set the laminated structure to a vacuum hot press device via a cushion paper, a metal plate such as a stainless plate (SUS plate), a release film, or the like. The laminated structure, for example, is laminated in the order of cushion paper/metal plate/release film/laminated structure (ie, resin sheet/inner layer substrate/resin sheet)/release film/SUS plate/cushion paper and set in a vacuum hot press device. . Here, the symbol "/" means that the constituent elements shown to be interposed therebetween are arranged so as to be in contact with each other (hereinafter, the same applies in the description of the laminated structure, etc.).

Next, a vacuum hot press process in which the laminated structure is heat-compressed under reduced pressure is performed.

The vacuum hot press process can be performed using a conventionally known vacuum hot press apparatus in which the laminated structure is pressed from both sides of the laminated structure with a heated metal plate such as a SUS plate. As a commercially available vacuum hot press apparatus, "MNPC-V-750-5-200" by Meiki Sesakusho Co., Ltd., "VH1-1603" by Kitagawa Seiki Co., Ltd. etc. are mentioned, for example. can

A vacuum hot press process may be performed only once, and may be performed repeatedly 2 or more times.

In the vacuum hot press treatment, the compression pressure (pressing force) is preferably 5 to 80 kgf/cm 2 (0.49 to 7.9 MPa), more preferably 10 to 60 kgf/cm 2 (0.98 to 5.9 MPa).

In the vacuum hot press treatment, the pressure of the atmosphere, that is, the pressure at the time of reduced pressure in the chamber in which the laminate structure to be treated is stored, is preferably 3×10 ^-2 MPa or less, more preferably 1×10 ^-2 MPa is below.

In the vacuum hot press treatment, the heating temperature T, although also depending on the composition of the resin layer, is usually 150°C or higher, preferably 160°C or higher, more preferably 170°C or higher, or 180°C or higher. . Although the upper limit of heating temperature T is not specifically limited, Usually, it can be set as 240 degrees C or less, etc.

From the viewpoint of suppressing cracks and deformation, the vacuum hot press treatment is preferably performed while raising the temperature stepwise or continuously and/or while lowering the temperature stepwise or continuously. In this case, it is preferable that the highest attained temperature satisfy|fills the said desired temperature condition.

The vacuum hot press treatment is, for example, from room temperature to the heating temperature (T) at a temperature increase rate (S ₁ ), and after holding for a predetermined time at the heating temperature (T), the heating temperature (S ₂ ) at the heating temperature ( What is necessary is just to carry out under the heating condition which temperature-falls from T) to room temperature. The temperature increase rate (S ₁ ) and the temperature decrease rate (S ₂ ) are usually 0.5 to 30°C/min, preferably 1 to 10°C/min, more preferably 2 to 8°C/min. The duration of 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 to 180 minutes, preferably 5 to 150 minutes, more preferably 10 to 120 minutes.

By vacuum hot press treatment, the resin layer is cured to form an insulating layer. Therefore, the obtained laminated board has a layer structure of metal foil/insulating layer/inner-layer substrate/insulating layer/metal foil.

-Second Embodiment-

In 2nd Embodiment, it is suitable to manufacture the laminated board of this invention by the method containing the following processes (I) and (II).

(I) A step of disposing an inner layer substrate between two resin sheets of the present invention so that the resin layer and the inner layer substrate are bonded to each other and performing vacuum lamination treatment

(II) Step of thermosetting the resin layer to form an insulating layer

In the step (I), between two resin sheets of the present invention, the inner layer substrate is disposed so that the resin layer and the inner layer substrate are bonded to each other, and vacuum lamination is carried out.

A vacuum lamination process can be performed by thermocompression-bonding a resin sheet to an inner-layer board|substrate from the metal foil side. As a member (hereinafter also referred to as a "thermocompression bonding member") which heat-compresses a resin sheet to an inner-layer board|substrate, a heated metal plate (SUS end plate etc.), a metal roll (SUS roll), etc. are mentioned, for example. In addition, it is preferable to press through an elastic material, such as a heat-resistant rubber, so that a resin sheet may fully be harvested to the surface unevenness|corrugation of an inner-layer board|substrate, rather than directly pressing a thermocompression-compression-bonding member to a resin sheet.

In the vacuum lamination treatment, the heating temperature is preferably in the range of 60 to 160°C, more preferably 80 to 140°C, and the pressing pressure is preferably 1 to 18 kgf/cm 2 (0.098 to 1.77 MPa), more It is preferably in the range of 3 to 15 kgf/cm 2 (0.29 to 1.47 MPa), and the compression time is preferably in the range of 20 to 400 seconds, more preferably in the range of 30 to 300 seconds. The vacuum lamination treatment is preferably performed under reduced pressure conditions of 26.7 hPa or less.

A vacuum lamination process can be implemented using a commercially available vacuum laminator. A commercially available vacuum laminator is as above-mentioned.

After the vacuum lamination treatment, the laminated resin sheet may be smoothed under normal pressure (under atmospheric pressure), for example, by pressing the thermocompression-bonding member from the metal foil side. The thermocompression bonding conditions of the smoothing process should just be the same conditions as the thermocompression bonding conditions of the said vacuum lamination process. A smoothing process can be implemented with a commercially available laminator. In addition, you may perform lamination|stacking and a smoothing process continuously using said commercially available vacuum laminator.

Step (II) WHEREIN: The resin layer is thermosetted and the insulating layer is formed.

The conditions for thermosetting are not specifically limited, What is necessary is just to use the conditions normally employ|adopted when forming the insulating layer of a printed wiring board.

For example, although the thermosetting conditions of a resin layer also change with the composition of a resin layer, the range of hardening temperature is 120-240 degreeC (preferably the range of 150-210 degreeC, More preferably, 170-190 degreeC) range) and curing time may be in the range of 5 to 90 minutes (preferably 10 to 75 minutes, more preferably 15 to 60 minutes).

Before thermosetting the resin layer, the resin layer may be preheated to a temperature lower than the curing temperature. For example, before thermosetting the resin layer, the resin layer is heated at a temperature of 50°C or more and less than 120°C (preferably 60°C or more and 110°C or less, more preferably 70°C or more and 100°C or less) for 5 minutes. You may preheat more than (preferably for 5 to 150 minutes, More preferably, for 15 to 120 minutes).

By the step (II), the resin layer is cured to form an insulating layer, and a laminate having a laminate structure of metal foil/insulating layer/inner layer substrate/insulating layer/metal foil is obtained.

Regardless of the first embodiment and the second embodiment, (A) a step of drilling, (B) a step of desmearing, and (C) forming a circuit by a subtractive method or a modified semiadditive method You may carry out the process of doing this additionally. Accordingly, in one embodiment, the laminate of the present invention includes a circuit formed by a subtractive method or a modified semi-additive method.

The step (A) is a step of drilling, whereby a via hole can be formed in the insulating layer. What is necessary is just to implement a process (A) by a well-known procedure using, for example, a drill, a laser, plasma, etc. according to the composition etc. of the resin layer used for formation of an insulating layer.

A process (B) is a process of performing a desmear process. Generally, a resin residue (smear) derived from an insulating layer adheres to the inside of the via hole formed in the step (A). Since such a smear becomes a cause of poor electrical connection between layers, the process (desmear process) which removes a smear in a process (B) is performed.

The procedure and conditions of a desmear process are not specifically limited, The well-known procedure and conditions normally used in manufacture of a printed wiring board are employable. For example, a desmear process can be performed by performing the swelling process by a swelling liquid, the oxidation process by an oxidizing agent solution, and the neutralization process by a neutralizing liquid in this order. As a swelling liquid, "Swelling Deep Securigansu P", "Swelling Deep Securigansu SBU" etc. by Atotech Japan Co., Ltd. product are mentioned, for example. It is preferable to perform a swelling process by immersing the laminated board in which the via hole was formed in the swelling liquid heated to 60-80 degreeC for 5 to 10 minutes. As an oxidizing agent solution, alkaline permanganic acid aqueous solution is preferable, for example, the solution which melt|dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. It is preferable to perform oxidation treatment by an oxidizing agent solution by immersing the laminated board after a swelling process in the oxidizing agent solution heated to 60-80 degreeC for 10 to 30 minutes. As a commercial item of alkaline permanganic acid aqueous solution, "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Atotech Japan Co., Ltd. are mentioned, for example. It is preferable to carry out the neutralization process by a neutralizing liquid by immersing the laminated board after an oxidation process in 30-50 degreeC neutralizing liquid for 3 to 10 minutes. As a neutralizing liquid, acidic aqueous solution is preferable, and as a commercial item, "Reduction Solution Secure P" manufactured by Atotech Japan Co., Ltd. is mentioned, for example.

Step (C) is a step of forming a circuit by a subtractive method or a modified semi-additive method.

In a process (C), a circuit can be formed by the subtractive method or a modified semiadditive method using the metal foil derived from the resin sheet of this invention.

In the subtractive method, an unnecessary part (non-circuit formation part) of metal foil is selectively removed by etching etc., and a circuit is formed. What is necessary is just to implement circuit formation by a subtractive method according to a well-known procedure. For example, circuit formation by the subtractive method includes i) providing an etching resist on the surface (ie, the second main surface) of the metal foil of the laminate, ii) exposing and developing the etching resist to form a wiring pattern and iii) etching away the exposed metal foil portion, and iv) removing the etching resist.

In the modified semi-additive method, the non-circuit forming part of the metal foil is protected with a plating resist, and a metal such as copper is thickened in the circuit forming part by electrolytic plating, then the plating resist is removed, The metal foil is removed by etching to form a circuit. The circuit formation by the modified semiadditive method may be performed according to a known procedure. For example, circuit formation by the modified semi-additive method includes: i) providing a plating resist on the surface (ie, the second main surface) of the metal foil of the laminate, ii) exposing and developing the plating resist to form a wiring pattern forming, iii) electrolytic plating through a plating resist, iv) removing the plating resist, v) etching and removing the metal foil other than the circuit forming portion. In addition, when the metal foil derived from the resin sheet is thick, before i), the entire surface of the metal foil may be thinned by etching or the like so that the metal foil has a desired thickness (usually 5 µm or less, 4 µm or less, or 3 µm or less).

It is calculated|required that an insulating layer and a circuit show sufficient adhesive strength (peel strength), and this adhesiveness is generally obtained by the anchor effect resulting from the interface roughness of an insulating layer and a circuit. However, if the surface irregularities are large, when removing the unnecessary portion (non-circuit forming portion) of the metal foil by etching during circuit formation, it is difficult to remove the metal foil from the anchor portion, and the condition is sufficient to remove the metal foil from the anchor portion. In the case of etching, the dissolution of the wiring pattern is remarkable, which hinders the miniaturization of the circuit. According to this point and the resin sheet of this invention, it is possible to use metal foil with a low surface roughness, realizing the favorable peeling strength of an insulating layer and a circuit. For this reason, in the laminate obtained by using the resin sheet of the present invention, the interface roughness between the metal foil and the insulating layer is low, and the unnecessary portion (non-circuit forming portion) of the metal foil can be easily removed by etching without dissolving the wiring pattern. can

In the present invention, a fine circuit can be formed. For example, a circuit having a circuit width (line; L) and a circuit width (space; S) ratio (L/S) of 35 µm/35 µm or less (ie, wiring pitch 70 µm or less) can be manufactured with good yield can be formed Further, L/S = 30 µm/30 µm or less (wiring pitch 60 µm or less), L/S = 25 µm/25 µm or less (wiring pitch 50 µm or less), or L/S = 20 µm/20 µm or less ( A fine circuit having a wiring pitch of 40 µm or less) can be formed with good manufacturing yield.

The laminate of the present invention can be used for various purposes depending on its manufacturing method and structure (the presence or absence of circuit formation, the type of inner-layer substrate to be used, etc.). For example, it may be used as a metal clad laminated board used for manufacture of a printed wiring board, or an inner-layer circuit board, and may be used as a printed wiring board.

[Semiconductor device]

A semiconductor device can be manufactured using the printed wiring board which consists of the laminated board of this invention, or using the printed wiring board manufactured using the laminated board of this invention.

Examples of the semiconductor device include various semiconductor devices provided for electric products (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trams, ships and airplanes, etc.). there is.

The semiconductor device of this invention can be manufactured by mounting a component (semiconductor chip) in the conduction|electrical_connection location of a printed wiring board. A "conduction location" is "a location through which an electric signal is transmitted in a printed wiring board", and the location may be a surface, a buried location, or any. In addition, a semiconductor chip will not be specifically limited if it is an electric circuit element which uses a semiconductor as a material.

Although the semiconductor chip mounting method at the time of manufacturing the semiconductor device of this invention is not specifically limited as long as the semiconductor chip functions effectively, Specifically, a wire bonding mounting method, a flip chip mounting method, and a bumpless build-up layer The mounting method by (BBUL), the mounting method by an anisotropic conductive film (ACF), the mounting method by a nonelectroconductive film (NCF), etc. are mentioned. Here, "a mounting method using a bumpless build-up layer (BBUL)" refers to a "mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board to connect the semiconductor chip and wiring on the printed wiring board".

[Example]

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In the following description, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Measuring method and evaluation method>

First, various measurement methods and evaluation methods are demonstrated.

[Preparation of substrate for measurement and evaluation]

(1) Treatment of the underlying substrate of the inner layer substrate

Both sides of the glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, 255 mm × 340 mm size, Panasonic Co. CZ8100"), 1 µm was etched to roughen the copper surface.

(2) Production of laminated board

The resin sheet produced in the following Production Example was cut to a size of 250 mm x 335 mm. Next, the inner layer substrate is disposed between the two resin sheets so that the resin layer and the inner layer substrate are bonded, and vacuum hot press treatment (Examples 1 to 3 and Comparative Examples 1 to 4) or vacuum lamination treatment (Example 4) ) to obtain a laminate having a layer structure of metal foil/insulating layer/inner layer substrate/insulating layer/metal foil. The vacuum hot press process and the vacuum lamination process were performed according to the following procedure.

(2A) vacuum heat press processing

The vacuum hot press process was performed using a vacuum hot press apparatus ("VH1-1603" manufactured by Kitagawa Seiki Co., Ltd.). Specifically, the following laminated structure was prepared, and the laminated structure was subjected to a vacuum hot press process with a vacuum hot press apparatus.

Laminate structure: cushion paper/SUS plate/release sheet/resin sheet (metal foil/resin layer)/inner layer substrate/resin sheet (resin layer/metal foil)/release sheet/SUS plate/cushion paper

As the cushion paper, "AACP-9N" (thickness: 800 µm) manufactured by Awasei City Co., Ltd. was used, and as the release film, "Aprex 50N NT" (thickness: 50 µm) manufactured by Asahi Glass Co., Ltd. was used. In addition, the thickness of the SUS plate was 1 micrometer.

The conditions of the vacuum heat press treatment are as follows.

Temperature: The temperature is raised from room temperature (room temperature) to the temperature (T) shown in Table 2 at a temperature increase rate of 5°C/min, held at the temperature (T) for 60 minutes, and thereafter, the temperature (T) at a temperature decrease rate of 5°C/min. temperature down to room temperature

Pressure (pressing force): When the temperature reaches about 125°C, the pressing force is set to 30 kgf/cm 2 (2.9 MPa), and this is maintained until the temperature drop is finished.

Atmospheric pressure: 70 to 74 mmHg (9.3×10 ^-3 MPa to 9.9×10 ^-3 MPa)

(2B) vacuum lamination

The vacuum lamination process was performed using the batch type vacuum pressurization laminator (2-stage build-up laminator "CVP7001" manufactured by Nichigo Morton Co., Ltd.). Specifically, the resin sheet was vacuum laminated on both surfaces of the inner layer substrate so that the resin layer and the inner layer substrate were bonded. After vacuum lamination process pressure-reduced for 30 second and air pressure was 13 hPa or less, 100 degreeC and pressure 0.74 Mpa were performed by pressing for 30 second. Next, the laminated resin sheet was smoothed by pressing for 60 seconds under atmospheric pressure at 100°C and at a pressure of 0.5 MPa. After smoothing, the resin layer was thermosetted at 180° C. for 60 minutes to form an insulating layer.

(3) circuit formation

A circuit was formed by a subtractive method (Examples 1 to 3 and Comparative Examples 1 to 4) or a modified semiadditive method (Example 4) using the metal foil (copper foil) of the laminate.

(3A) Subtractive method

(3A-1) Dry film development

The surface of the laminate was treated with 5% sulfuric acid aqueous solution for 30 seconds. On both sides of the obtained laminated board, a dry film with PET film ("ALPHO NIT3025" manufactured by Nichigo Morton Co., Ltd., dry film thickness of 25 µm) was applied to both sides of the obtained laminated board, and a batch vacuum pressurized laminator (( Note) It was laminated using "MVLP-500" manufactured by Meiki Sesakusho). After lamination|stacking was pressure-reduced for 30 second, and atmospheric|air pressure was 13 hPa or less, it performed by pressing for 20 second at the temperature of 70 degreeC and the pressure of 0.1 Mpa.

Thereafter, a glass mask (photomask) having a wiring pattern (shown below in detail) is placed on the PET film as a protective layer of the dry film, and ultraviolet light is irradiated with an irradiation intensity of 150 mJ/cm 2 by means of a UV lamp. did After UV irradiation, a 1% sodium carbonate aqueous solution at 30° C. was spray-treated at a spray pressure of 0.15 MPa for 30 seconds. Then, it washed with water and developed the dry film (pattern formation).

Wiring pattern for glass mask:

A glass mask having 10 comb teeth patterns of the following i) to iv) and 5 copper beta patterns of the following v) was used. In addition, the comb pattern of the following i) to iv) is for evaluation of the fine circuit forming ability, and the copper beta pattern of the following v) is for measuring the peeling strength of an insulating layer and metal foil (copper foil).

i) L/S = 20㎛/20㎛, that is, a comb pattern with a wiring pitch of 40㎛ (wiring length 15mm, 16 lines)

ii) L/S = 25㎛/25㎛, that is, a comb pattern with a wiring pitch of 50㎛ (wiring length 15mm, 16 lines)

iii) L/S = 30㎛/30㎛, that is, a comb pattern with a wiring pitch of 60㎛ (wiring length 15mm, 16 lines)

iv) L/S = 35㎛/35㎛, that is, a comb pattern with a wiring pitch of 70㎛ (wiring length 15mm, 16 lines)

v) Copper beta pattern 10mm wide and 150mm long

(3A-2) Formation of circuit

Then, using a cupric chloride-based etching solution (copper chloride: 1 × 10 ³ mol/m 3 , hydrochloric acid: 2.9 × 10 ³ mol/m 3 ), horizontal spray treatment is performed at 40° C., and the copper foil is etched, A circuit was formed. Then, the 50 degreeC 3% sodium hydroxide solution was spray-processed by 0.2 MPa of injection pressure, and the dry film with PET was peeled.

(3B) Modified semiadditive method

(3B-1) Copper foil etching

With respect to the copper foil of a laminated board, it etched all over so that the thickness of copper foil might be set to about 3 micrometers using cupric chloride type etching liquid.

(3B-2) Dry film development

Next, development (pattern formation) of the dry film was performed in the same manner as in (3A-1) above.

(3B-3) Electrolytic plating

After dry film development, electrolytic copper plating was performed to form a conductor layer (copper layer) with a thickness of about 17 µm (total thickness with copper foil derived from a resin sheet was about 20 µm).

(3B-4) Formation of circuit

Next, the 50 degreeC 3% sodium hydroxide solution was spray-processed by 0.2 MPa of injection pressure, and the dry film with PET film was peeled. After performing annealing treatment by heating at 190°C for 60 minutes, horizontal spray treatment was performed at 30°C using an etchant for flash etching (“CPE-800D” manufactured by Ryoko Chemical Co., Ltd.), and unnecessary copper foil (resin sheet) The circuit was formed by removing the derived copper foil).

<Measurement of arithmetic mean roughness (Ra) of metal foil surface>

Numerical values obtained with respect to the metal foil used in the following production examples, using a non-contact type surface roughness meter (“WYKO NT3300” manufactured by BCoin Instruments), VSI contact mode, 50x lens, measuring range of 121 μm × 92 μm to obtain the Ra value. For each sample, an average value of 10 randomly selected points was obtained.

<Measurement of Minimum Melt Viscosity of Resin Layer>

About the resin layer of the resin sheet produced in the following preparation example, melt viscosity was measured using the dynamic viscoelasticity measuring apparatus ("Rheosol-G3000" manufactured by U.B.M.). For 1 g of the sample resin composition, using a parallel plate having a diameter of 18 mm, the temperature was raised from the starting temperature of 60 ° C. to 200 ° C. at a temperature increase rate of 5 ° C./min. The viscoelastic modulus was measured and the lowest melt viscosity (poise) was calculated.

<Measurement of Peel Strength of Insulation Layer and Circuit>

(1) Peel strength before HAST

The load (kgf) when peeling off one end of the copper beta pattern portion (width 10 mm, length 150 mm) of the substrate for measurement and evaluation, and holding it with tongs, and pulling 35 mm in the vertical direction at a speed of 50 mm/min at room temperature (kgf) /cm) was measured. A tensile tester (Autocom type tester "AC-50C-SL" manufactured by TSE Corporation) was used for the measurement. Table 2 shows the average value for 5 copper beta patterns.

About the board|substrate which showed favorable peeling strength (0.5 kgf.cm or more) before HAST, the measurement of the peeling strength after HAST and evaluation of the fine circuit formation ability were performed.

(2) Peel strength after HAST

High-accelerated high-temperature, high-humidity lifetime device (HAST) for 100 hours under conditions of 130°C and 85% RH, using a highly accelerated life tester (“PM422” manufactured by Kusumoto Chemical Co., Ltd.) for the substrate for measurement and evaluation was carried out. After HAST, the peel strength was measured in the same manner as in (1) above. Table 2 lists the average values for five copper beta patterns.

<Evaluation of microcircuit forming ability>

Regarding the comb pattern of the above i) to iv) of the substrate for measurement and evaluation, the presence or absence of peeling of the circuit was confirmed with an optical microscope, and the presence or absence of unnecessary copper foil residue was confirmed by measuring the insulation resistance of the comb pattern. And when there was no problem with respect to all 10 comb-tooth patterns, it judged as passing. The fine circuit formation ability was evaluated by the minimum wiring pitch judged as passing. In the said evaluation, it is excellent in the fine circuit formation ability, so that the minimum wiring pitch judged as pass is small.

<Preparation Example 1> Preparation of resin varnish 1

5 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Shin-Nittetsu Chemical Co., Ltd., epoxy equivalent about 169, 1:1 mixture of bisphenol A type and bisphenol F type) 5 parts, bixylenol type epoxy resin (Mitsubishi Chemical) Co., Ltd. "YX4000HK", epoxy equivalent about 185) 10 parts, dicyclopentadiene type epoxy resin (DIC Co., Ltd. "HP7200HH", epoxy equivalent 280) 10 parts, and phenoxy resin (Mitsubishi Chemical Co., Ltd.) 20 parts of manufacture "YL7553BH30", cyclohexanone with a solid content of 30 mass %: 1:1 solution of MEK) were dissolved by heating while stirring in 25 parts of solvent naphtha. After cooling to room temperature, 30 parts of an active ester curing agent (“HPC8000-65T” manufactured by DIC Corporation, an active group equivalent of about 223, a toluene solution containing 65% by mass of a nonvolatile component) 30 parts, an amine curing accelerator (4 -Dimethylaminopyridine (DMAP), MEK solution with a solid content of 5% by mass) 3 parts, imidazole-based curing accelerator (“P200H50” manufactured by Mitsubishi Chemical Co., Ltd., adduct body of imidazole-epoxy resin, nonvolatile component 50 1.5 parts of propylene glycol monomethyl ether solution in mass%), flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phos Parphenanthrene-10-oxide, average particle diameter 2 μm) 2 parts, spherical silica surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (manufactured by Adomatex Co., Ltd.) SO-C2", average particle diameter 0.5 micrometer, carbon amount per unit surface area 0.38 mg/m2) 120 parts were mixed, and it disperse|distributed uniformly with a high-speed rotary mixer, and resin varnish 1 was prepared.

<Preparation Example 2> Preparation of resin varnish 2

5 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Shin-Nittetsu Chemical Co., Ltd., epoxy equivalent about 169, 1:1 mixture of bisphenol A type and bisphenol F type) 5 parts, bixylenol type epoxy resin (Mitsubishi Chemical) Co., Ltd. "YX4000HK", epoxy equivalent about 185) 10 parts, biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Chemical Co., Ltd., epoxy equivalent 269) 10 parts, and phenoxy resin (Mitsubishi Chemical Co., Ltd.) 15 parts of manufacture "YL7553BH30", 1:1 solution of cyclohexanone:MEK with a solid content of 30 mass %) were heat-dissolved, stirring 30 parts of solvent naphtha. After cooling to room temperature, thereto, 10 parts of an active ester curing agent (“HPC8000-65T” manufactured by DIC Co., Ltd., an active group equivalent of about 223, a toluene solution containing 65% by mass of a nonvolatile component), a triazine structure-containing phenolic Hardening agent (hydroxyl equivalent 151, DIC Co., Ltd. "LA-3018", 50% solid content 2-methoxypropanol solution) 10 parts, amine curing accelerator (DMAP, 5 mass % solid MEK solution) 2 parts already Dazole-based curing accelerator (“P200H50” manufactured by Mitsubishi Chemical Co., Ltd., adduct body of imidazole-epoxy resin, propylene glycol monomethyl ether solution containing 50% by mass of nonvolatile component) 1.8 parts, flame retardant (Sanko Co., Ltd.) “HCA-HQ”, average particle diameter 2 μm) 2 parts, spherical silica surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd. “SO- C2", average particle diameter 0.5㎛, carbon amount per unit surface area 0.38mg/m2) 80 parts, silica surface-treated with aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) (manufactured by Unimin) IMSIL A-8", average particle diameter 2.2 µm, carbon amount per unit surface area 0.29 mg/m 2) 60 parts were mixed and uniformly dispersed with a high-speed rotary mixer to prepare resin varnish 2.

<Preparation Example 3> Preparation of resin varnish 3

3 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Shin-Nittetsu Chemical Co., Ltd., epoxy equivalent about 169, 1:1 mixture of bisphenol A type and bisphenol F type) 3 parts, naphthalene type epoxy resin (DIC Ltd.) "HP4032SS", epoxy equivalent about 144) 5 parts, bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent about 185) 10 parts, biphenyl type epoxy resin (manufactured by Nihon Kayaku Co., Ltd.) "NC3000L", 10 parts of epoxy equivalent 269) were heat-dissolved, stirring 15 parts of solvent naphtha. After cooling to room temperature, 12 parts of a phenolic curing agent containing a triazine structure (hydroxyl equivalent of 125, “LA-7054” manufactured by DIC Corporation, MEK solution having a solid content of 60%), a phenol novolac curing agent (hydroxyl group) Equivalent 105, “TD-2090” manufactured by DIC Co., Ltd., MEK solution with a solid content of 60%) 10 parts, polyvinyl butyral resin (glass transition temperature 105° C., “KS-1” manufactured by Sekisui Chemical Co., Ltd.) , 15% solid content ethanol:toluene 1:1 solution) 15 parts, amine-based curing accelerator (DMAP, MEK solution with 5 mass% solid content) 1 part, imidazole-based curing accelerator (Mitsubishi Chemical Co., Ltd. “P200H50”) , imidazole-epoxy resin adduct, propylene glycol monomethyl ether solution containing 50 mass% of nonvolatile components) 2 parts, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., average particle diameter 2 μm) 2 parts , silica surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“IMSIL A-8” manufactured by Unimin, average particle diameter of 2.2 μm, carbon content per unit surface area 0.29 mg/m2 ) 90 parts were mixed, it was made to disperse|distribute uniformly with a high-speed rotation mixer, and the resin varnish 3 was prepared.

<Preparation example 4> (Preparation of resin varnish 4)

5 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Shin-Nittetsu Chemical Co., Ltd., epoxy equivalent of about 169, 1:1 mixture of bisphenol A type and bisphenol F type) 5 parts, naphthalene type epoxy resin (DIC Ltd.) "HP4032SS", epoxy equivalent about 144) 5 parts, bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent about 185) 10 parts, biphenyl type epoxy resin (manufactured by Nihon Kayaku Co., Ltd.) "NC3000L", epoxy equivalent 269) 10 parts, and phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., 1:1 solution of cyclohexanone:MEK having a solid content of 30% by mass) 10 parts, solvent naphtha 15 parts It was dissolved by heating while stirring. After cooling to room temperature, 12 parts of a phenolic curing agent containing a triazine structure (hydroxyl equivalent of 125, “LA-7054” manufactured by DIC Co., Ltd., MEK solution with a solid content of 60%), a naphthalene curing agent (New Nittetsu Sumi) “SN-485” manufactured by King Chemical Co., Ltd., 215 hydroxyl equivalent, MEK solution with a solid content of 60%) 10 parts, polyvinyl butyral resin (glass transition temperature 105° C., “KS-” manufactured by Sekisui Chemical Co., Ltd.) 1", 15% solid content ethanol:toluene 1:1 solution) 10 parts, imidazole-based curing accelerator (1-benzyl-2-phenylimidazole (1B2PZ), 5% solid content MEK solution) 1.5 parts, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., average particle diameter 2 μm) 2 parts, spherical silica surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (Ah Co., Ltd.) 90 parts of "SO-C2" manufactured by DOMATEX, average particle diameter of 0.5 µm, carbon amount per unit surface area of 0.38 mg/m 2) were mixed, and uniformly dispersed with a high-speed rotary mixer to prepare resin varnish 4.

<Preparation example 5> Preparation of resin varnish 5

Triazine structure-containing phenolic curing agent (hydroxyl equivalent of 125, “LA-7054” manufactured by DIC Co., Ltd., MEK solution with a solid content of 60%) is not used, and phenol novolac curing agent (hydroxyl equivalent of 105, DIC (Co.) ) Manufactured "TD-2090", a resin varnish 5 was prepared in the same manner as in Preparation Example 3 except that the blending amount of the 60% solids MEK solution) was changed to 22 parts.

<Preparation Example 6> Preparation of resin varnish 6

6 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Shin-Nittetsu Chemical Co., Ltd., about 169 epoxy equivalent, 1:1 mixture of bisphenol A type and bisphenol F type), bixylenol type epoxy resin (Mitsubishi Chemical) Co.) manufactured "YX4000HK", epoxy equivalent of about 185) 10 parts, and 20 parts of phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., a 1:1 solution of cyclohexanone:MEK having a solid content of 30% by mass), It was heat-dissolved, stirring 25 parts of solvent naphtha. After cooling to room temperature, 45 parts of an acid anhydride curing agent (“SMA EF30” manufactured by Cray Valley HSC, an acid value of 280 mgKOH/g, a 1:1 solution of toluene:MEK having a solid content of 60%) 45 parts, an amine curing accelerator (DMAP, MEK solution having a solid content of 5% by mass) 2 parts, an imidazole-based curing accelerator (“P200H50” manufactured by Mitsubishi Chemical Co., Ltd., an adduct of imidazole-epoxy resin, propylene glycol of 50% by mass of a nonvolatile component) Monomethyl ether solution) 1.5 parts, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., average particle diameter 2 μm) 2 parts, aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 120 parts of treated spherical silica (“SO-C2” manufactured by Adomatex Co., Ltd., average particle diameter of 0.5 μm, carbon amount per unit surface area of 0.38 mg/m 2 ) was mixed and uniformly dispersed with a high-speed rotary mixer, followed by a resin varnish 6 was prepared.

<Preparation Example 7> Preparation of resin varnish 7

3 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Shin-Nittetsu Chemical Co., Ltd., epoxy equivalent 169, 1:1 mixture of bisphenol A type and bisphenol F type) 3 parts, bixylenol type epoxy resin (Mitsubishi Chemical Co., Ltd.) ) manufactured “YX4000HK”, epoxy equivalent about 185) 7 parts, dicyclopentadiene type epoxy resin (“HP7200HH” manufactured by DIC Co., Ltd., epoxy equivalent 280) 8 parts, and phenoxy resin (manufactured by Mitsubishi Chemical Co., Ltd.) "YL7553BH30", cyclohexanone: a 1:1 solution of MEK with a solid content of 30% by mass) 20 parts, cyanate ester curing agent ("BADCy" manufactured by Ronjapan Co., Ltd., bisphenol A dicyanate) 7 parts, solvent naphtha It was made to heat-dissolve, stirring in 15 parts. After cooling to room temperature, thereto, a cyanate ester curing agent ("PT30S" manufactured by Ronjapan Co., Ltd., phenol novolak type polyfunctional cyanate ester resin, a cyanate equivalent of about 133, and a non-volatile content of 85% by mass MEK Solution) 9 parts, amine-based curing accelerator (DMAP, MEK solution having a solid content of 5% by mass) 0.6 parts, metal-based curing accelerator ((Tokyo Kasei Co., Ltd. zinc (II) naphthenate), mineral spirit with a zinc content of 8% solution) of 3% by mass cyclohexanone solution) 4 parts, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., average particle diameter 2 µm) 2 parts, aminosilane-based coupling agent (Shin-Etsu Chemical Co., Ltd.) 90 parts of spherical silica surface-treated with "KBM573") ("SO-C2" manufactured by Adomatex Co., Ltd., average particle diameter of 0.5 µm, carbon content per unit surface area of 0.38 mg/m2) is mixed, and uniformly with a high-speed rotary mixer and dispersed to prepare a resin varnish 7.

The compositions of the resin varnishes 1 to 7 are shown in Table 1.

<Production Example 1> Preparation of resin sheet 1

As the metal foil, a copper foil (HLP foil manufactured by JX Nikko Nikkei Kinzoku Co., Ltd., 18 µm in thickness) was prepared. Hereinafter, the said copper foil is also called "copper foil 1". Ra of the 1st main surface of copper foil 1 was 160 nm, and Ra of the 2nd main surface was 390 nm. The resin varnish 1 was apply|coated to the 1st main surface of the said copper foil 1 with a die coater, and it dried at 80-120 degreeC (average 100 degreeC) for 5 minutes, and the resin sheet 1 which has a 40-micrometer-thick resin layer was produced.

<Production Example 2> Preparation of resin sheet 2

A resin sheet 2 was produced in the same manner as in Production Example 1 except that the resin varnish 2 was used instead of the resin varnish 1.

<Production Example 3> Preparation of resin sheet 3

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

<Production Example 4> Preparation of resin sheet 4

(1) Preparation of adhesive film

As the support, a PET film (“Lumira T6AM” manufactured by Toray Co., Ltd., 25 μm thick) that was subjected to release treatment with an alkyd resin mold release agent (“AL-5” manufactured by Lintec Co., Ltd.) was prepared. Resin varnish 4 was applied to the release surface of the support with a die coater, and dried at 80 to 110°C (average 100°C) for 5 minutes to prepare an adhesive film having a resin layer having a thickness of 40 µm.

(2) Preparation of resin sheet

As the metal foil, copper foil (TP-III foil manufactured by Mitsui Kinzoku Kosan Co., Ltd., 11 µm in thickness) was prepared. Hereinafter, the said copper foil is also called "copper foil 2". Ra of the 1st main surface of copper foil 2 was 290 nm, and Ra of the 2nd main surface was 610 nm. The copper foil 2 was laminated to the adhesive film obtained in (1) above with a heating roll (60° C.) so that the resin layer of the adhesive film and the first main surface of the copper foil 2 were bonded to each other to prepare a resin sheet 4 did The said resin sheet 4 was used after peeling the PET film which is a support body derived from an adhesive film at the time of preparation of the board|substrate for measurement and evaluation.

<Production Example 5> Preparation of resin sheet 5

Except having used the resin varnish 5 instead of the resin varnish 1, it carried out similarly to Production Example 1, and produced the resin sheet 5.

<Production Example 6> Preparation of resin sheet 6

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

<Production Example 7> Preparation of resin sheet 7

A resin sheet 7 was produced in the same manner as in Production Example 1 except that copper foil 3 (3EC-M3-VLP foil manufactured by Mitsui Kinzoku Kosan Co., Ltd., thickness of 18 µm) was used instead of copper foil 1. In addition, Ra of the 1st main surface of the copper foil 3 was 630 nm, and Ra of the 2nd main surface was 410 nm.

<Production Example 8> Preparation of resin sheet 8

Except having used the resin varnish 7 instead of the resin varnish 1, it carried out similarly to Production Example 1, and produced the resin sheet 8.

<Example 1>

Using the resin sheet 1, according to the above [Preparation of the substrate for measurement and evaluation], a substrate for measurement and evaluation was prepared and each evaluation was performed.

<Example 2>

Using the resin sheet 2, according to the above [Preparation of the substrate for measurement and evaluation], a substrate for measurement and evaluation was prepared and each evaluation was performed.

<Example 3>

Using the resin sheet 3, according to the above [Preparation of the substrate for measurement and evaluation], a substrate for measurement and evaluation was prepared, and each evaluation was performed.

<Example 4>

Using the resin sheet 4, according to the above [Preparation of the substrate for measurement and evaluation], a substrate for measurement and evaluation was prepared, and each evaluation was performed.

<Comparative Example 1>

Using the resin sheet 5, according to the above [Preparation of the substrate for measurement and evaluation], a substrate for measurement and evaluation was prepared and each evaluation was performed.

<Comparative Example 2>

Using the resin sheet 6, according to the above [Preparation of the substrate for measurement and evaluation], a substrate for measurement and evaluation was prepared, and each evaluation was performed.

<Comparative Example 3>

Using the resin sheet 7, according to the above [Preparation of the substrate for measurement and evaluation], a substrate for measurement and evaluation was prepared, and each evaluation was performed.

<Comparative Example 4>

Using the resin sheet 8, according to the above [Preparation of the substrate for measurement and evaluation], a substrate for measurement and evaluation was prepared and each evaluation was performed.

Claims (24)

A resin sheet for circuit formation by a subtractive method or a modified semi-additive method, comprising:
A metal foil having first and second main surfaces, and
The resin layer joined to the first main surface of the metal foil
including,
The arithmetic mean roughness (Ra) of the first main surface of the metal foil is 300 nm or less,
The arithmetic mean roughness (Ra) of the second main surface of the metal foil is 300 nm or more,
The thickness of the resin layer is 8 to 400 μm,
A resin sheet, wherein the resin layer contains at least one curing agent selected from the group consisting of (a) an epoxy resin, (b) an active ester curing agent and a triazine structure-containing phenol curing agent. The resin sheet according to claim 1, wherein the resin layer further contains (c) an inorganic filler. The resin sheet according to claim 2, wherein (c) the inorganic filler is silica. The resin sheet of Claim 2 whose content of the (c) inorganic filler in a resin layer is 40-85 mass %, when the non-volatile component in a resin layer makes 100 mass %. The resin sheet according to claim 1, wherein the resin layer further contains (d) a polymer component, and (d) the polymer component is selected from the group consisting of an organic filler and a thermoplastic resin. The resin sheet according to claim 5, wherein the polymer component (d) contains at least one selected from the group consisting of an organic filler, a phenoxy resin, and a polyvinyl acetal resin. The resin sheet according to claim 5, wherein the content of the polymer component (d) in the resin layer is 0.5 to 10 mass% when the nonvolatile component in the resin layer is 100 mass%. The resin sheet according to claim 1, wherein the resin layer further contains (e) a curing accelerator. The resin sheet of Claim 8 whose content of (e) hardening accelerator in a resin layer is 0.03-4 mass %, when the resin component in a resin layer is 100 mass %. The resin sheet according to claim 8, wherein the content of the (e) curing accelerator in the resin layer is 0.3 to 3% by mass when the resin component in the resin layer is 100% by mass. The resin sheet according to claim 8, wherein (e) the curing accelerator contains at least one selected from the group consisting of an imidazole-based curing accelerator and an amine-based curing accelerator. The resin sheet according to claim 8, wherein (e) the curing accelerator contains at least one selected from the group consisting of an adduct of imidazole-epoxy resin and 4-dimethylaminopyridine. The resin layer according to claim 1, further comprising (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 nonvolatile component in the resin layer is 100% by mass, (c) the content of the inorganic filler is 40 to 85% by mass, (d) the content of the polymer component is 0.5 to 10% by mass,
When the resin component of a resin layer is 100 mass %, content of (e) hardening accelerator is 0.03-4 mass %, The resin sheet. 14. The method of claim 13, wherein (c) the inorganic filler is silica,
(d) the polymer component contains at least one selected from the group consisting of organic fillers, phenoxy resins and polyvinyl acetal resins,
(e) A resin sheet in which the curing accelerator contains at least one selected from the group consisting of an adduct of an imidazole-epoxy resin and 4-dimethylaminopyridine. The resin sheet according to claim 1, wherein the minimum melt viscosity of the resin layer is 8000 to 40000 poise. The resin sheet according to claim 1, wherein the minimum melt viscosity of the resin layer is 300 to 12000 poise. The peeling strength of the said insulating layer and the circuit of Claim 1 after hardening the resin layer to form an insulating layer, and forming a circuit by a subtractive method or a modified semi-additive method is 0.5 kgf/cm or more ego,
The insulating layer and the circuit after curing the resin layer to form an insulating layer, forming a circuit by a subtractive method or a modified semi-additive method, and lapse of 100 hours under the conditions of 130°C and 85%RH A resin sheet having a peel strength of 0.3 kgf/cm or more. The resin sheet according to claim 1, wherein the metal foil has a thickness of 1 to 40 µm. The resin sheet according to claim 1, wherein the arithmetic mean roughness (Ra) of the first main surface of the metal foil is 250 nm or less. The resin sheet according to claim 1, wherein the metal foil has a thickness of 10 to 40 µm. 21. An inner layer substrate is disposed between two resin sheets according to any one of claims 1 to 20 so that the resin layer and the inner layer substrate are bonded, and is obtained by batch molding by vacuum hot press treatment or vacuum lamination treatment. , laminates. The laminate according to claim 21, comprising a circuit formed by a subtractive method or a modified semiadditive method. The laminate according to claim 22, comprising circuits having a wiring pitch of 50 mu m or less. A semiconductor device obtained by using the laminate according to claim 21.