TW202233761A - Resin sheet with support - Google Patents

Abstract

The present invention addresses the problem of providing a support-equipped resin sheet and a cured product which are capable of suppressing the dielectric loss tangent of the entire cured layer to a low level and suppressing the halo phenomenon. The solution of the present invention is a resin sheet with a support body, which is provided with a support body and a resin sheet layer that is provided on the support body, the resin sheet layer has, in order from the support body side, a first resin composition layer comprising a first resin composition and a second resin composition layer comprising a second resin composition having a composition different from that of the first resin composition, and satisfies predetermined conditions.

Description

Resin sheet with support

The present invention relates to a resin sheet with a support. In addition, it is related to the cured product of the resin sheet layer of the resin sheet with a support, a printed wiring board, and a semiconductor device.

In recent years, the demand for small high-performance electronic devices such as smart phones and tablet devices has increased, and along with this demand, insulating materials (insulating layers) for semiconductor packaging used in these small electronic devices are also required to be more functional. Such an insulating layer is known by curing a resin composition and the like (for example, refer to Patent Document 1).

In recent years, the miniaturization of electronic devices has become popular, and along with this, an insulating layer with a lower dielectric tangent is required. However, when a material with a lower dielectric tangent is used, the adhesion decreases, the hardening stress tends to accumulate, and the white fringing phenomenon that occurs after the via hole is formed tends to occur remarkably.

The white fringing phenomenon refers to the occurrence of peeling between the insulating layer and the inner layer substrate around the guide hole. This white fringing phenomenon usually means that the resin around the via hole is degraded, and the degraded part is easily corroded during the roughening treatment. In addition, the said deteriorated part can usually be observed as a discolored part. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2017-008312

[The problem to be solved by the invention]

The present invention provides a resin sheet and a cured product with a support that can reduce the dielectric tangent of the entire hardened layer while suppressing the white fringing phenomenon. [means to solve the problem]

In order to solve the above-mentioned problems, the present inventors made careful examinations, and determined the ratio of the thickness of each layer, the ratio of elastic modulus, and When the ratio of the dielectric tangent is set to satisfy the predetermined condition, it was unexpectedly found that the dielectric tangent of the entire hardened layer can be lowered and the white fringing phenomenon can be suppressed, thereby completing the present invention. That is, the present invention includes the following contents.

。 [2]如上述[1]之附支撐體之樹脂薄片，其中第2樹脂組成物含有(A)熱硬化性樹脂。 [3]如上述[1]或[2]之附支撐體之樹脂薄片，其中第1樹脂組成物及第2樹脂組成物，各自含有(B)無機填充材。 [4]如上述[3]之附支撐體之樹脂薄片，其中第2樹脂組成物中之(B)無機填充材之含有率(質量%)對第1樹脂組成物中之(B)無機填充材之含有率(質量%)之比(第2樹脂組成物/第1樹脂組成物)為0.30以下。 [5]如上述[3]或[4]之附支撐體之樹脂薄片，其中第2樹脂組成物中之(B)無機填充材之含有率(質量%)對第1樹脂組成物中之(B)無機填充材之含有率(質量%)之比(第2樹脂組成物/第1樹脂組成物)為0.25以上。 [6]上述[1]~[5]中任一項之附支撐體之樹脂薄片，其中第1樹脂組成物含有(C)自由基聚合性化合物。 [7]上述[1]~[6]中任一項之附支撐體之樹脂薄片，其中式(2)之條件中，y ₂/y ₁為0.28以上。 [8]上述[1]~[7]中任一項之附支撐體之樹脂薄片，其中式(3)之條件中，d ₂/d ₁為4以下。 [9]上述[1]~[8]中任一項之附支撐體之樹脂薄片，其中式(3)之條件中，d ₂/d ₁為2以上。 [10]上述[9]之附支撐體之樹脂薄片，其中式(3)之條件中，d ₂/d ₁為2.5以上。 [11]上述[1]~[10]中任一項之附支撐體之樹脂薄片，其中第1硬化層之彈性模數y ₁為11.5GPa以下。 [12]上述[1]~[11]中任一項之附支撐體之樹脂薄片，其中第1硬化層之彈性模數y ₁為8.5GPa以上。 [13]上述[1]~[12]中任一項之附支撐體之樹脂薄片，其中第2硬化層之彈性模數y ₂為3.3GPa以下。 [14]上述[1]~[13]中任一項之附支撐體之樹脂薄片，其中第1硬化層之介電正切d ₁為0.004以下。 [15]上述[1]~[14]中任一項之附支撐體之樹脂薄片，其中第2硬化層之介電正切d ₂為0.008以下。 [16]上述[1]~[15]中任一項之附支撐體之樹脂薄片，其中第1硬化層之比電容量(測定頻率5.8GHz、測定溫度23℃)設為p ₁，第2硬化層之比電容量(測定頻率5.8GHz、測定溫度23℃)設為p ₂時，進一步，滿足下述式(4)之條件，

。 [17]上述[1]~[16]中任一項之附支撐體之樹脂薄片，其中藉由下述式(5)所算出之第1硬化層及第2硬化層之2層所構成之硬化層全體的介電正切d _all為0.005以下，

。 [18]一種硬化物，其係具有第1樹脂組成物之硬化物所形成的第1硬化層，及形成於該第1硬化層上，藉由與第1樹脂組成物不同組成之第2樹脂組成物之硬化物所形成的第2硬化層， 將第1硬化層之厚度設為t _1’(μm)，將第2硬化層之厚度設為t _2’(μm)，將第1硬化層之彈性模數(測定溫度23℃)設為y ₁(GPa)，將第2硬化層之彈性模數(測定溫度23℃)設為y ₂(GPa)，將第1硬化層之介電正切(測定頻率5.8GHz、測定溫度23℃)設為d ₁，將第2硬化層之介電正切(測定頻率5.8GHz、測定溫度23℃)設為d ₂時，滿足所有下述式(1’)、(2)及(3)之條件，

。 [19]一種印刷配線板，其係具備上述[18]之硬化物所構成的絕緣層。 [20]一種半導體裝置，其係包含上述[19]之印刷配線板。 [發明效果] [1] A resin sheet with a support, comprising a support, and a resin sheet with a support provided on the support, and a resin sheet layer provided on the support, wherein the resin sheet layer is sequentially provided from the side of the support by the first 1. A first resin composition layer formed by a resin composition, and a second resin composition layer formed by a second resin composition having a different composition from the first resin composition. The thickness of the first resin composition layer is set. is t ₁ (μm), the thickness of the second resin composition layer is t ₂ (μm), and the elastic modulus of the first cured layer formed by curing the first resin composition layer at 190° C. for 90 minutes (measurement temperature 23° C.) is set as y ₁ (GPa), the elastic modulus (measurement temperature 23° C.) of the second hardened layer formed by curing the second resin composition layer at 190° C. for 90 minutes is set as y ₂ (GPa), and the first When the dielectric tangent (measurement frequency 5.8GHz, measurement temperature 23°C) of 1 hardened layer is set as d ₁ , and the dielectric tangent of the second hardened layer (measurement frequency 5.8GHz, measurement temperature 23°C) is set as d ₂ , all conditions are satisfied. Conditions of the following formulas (1), (2) and (3),

. [2] The resin sheet with a support according to the above [1], wherein the second resin composition contains (A) a thermosetting resin. [3] The resin sheet with a support according to the above [1] or [2], wherein the first resin composition and the second resin composition each contain (B) an inorganic filler. [4] The resin sheet with a support according to the above [3], wherein the content (% by mass) of the (B) inorganic filler in the second resin composition is relative to the (B) inorganic filler in the first resin composition The ratio (2nd resin composition / 1st resin composition) of the content rate (mass %) of a material is 0.30 or less. [5] The resin sheet with a support according to the above [3] or [4], wherein the content (% by mass) of the (B) inorganic filler in the second resin composition is greater than the content (% by mass) of the inorganic filler in the first resin composition. B) The ratio (2nd resin composition / 1st resin composition) of the content rate (mass %) of an inorganic filler is 0.25 or more. [6] The resin sheet with a support according to any one of the above [1] to [5], wherein the first resin composition contains (C) a radically polymerizable compound. [7] The resin sheet with a support according to any one of the above [1] to [6], wherein in the conditions of the formula (2), y ₂ /y ₁ is 0.28 or more. [8] The resin sheet with a support according to any one of the above [1] to [7], wherein in the conditions of the formula (3), d ₂ /d ₁ is 4 or less. [9] The resin sheet with a support according to any one of the above [1] to [8], wherein in the conditions of the formula (3), d ₂ /d ₁ is 2 or more. [10] The resin sheet with a support according to the above [9], wherein d ₂ /d ₁ is 2.5 or more in the conditions of the formula (3). [11] The resin sheet with a support according to any one of the above [1] to [10], wherein the elastic modulus y ₁ of the first hardened layer is 11.5 GPa or less. [12] The resin sheet with a support according to any one of the above [1] to [11], wherein the elastic modulus _y1 of the first hardened layer is 8.5 GPa or more. [13] The resin sheet with a support according to any one of the above [1] to [12], wherein the elastic modulus y ₂ of the second hardened layer is 3.3 GPa or less. [14] The resin sheet with a support according to any one of the above [1] to [13], wherein the dielectric tangent d ₁ of the first hardened layer is 0.004 or less. [15] The resin sheet with a support according to any one of the above [1] to [14], wherein the dielectric tangent d ₂ of the second hardened layer is 0.008 or less. [16] The resin sheet with a support according to any one of the above [1] to [15], wherein the specific capacitance (measurement frequency 5.8 GHz, measurement temperature 23° C.) of the first hardened layer is set to p ₁ , and the second When the specific capacitance of the hardened layer (measurement frequency 5.8 GHz, measurement temperature 23° C.) is set to p ₂ , further, the condition of the following formula (4) is satisfied,

. [17] The resin sheet with a support according to any one of the above [1] to [16], wherein the resin sheet is composed of two layers of the first hardened layer and the second hardened layer calculated by the following formula (5). The dielectric tangent d _all of the entire hardened layer is 0.005 or less,

. [18] A hardened product comprising a first hardened layer formed by a hardened product of a first resin composition, and a second resin having a different composition from the first resin composition formed on the first hardened layer For the second hardened layer formed by the cured product of the composition, let the thickness of the first hardened layer be t _1' (μm), the thickness of the second hardened layer be t _2' (μm), and the first hardened layer The elastic modulus (measurement temperature of 23°C) is set to y ₁ (GPa), the elastic modulus of the second hardened layer (measurement temperature of 23° C.) is set to y ₂ (GPa), and the dielectric tangent of the first hardened layer is set to y 2 (GPa). (measurement frequency 5.8 GHz, measurement temperature 23° C.) is set to d ₁ , and the dielectric tangent of the second hardened layer (measurement frequency 5.8 GHz, measurement temperature 23° C.) is set to d ₂ , all of the following formulas (1′ are satisfied) ), (2) and (3) conditions,

. [19] A printed wiring board including an insulating layer composed of the cured product of the above [18]. [20] A semiconductor device comprising the printed wiring board of the above [19]. [Inventive effect]

According to the present invention, it is possible to provide a resin sheet and a cured product with a support that can reduce the dielectric tangent of the entire hardened layer while suppressing the white fringing phenomenon.

[Form of implementing the invention]

Embodiments and examples are shown below, and the present invention is explained in detail. However, the present invention is not limited to the embodiments and examples listed below, and can be implemented with arbitrary modifications within the scope of the claims and equivalents of the present invention.

[Resin sheet with support] The resin sheet with a support of the present invention comprises a support and a resin sheet layer provided on the support, and the resin sheet layer has a first resin composition formed by a first resin composition in order from the side of the support. 1. A resin composition layer and a second resin composition layer formed of a second resin composition having a composition different from that of the first resin composition.

Hereinafter, when the first resin composition and the second resin composition are integrated, it may be referred to as "resin composition", and the first resin composition layer and the second resin composition layer may be integrated, and may be referred to as "resin composition" layer" situation.

FIG. 1 is a schematic cross-sectional view showing an example of a resin sheet with a support of the present invention. The resin sheet 1 with a support of the present invention includes a support 3 and a resin sheet layer 2 . The resin sheet layer 2 includes the first resin composition layer 10 and the second resin composition layer 20 in this order from the support body 3 side. The resin sheet layer 2 may include an additional layer between the first resin composition layer 10 and the second resin composition layer 20, but preferably includes only the first resin composition layer and the second resin composition layer.

<Resin composition layer> The first resin composition layer formed by the first resin composition and the second resin composition layer formed by the second resin composition have different types of components and/or their blending ratios from each other, thereby satisfying All of the conditions (1), (2) and (3) described below.

As condition (1), the following formula is satisfied when the thickness of the resin composition layer is t ₁ (μm) and the thickness of the second resin composition layer is t ₂ (μm) (1) conditions.

Among the conditions of the formula (1), t ₁ /t ₂ is more remarkably obtained from the viewpoint of obtaining the desired effect of the present invention, preferably 2 or more, more preferably 3 or more, particularly preferably 4 or more, and the upper limit is preferably 9 Hereinafter, it is more preferably 8 or less, still more preferably 7 or less, and particularly preferably 6 or less.

As condition (2), the elastic modulus (measurement temperature: 23° C.) of the first cured layer formed by curing the first resin composition layer at 190° C. for 90 minutes was set to y ₁ (GPa) for the resin composition layer. The condition of the following formula (2) is satisfied when the elastic modulus (measurement temperature: 23°C) of the second cured layer formed by curing the second resin composition layer at 190°C for 90 minutes is y ₂ (GPa).

Among the conditions of the formula (2), y ₂ /y ₁ is preferably 0.60 or less, more preferably 0.50 or less, still more preferably 0.45 or less, particularly preferably 0.40, from the viewpoint of obtaining the desired effect of the present invention more significantly. Hereinafter, the lower limit is preferably 0.10 or more, more preferably 0.20 or more, still more preferably 0.25 or more, and particularly preferably 0.28 or more.

In addition, the elastic modulus y ₁ of the first hardened layer and the elastic modulus y ₂ of the second hardened layer can be measured, for example, by the method of Reference Test Example 1 below.

As condition (3), the dielectric tangent (measurement frequency of 5.8 GHz, measurement temperature of 23° C.) of the first cured layer formed by curing the first resin composition layer at 190° C. for 90 minutes was set as d ₁ for the resin composition layer. , when the dielectric tangent (measurement frequency 5.8GHz, measurement temperature 23°C) of the second hardened layer formed by hardening the second resin composition layer at 190°C for 90 minutes is set as _d2 , the following formula (3) is satisfied. condition.

Among the conditions of the formula (3), d ₂ /d ₁ is preferably 1.5 or more, more preferably 2 or more, still more preferably 2.5 or more, and particularly preferably 3, from the viewpoint of remarkably obtaining the desired effect of the present invention. In the above, the upper limit is preferably 10 or less, more preferably 7 or less, still more preferably 5 or less, particularly preferably 4 or less.

In addition, the dielectric tangent d1 of the _1st hardened layer and the dielectric tangent d2 of the 2nd hardened layer can be measured by the method of the following reference test example ₂ , for example.

The thickness t1 of the first resin composition layer is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 30 μm or less, and the lower limit is preferably ₁ μm or more, from the viewpoint of obtaining the desired effect of the present invention more significantly. , more preferably 10 μm or more, and still more preferably 20 μm or more.

The thickness _t2 of the second resin composition layer is preferably 50 μm or less, more preferably 20 μm or less, still more preferably 10 μm or less, from the viewpoint of obtaining the desired effect of the present invention more significantly, and the lower limit is preferably 0.1 μm Above, more preferably 0.5 μm or more, and still more preferably 1 μm or more.

The sum of the thickness _t1 of the first resin composition layer and the thickness _t2 of the second resin composition layer is preferably 150 μm or less, more preferably 70 μm or less, from the viewpoint of obtaining the desired effect of the present invention more significantly. Still more preferably, it is 40 μm or less, and the lower limit thereof is preferably 1 μm or more, more preferably 10 μm or more, and still more preferably 20 μm or more.

The elastic modulus y ₁ (measurement temperature of 23° C.) of the first hardened layer formed by hardening the first resin composition layer at 190° C. for 90 minutes is preferable from the viewpoint of obtaining the desired effect of the present invention more significantly. 5.0GPa or more, more preferably 7.0GPa or more, still more preferably 8.0GPa or more, particularly preferably 8.5GPa or more, and the upper limit is preferably 20.0GPa or less, 17.0GPa or less, more preferably 15.0GPa or less, 14.0GPa or less, Still more preferably, it is 13.0 GPa or less, 12.0 GPa or less, and particularly preferably 11.5 GPa or less.

The elastic modulus y ₂ (measurement temperature of 23° C.) of the second hardened layer formed by hardening the second resin composition layer at 190° C. for 90 minutes is preferable from the viewpoint of obtaining the desired effect of the present invention more significantly. 1.0GPa or more, more preferably 2.0GPa or more, still more preferably 2.5GPa or more, particularly preferably 3.0GPa or more, and the upper limit is preferably 10.0GPa or less, more preferably 7.0GPa or less, 5.0GPa or less, and more preferably 4.0GPa or less, 3.7GPa or less, particularly preferably 3.5GPa or less, 3.3GPa or less.

The dielectric tangent d ₁ (measurement frequency of 5.8 GHz, measurement temperature of 23° C.) of the first cured layer formed by curing the first resin composition layer at 190° C. for 90 minutes can more significantly obtain the desired effect of the present invention. From a viewpoint, it is preferably 0.010 or less, 0.009 or less, more preferably 0.008 or less, 0.007 or less, still more preferably 0.006 or less, 0.005 or less, still more preferably 0.004 or less, and particularly preferably 0.003 or less.

The dielectric tangent d ₂ (measurement frequency of 5.8 GHz, measurement temperature of 23° C.) of the second cured layer formed by curing the second resin composition layer at 190° C. for 90 minutes can more significantly obtain the desired effect of the present invention. From a viewpoint, it is preferably 0.030 or less, 0.020 or less, more preferably 0.018 or less, 0.016 or less, still more preferably 0.014 or less, 0.012 or less, still more preferably 0.010 or less, and particularly preferably 0.008 or less.

As a resin sheet with a support, by using a resin sheet with a support that satisfies all the conditions of the above formulas (1), (2) and (3), the dielectric tangent of the entire hardened layer can be lowered, and the whitening can be suppressed. edge phenomenon.

The first resin composition layer formed from the first resin composition and the second resin composition layer formed from the second resin composition are preferably obtained by curing the first resin composition layer at 190° C. for 90 minutes. The specific capacitance of the first hardened layer formed (measurement frequency 5.8 GHz, measurement temperature 23° C.) was set to p ₁ , and the specific capacitance of the second hardened layer formed by hardening the second resin composition layer at 190° C. for 90 minutes When (measurement frequency 5.8 GHz, measurement temperature 23 degreeC) is set to p ₂ , in addition to the above-mentioned conditions (1), (2) and (3), the condition of Formula (4) is further satisfied.

In the condition of formula (4), the lower limit of p ₂ /p ₁ is preferably 0.7 or more, more preferably 0.8 or more, still more preferably 0.85 or more, and particularly preferably 0.9 or more. The lower limit of p ₂ /p ₁ is preferably 0.98 or less, particularly preferably 0.95 or less.

In addition, the specific capacitance p ₁ of the first hardened layer and the specific capacitance p ₂ of the second hardened layer can be measured, for example, by the method of Reference Test Example 2 below.

The specific capacitance p ₁ (measurement frequency 5.8GHz, measurement temperature 23°C) of the first hardened layer formed by hardening the first resin composition layer at 190°C for 90 minutes can more significantly obtain the desired effect of the present invention. From a viewpoint, it is preferably 4.0 or less, 3.9 or less, more preferably 3.8 or less, 3.7 or less, still more preferably 3.6 or less, 3.5 or less, still more preferably 3.4 or less, and particularly preferably 3.3 or less.

The specific capacitance p ₂ (measurement frequency 5.8GHz, measurement temperature 23°C) of the second hardened layer formed by hardening the second resin composition layer at 190°C for 90 minutes can more significantly obtain the desired effect of the present invention. From a viewpoint, it is preferably 4.0 or less, 3.8 or less, more preferably 3.7 or less, 3.5 or less, still more preferably 3.4 or less, 3.3 or less, still more preferably 3.2 or less, 3.1 or less, and particularly preferably 3.0 or less.

The first resin composition forming the first resin composition layer and the second resin composition forming the second resin composition layer may each contain a material selected from the group consisting of (A) a thermosetting resin, (B) an inorganic filler, ( C) Components of a radical polymerizable compound, (D) radical polymerization initiator, (E) thermoplastic resin, (F) hardening accelerator, (G) other additives, and (H) organic solvent. Those skilled in the art can appropriately adjust the ratio of elastic moduli and the ratio of dielectric tangents (and arbitrary ratios) of the two hardened layers formed by each resin composition layer by selecting and changing the contents of these components. Capacitance ratio) can be set within the range of the above conditions (2) and (3) (and optionally, within the range of the above condition (4)). Each component contained in the resin composition will be described in detail below.

<(A) Thermosetting resin> Each of the first resin composition and the second resin composition may contain (A) a thermosetting resin. In one embodiment, the first resin composition preferably contains (A) a thermosetting resin. In one embodiment, the second resin composition preferably contains (A) a thermosetting resin. As the thermosetting resin, a thermosetting resin in which a cured layer of a cured product of a resin composition can be used as an insulating member such as an insulating layer can be used. (A) Thermosetting resin, for example, epoxy resin, epoxy acrylate resin, urethane acrylate resin, urethane resin, cyanate resin, polyimide resin, benzoate Oxazine resin, unsaturated polyester resin, phenol resin, melamine resin, polysiloxane resin, etc.

<(A-1) Epoxy resin> Each of the first resin composition and the second resin composition may contain (A-1) epoxy resin as (A) thermosetting resin. In one embodiment, the first resin composition preferably contains (A-1) epoxy resin. In one embodiment, the second resin composition preferably contains (A-1) epoxy resin. (A-1) Epoxy resin means a resin having an epoxy group.

(A-1) Epoxy resin, for example, bis-xylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, for example Oxygen resin, dicyclopentadiene type epoxy resin, triphenol 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, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type ring Oxygen resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro-containing epoxy resin, cyclohexane epoxy resin, Cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. One type of epoxy resin may be used alone, or two or more types may be used in combination.

Each of the first resin composition and the second resin composition may contain an epoxy resin as (A-1), preferably an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the nonvolatile content of the epoxy resin (A-1) , preferably at least 50 mass %, more preferably at least 60 mass %, particularly preferably at least 70 mass %.

(A-1) The epoxy resin has a liquid epoxy resin at a temperature of 25°C (hereinafter sometimes referred to as "liquid epoxy resin") and a solid epoxy resin at a temperature of 25°C (hereinafter sometimes referred to as "liquid epoxy resin"). called "solid epoxy resin"). Each of the first resin composition and the second resin composition may contain only a solid epoxy resin, only a liquid epoxy resin, or a combination of liquid epoxy resins as the epoxy resin (A-1). Resins and solid epoxy resins.

The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

Liquid epoxy resin, preferably glycyrrhizol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane dimethanol type epoxy resin, cyclic aliphatic glycidyl ether , and an epoxy resin having a butadiene structure, more preferably a glycyrrhizol type epoxy resin, a cyclic aliphatic glycidyl ether, a bisphenol A type epoxy resin, and a bisphenol F type epoxy resin.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US" and "jER828EL" (bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Corporation. type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin); "630", "630LSD" manufactured by Mitsubishi Chemical, "630LSD" manufactured by ADEKA ED-523T" (ADEKA GLYCIROL), "EP-3980S" (glycidyl amine epoxy resin), "EP-4088S" (dicyclopentadiene epoxy resin); "ZX1059" manufactured by NIPPON STEEL Chemical & Material (mixture of bisphenol A epoxy resin and bisphenol F epoxy resin); "EX-721" manufactured by nagase chemtex (glycidyl ester epoxy resin) resin); "CELLOXID2021P" (alicyclic epoxy resin with ester skeleton), "PB-3600" (epoxy resin with butadiene structure) manufactured by DAICEL; "ZX1658" manufactured by NIPPON STEEL Chemical & Material ", "ZX1658GS" (liquid 1,4-glycidyl cyclohexane); "EX-201" (cyclic aliphatic glycidyl ether) manufactured by Nagase Chemtex Corporation.

A solid epoxy resin, preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule resin.

Solid epoxy resin, preferably bis-xylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type 4-functional epoxy resin, naphthol novolak type epoxy resin, cresol novolak type epoxy resin, Dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type ring Oxygen resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenolphthalimide type epoxy resin, phenolphthalein type epoxy resin.

Specific examples of the solid epoxy resin are preferably "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin manufactured by DIC Corporation) ); "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200" manufactured by DIC Corporation ", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene epoxy resin); "EXA-7311", "EXA-7311-G3", " EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolac type epoxy resin) manufactured by Pharma; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku ); "ESN475V" (naphthalene-type epoxy resin) manufactured by NIPPON STEEL Chemical &Material; "ESN485" (naphthol-type epoxy resin) manufactured by NIPPON STEEL Chemical &Material; "ESN485" (naphthol-type epoxy resin) manufactured by NIPPON STEEL Chemical & Material ESN375" (dihydroxynaphthalene type epoxy resin); "YX4000H", "YX4000", "YX4000HK", "YL7890" (bis-xylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" manufactured by Mitsubishi Chemical Corporation "(biphenyl type epoxy resin); "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical; "YX7700" (phenol aralkyl type epoxy resin) manufactured by Mitsubishi Chemical; Osaka Gas Chemical Co., Ltd. "PG-100", "CG-500"; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YL7800" (Plenum type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; Mitsubishi Chemical Co., Ltd. "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR991S" (phenolphthalimide type epoxy resin manufactured by Nippon Kayaku Co., Ltd.) epoxy resin) etc. These may be used individually by 1 type, and may be used in combination of 2 or more types.

As the epoxy resin (A-1), when a liquid epoxy resin and a solid epoxy resin are used in combination, their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 20:1 ~1:20, more preferably 10:1~1:10, particularly preferably 7:1~1:7.

(A-1) The epoxy equivalent of the epoxy resin is preferably 50g/eq.~5000g/eq., more preferably 50g/eq.~3000g/eq., still more preferably 80g/eq.~2000g/ eq., more preferably 110g/eq.~1000g/eq.. The epoxy equivalent is the mass of the epoxy group per 1 equivalent of the resin. This epoxy equivalent can be measured according to JIS K7236.

(A-1) The weight average molecular weight (Mw) of the epoxy resin, from the viewpoint of obtaining the desired effect of the present invention, is preferably 100-5000, more preferably 250-3000, and more preferably 400- 1500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

The content rate (mass %) of the (A-1) epoxy resin in the first resin composition is not particularly limited, but when the non-volatile component in the first resin composition is set to 100 mass %, it is more remarkably obtained. From the viewpoint of the desired effect of the present invention, it is preferably 50 mass % or less, more preferably 30 mass % or less, particularly preferably 20 mass % or less, and the lower limit thereof is, for example, 0 mass % or more, 0.1 mass % or more, preferably It is 1 mass % or more, More preferably, it is 10 mass % or more, Especially preferably, it is 15 mass % or more.

The content rate (mass %) of the (A-1) epoxy resin in the second resin composition is not particularly limited, but when the nonvolatile content in the second resin composition is set to 100 mass %, it is more remarkably obtained. From the viewpoint of the desired effect of the present invention, it is preferably 70 mass % or less, more preferably 60 mass % or less, particularly preferably 50 mass % or less, and the lower limit thereof is, for example, 0 mass % or more, 0.1 mass % or more, and 1 mass % or more. % or more, preferably 10 mass % or more, more preferably 30 mass % or more, particularly preferably 40 mass % or more.

<(A-2) Epoxy hardener> When the first resin composition and the second resin composition each contain (A-1) epoxy resin as (A) thermosetting resin, (A-2) epoxy curing agent may be further contained as an optional component. In one embodiment, the first resin composition preferably contains (A-2) an epoxy curing agent. In one embodiment, the second resin composition preferably contains (A-2) an epoxy curing agent. (A-2) The epoxy hardener has a function of reacting with the (A-1) epoxy resin to harden the resin composition.

(A-2) Epoxy curing agent is not particularly limited, and examples thereof include active ester-based curing agents, phenol-based curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, and benzoxazine type hardener, cyanate ester type hardener, thiol type hardener, etc. (A-2) An epoxy hardener may be used individually by 1 type, and may be used in combination of 2 or more types. (A-2) The epoxy hardener preferably contains an epoxy hardener selected from an active ester type hardener and a phenol type hardener.

As the active ester-based hardener, it is generally preferable to use esters having two or more high reactivity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. base compounds.

The active ester-based hardener is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred.

Examples of the active ester-based curing agent include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxyl Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene-type diphenol compounds, Phenol novolac, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene and two molecules of phenol.

Specifically, the active ester-based curing agent is preferably a dicyclopentadiene-type active-ester-based curing agent, a naphthalene-type active ester-based curing agent containing a naphthalene structure, and an active ester-based curing agent containing an acetate of a phenol novolac. Agents and active ester-based hardeners containing benzyl compounds of phenol novolacs, more preferably at least one selected from the group consisting of dicyclopentadiene-type active-ester-based hardeners and naphthalene-type active-ester-based hardeners. The dicyclopentadiene-type active ester-based curing agent is preferably an active-ester-based curing agent containing a dicyclopentadiene-type diphenol structure.

Commercially available active ester-based hardeners are active ester-based hardeners containing dicyclopentadiene-type diphenol structures, such as "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB- 8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM", ( DIC Corporation); active ester-based hardeners containing a naphthalene structure, such as "EXB-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", " EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T" (manufactured by DIC Corporation); phosphorus-containing active ester-based hardeners include "EXB9401" (manufactured by DIC Corporation), phenol novolac "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) is mentioned as the active ester-based hardener of the acetylated compound of varnish, and "YLH1026", "YLH1030", "YLH1026", "YLH1030", " YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.), an active ester-based hardener containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Air Water Co., Ltd.), etc. are mentioned.

The phenol-based curing agent is not particularly limited, but is preferably a biphenyl-based curing agent, a naphthalene-based curing agent, a phenol novolac-based curing agent, a naphthylene ether-based curing agent, and a phenol-based curing agent containing a triazine skeleton. Specifically, "MEH-7700", "MEH-7810", "MEH-7851" (manufactured by Meiwa Chemical Co., Ltd.) of biphenyl type hardeners, "NHN", "CBN", " GPH" (manufactured by Nippon Kayaku Co., Ltd.), "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395" (manufactured by Nippon Steel Chemical Co., Ltd.), "EXB9500" (manufactured by DIC Corporation), "TD2090" (manufactured by DIC Corporation) of a phenol novolak type hardener, "EXB-6000" (manufactured by DIC Corporation) of a naphthylene ether type hardener, etc. "LA3018", "LA7052", "LA7054", "LA1356" (manufactured by DIC Corporation) etc. are mentioned as a specific example of the phenol type hardening|curing agent containing a triazine skeleton. In particular, a naphthalene-type hardener and a phenol-type hardener containing a triazine skeleton are more preferable.

Examples of the carbodiimide-based curing agent include one or more, preferably two or more, carbodiimide structures in one molecule, and examples thereof include tetramethylene-bis(t-butyl) carbodiimide), cyclohexane bis(methylene-t-butylcarbodiimide) and other aliphatic biscarbodiimides; phenylene-bis(xylylcarbodiimide), etc. Bicarbodiimide such as aromatic biscarbodiimide; polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(imide) aliphatic polycarbodiimide such as methyl dicyclohexylene carbodiimide), poly(isophorone carbodiimide); poly(phenylene carbodiimide), poly(naphthylene carbodiimide) diimide), poly(methylphenylcarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylene) phenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(diisopropylphenylenecarbodiimide) (Tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), poly[methylenebis(methylphenylene)carbodiimide], etc. Polycarbodiimides such as polycarbodiimides.

Commercially available carbodiimide-based hardeners include "CARBODILITE V-02B", "CARBODILITE V-03", "CARBODILITE V-04K", "CARBODILITE V-07", and "CARBODILITE V-07" manufactured by Nisshinbo Chemical Co., Ltd. V-09"; "Stabaxol P", "Stabaxol P400", "Hycazil 510" manufactured by rheinchemie, etc.

As an acid anhydride type hardening|curing agent, the hardening agent which has 1 or more of acid anhydride groups in 1 molecule is mentioned, Preferably it is a hardening agent which has 2 or more acid anhydride groups in 1 molecule. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride Acid anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl )-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, Naphthalene tetracarboxylic dianhydride, Oxydiphthalic anhydride, 3,3'-4,4'-diphenyltetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro- 5-(Tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride), styrene and maleic Acid-copolymerized styrene and maleic acid resins, such as polymer-type acid anhydrides, etc. Commercially available acid anhydride-based hardeners include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" and "YH" manufactured by Mitsubishi Chemical Co., Ltd. -306", "YH-307", "HN-2200", "HN-5500" manufactured by Hitachi Chemical Co., Ltd.

Amine-based hardeners include those having one or more, preferably two or more amine groups in one molecule, and examples thereof include aliphatic amines, polyetheramines, alicyclic amines, and aromatic amines. Among them, aromatic amines are preferred from the viewpoint of exhibiting the desired effects of the present invention. The amine-based hardener is preferably a primary amine or a secondary amine, more preferably a primary amine. Specific examples of the amine-based curing agent include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, and 4,4'-diamine Diphenyldiphenyl, 3,3'-diaminodiphenyldiamine, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiamine Phenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxy Benzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2 ,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy) Benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl Benzene, bis(4-(4-aminophenoxy)phenyl)sine, bis(4-(3-aminophenoxy)phenyl)sine, and the like. Commercially available amine hardeners can be used, for example, "SEIKACURE-S" manufactured by SEIKA, "KAYABOND C-200S", "KAYABOND C-100", "Kayahard A-A", and "Kayahard A-B" manufactured by Nippon Kayaku Co., Ltd. ", "Kayahard A-S", "Epicure W" manufactured by Mitsubishi Chemical Corporation, etc.

Specific examples of benzoxazine-based hardeners include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; "P-d" manufactured by Shikoku Chemical Industry Co., Ltd. , "F-a", etc.

Examples of cyanate-based curing agents include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'- Methylene bis(2,6-dimethylphenylcyanate), 4,4'-ethylene diphenyl dicyanate, 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-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl) sulfide, and bis(4-cyanate phenyl) ether, etc. Bifunctional cyanate resins, polyfunctional cyanate resins derived from phenol novolacs and cresol novolacs, etc., and prepolymers in which these cyanate resins are partially triazinated, etc. Specific examples of the cyanate-based hardener include "PT30" and "PT60" (both are phenol novolac type polyfunctional cyanate resins), "BA230", and "BA230S75" (bisphenol A) manufactured by Lonza Japan. Part or all of the dicyanate is triazinated to become a prepolymer of a trimer) and the like.

The thiol-based curing agent includes, for example, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl)isocyanurate, and the like.

(A-2) The reactive group equivalent of the epoxy hardener is preferably 50g/eq.~3000g/eq., more preferably 100g/eq.~1000g/eq., still more preferably 100g/eq.~500g /eq., especially 100g/eq.~300g/eq.. The equivalent of reactive groups is the mass of the hardener with 1 equivalent of reactive groups.

The content rate (mass %) of the (A-2) epoxy curing agent in the first resin composition is not particularly limited, but it is more remarkable when the nonvolatile content in the first resin composition is 100 mass % From the viewpoint of obtaining the desired effect of the present invention, it is preferably 40 mass % or less, more preferably 20 mass % or less, particularly preferably 10 mass % or less, and the lower limit thereof is, for example, 0 mass % or more, 0.01 mass % or more, and 0.1 mass % or more is preferable, 1 mass % or more is more preferable, and 3 mass % or more is especially preferable.

The content rate (mass %) of the (A-2) epoxy curing agent in the second resin composition is not particularly limited, but it is more significant when the nonvolatile content in the second resin composition is 100 mass % From the viewpoint of obtaining the desired effect of the present invention, it is preferably 40 mass % or less, more preferably 30 mass % or less, particularly preferably 20 mass % or less, and the lower limit thereof is, for example, 0 mass % or more, 0.01 mass % or more, and 0.1 mass % or more. It is at least 1 mass %, preferably at least 3 mass %, more preferably at least 5 mass %, and particularly preferably at least 10 mass %.

<(B) Inorganic filler> The first resin composition and the second resin composition preferably each contain (B) an inorganic filler. In an embodiment in which the first resin composition or the second resin composition contains the (B) inorganic filler, a method for adjusting the elastic modulus of the hardened layer by adjusting the content of the (B) inorganic filler in the resin composition one.

(B) An inorganic compound is used as the material of the inorganic filler. Examples of materials for inorganic fillers include silica, alumina, glass, lapis lazuli, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, diaspore, hydrogen Alumina, 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 titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphotungstate, etc. Of these, particularly preferred is silicon dioxide. Silica includes, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. In addition, the silica is preferably spherical silica. (B) Inorganic fillers may be used alone or in combination of two or more.

(B) Commercial products of inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by NIPPON STEEL & SUMIKIN MATERIALS; "YC100C", "YA050C", "YA050C-MJE" manufactured by admatechs ", "YA010C"; "UFP-30" manufactured by Denka Corporation; "SilFile NSS-3N", "SilFile NSS-4N", "SilFile NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ" manufactured by admatechs Corporation, "SO-C4", "SO-C2", "SO-C1"; etc.

(B) The average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and more preferably 5 μm, from the viewpoint of obtaining the desired effect of the present invention more remarkably. Below, it is more preferable that it is 2 micrometers or less, and it is still more preferable that it is 1 micrometer or less.

(B) The average particle size of the inorganic filler can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the (B) inorganic filler is prepared on a volume basis by a laser diffraction scattering particle size distribution analyzer, and the median particle size can be measured as an average particle size. For the measurement sample, one that weighs (B) 100 mg of the inorganic filler and 10 g of methyl ethyl ketone in a small glass bottle and disperses it with ultrasonic waves for 10 minutes can be used. Using a laser diffraction particle size distribution measuring device, and using the light source wavelengths as blue and red, the measurement sample is measured by a flow battery method (B) The volume-based particle size distribution of the inorganic filler is obtained from the particle size. distribution, and the average particle diameter was calculated from the median particle diameter. As a laser diffraction particle size distribution measuring apparatus, "LA-960" manufactured by Horiba, Ltd., etc. is mentioned, for example.

(B) The specific surface area of the inorganic filler is preferably 1 m ² /g or more, more preferably 2 m ² /g or more, particularly preferably 3 m ² /g or more, from the viewpoint of obtaining the desired effect of the present invention more significantly. . The upper limit is not particularly limited, but is preferably not more than 60 m ² /g, not more than 50 m ² /g, or not more than 40 m ² /g. The specific surface area was obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH) based on the BET method, and calculating the specific surface area using the BET multipoint method.

The inorganic filler (B) is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Surface treatment agents include, for example, fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilanes, and organosilazane compounds , titanate coupling agent, etc. Moreover, a surface treatment agent may be used individually by 1 type, and may be used in arbitrary combination of 2 or more types.

Commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. oxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (Long-chain epoxy type silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

From the viewpoint of improving the dispersibility of the (B) inorganic filler by the degree of surface treatment of the surface treatment agent, it is preferable to store it in a specific range. Specifically, (B) 100 parts by mass of the inorganic filler, preferably 0.2 to 5 parts by mass of a surface treatment agent, preferably 0.2 to 3 parts by mass, preferably 0.2 to 3 parts by mass 0.3 parts by mass to 2 parts by mass of surface treatment.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the (B) inorganic filler. (B) The carbon content per unit surface area of the inorganic filler, from the viewpoint of improving the dispersibility of the (B) inorganic filler, is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, still more preferably 0.2 mg/m ² or more. Furthermore, from the viewpoint of suppressing the increase in the melt viscosity of the resin varnish and the melt viscosity of the resin sheet layer, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and still more preferably 0.5 mg/m ² or less.

(B) The carbon content per unit surface area of the inorganic filler can be measured by washing the surface-treated (B) inorganic filler with a solvent (eg, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent was added to the (B) inorganic filler surface-treated with a surface-treating agent, and ultrasonic cleaning was performed at 25° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per surface area of the (B) inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd., etc. can be used.

The content (% by mass) of the (B) inorganic filler in the first resin composition is not particularly limited, but the present invention is more remarkably obtained when the nonvolatile component in the first resin composition is set to 100% by mass From the viewpoint of the desired effect, it is preferably 90 mass % or less, more preferably 80 mass % or less, particularly preferably 75 mass % or less, and 73 mass % or less, and the lower limit thereof is, for example, 0 mass % or more and 1 mass % or more. , 10 mass % or more, 30 mass % or more, preferably 40 mass % or more, more preferably 50 mass % or more, particularly preferably 60 mass % or more, 65 mass % or more.

The content (% by mass) of the (B) inorganic filler in the second resin composition is not particularly limited, but the present invention is more remarkably obtained when the non-volatile component in the second resin composition is set to 100% by mass From the viewpoint of the desired effect, it is preferably 80 mass % or less, more preferably 50 mass % or less, particularly preferably 30 mass % or less, and the lower limit thereof is, for example, 0 mass % or more, 1 mass % or more, preferably 5 % by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more.

Ratio of the content (% by mass) of the (B) inorganic filler in the second resin composition to the content (% by mass) of the (B) inorganic filler in the first resin composition (second resin composition/ The first resin composition), from the viewpoint of obtaining the desired effect of the present invention more remarkably, is preferably 1.00 or less, more preferably 0.70 or less, still more preferably 0.50 or less, still more preferably 0.40 or less, particularly preferably 0.30 or less, the lower limit is preferably 0.10 or more, more preferably 0.15 or more, still more preferably 0.20 or more, and particularly preferably 0.25 or more.

<(C) Radically polymerizable compound> Each of the first resin composition and the second resin composition may contain (C) a radically polymerizable compound. In one embodiment, the first resin composition preferably contains (C) a radically polymerizable compound. (C) A radical polymerizable compound may be used individually by 1 type, and may be used in arbitrary combination of 2 or more types.

(C) Radical polymerizable compound In one embodiment, it is a radical polymerizable compound which has an ethylenically unsaturated bond. (C) Radically polymerizable compound, although not particularly limited, may have, for example, allyl, 3-cyclohexenyl, 3-cyclopentenyl, p-vinylphenyl, m-vinylphenyl, o- Unsaturated hydrocarbon groups such as vinylphenyl; acrylyl, methacryloyl, maleimide (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl), etc. Radical polymerizable groups such as α, β-unsaturated carbonyl groups. (C) The radically polymerizable compound preferably has two or more radically polymerizable groups in one molecule.

(C) Radical polymerizable compound, such as (meth)acrylic radical polymerizable compound, styrene radical polymerizable compound, allyl radical polymerizable compound, maleimide radical polymerizable compound base polymerizable compounds, etc. (C) In one embodiment, the radical polymerizable compound preferably contains a (meth)acrylic radical polymerizable compound, a styrene radical polymerizable compound, or a maleimide radical polymerizable compound. compound.

The (meth)acrylic radical polymerizable compound is a compound having two or more acryl group and/or methacryl group. (Meth)acrylic radical polymerizable compounds, for example, cyclohexane-1,4-dimethanol di(meth)acrylate and cyclohexane-1,3-dimethanol di(meth)acrylate , tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate (Meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate ester, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc. Aliphatic (meth)acrylate compounds with low molecular weight (less than 1000 molecular weight); dioxaneethylene glycol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di( Meth)acrylate, 3,6,9-Trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol Di(meth)acrylate, 9,9-bis[4-(2-propenyloxyethoxy)phenyl]phenanium, ethoxylated bisphenol A di(meth)acrylate, propoxy Low molecular weight (less than 1000 molecular weight) ether-containing (meth)acrylate compounds such as bisphenol A di(meth)acrylate; tris(3-hydroxypropyl)isocyanurate tris(methyl) ) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, etc. low molecular weight (less than 1000 molecular weight) ) containing isocyanurate (meth)acrylate compounds; (meth)acryloyl group-modified polyphenylene ether resins and other high molecular weight (molecular weight 1000 or more) acrylate compounds, etc. Commercial products of (meth)acrylic radical polymerizable compounds include, for example, "A-DOG" (dioxane ethylene glycol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., and "A-DOG" manufactured by Kyōeisha Chemical Co., Ltd. "DCP-A" (tricyclodecane dimethanol diacrylate), "DCP" (tricyclodecane dimethanol dimethacrylate), "KAYARAD R-684" (tricyclodecane dimethacrylate) from Nippon Kayaku Co., Ltd. Alkane dimethanol diacrylate), "KAYARAD R-604" (dioxane ethylene glycol diacrylate), "SA9000", "SA9000-111" (methacryloyl-modified polyacrylate) manufactured by SABIC Innovative Plastics phenyl ether) etc.

The styrene-based radically polymerizable compound is a compound having two or more vinyl groups directly bonded to an aromatic carbon atom. Examples of the styrene-based radical polymerizable compound include divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, and 4,4'-divinylnaphthalene. Low molecular weight of vinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, bis(4-vinylphenyl)ether, etc. Styrene-based compounds (less than 1000 molecular weight); vinylbenzyl-modified polyphenylene ether resins, styrene-divinylbenzene copolymers, etc. high molecular weight (more than 1000 molecular weight) styrene-based compounds, etc. Commercially available styrene-based radically polymerizable compounds include, for example, "ODV-XET(X03)", "ODV-XET(X04)", and "ODV-XET(X05)" manufactured by NIPPON STEEL Chemical & Material Co., Ltd. (Styrene-divinylbenzene copolymer), "OPE-2St 1200", "OPE-2St 2200" (vinylbenzyl modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Corporation.

The allyl-based radically polymerizable compound is a compound having two or more allyl groups. Allyl-based radically polymerizable compounds include, for example, diallyl diphenic acid, triallyl trimellitic acid, diallyl phthalate, and diisophthalic acid. Aromatic carboxylic acid allyl ester compounds such as allyl ester, diallyl terephthalate, diallyl 2,6-naphthalene dicarboxylate, diallyl 2,3-naphthalene carboxylate; 1, Allyl isocyanurate compounds such as triallyl 3,5-isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; 2,2-bis[ Aromatic allyl compounds containing epoxy groups such as 3-allyl-4-(glycidyloxy)phenyl]propane; bis[3-allyl-4-(3,4-dihydro- Aromatic allyl compounds containing benzoxazine such as 2H-1,3-benzoxazin-3-yl)phenyl]methane; ether-containing compounds such as 1,3,5-triallyl ether benzene Aromatic allyl compounds; allyl silane compounds such as diallyl diphenyl silane, etc. Commercially available allyl radically polymerizable compounds include "TAIC" (triallyl 1,3,5-isocyanurate) manufactured by Nippon Chemical Co., Ltd., "DAD" manufactured by Nisshoku Techno Fine Chemical Co., Ltd. "(diallyl biphthalate), "TRIAM-705" (triallyl trimellitate) manufactured by Wako Pure Chemical Industries, Ltd., trade name "DAND" manufactured by Nippon Distillery Industries Co., Ltd. (2, Diallyl 3-naphthalene carboxylate), "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxa]) manufactured by Shikoku Chemical Industry Co., Ltd. oxazin-3-yl)phenyl]methane), "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane) manufactured by Nippon Kayaku Co., Ltd., "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Chemical Co., Ltd., etc.

The maleimide-based radically polymerizable compound is a compound having two or more maleimide groups. Maleimide-based radically polymerizable compounds, which may include aliphatic maleimide compounds having an aliphatic amine skeleton, or aromatic maleimide compounds that may include an aromatic amine skeleton, are commercially available. For example, "SLK-2600" manufactured by Shin-Etsu Chemical Co., Ltd., "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", "BMI-2500" manufactured by Designer molecules Corporation ( Maleimide compound containing dimer diamine structure), "BMI-6100" (aromatic maleimide compound) manufactured by Designer molecules, "MIR-5000-60T" manufactured by Nippon Kayaku Co., Ltd. , "MIR-3000-70MT" (biphenyl aralkyl maleimide compound), "BMI-70", "BMI-80" manufactured by ki-chemica, "BMI-80" manufactured by Yamato Chemical Co., Ltd. 2300", "BMI-TMH", etc. In addition, as the maleimide-based radical polymerizable compound, the maleimide resin (maleimide containing an indane ring skeleton) disclosed in the Published Technical Gazette No. 2020-500211 of the Institute of Invention can be used. compound).

(C) The ethylenically unsaturated bond equivalent of the radically polymerizable compound is preferably 20 g/eq. to 3000 g/eq., more preferably 50 g/eq. to 2500 g/eq., and still more preferably 70 g/eq. .~2000g/eq., preferably 90g/eq.~1500 g/eq.. The ethylenically unsaturated bond equivalent is the mass of the radically polymerizable compound per equivalent of the ethylenically unsaturated bond.

(C) The weight average molecular weight (Mw) of the radically polymerizable compound is preferably 40,000 or less, more preferably 10,000 or less, still more preferably 5,000 or less, and particularly preferably 3,000 or less. The lower limit is not particularly limited, and may be, for example, 150 or more.

The content (% by mass) of the (C) radically polymerizable compound in the first resin composition is not particularly limited, but when the non-volatile component in the first resin composition is set to 100% by mass, the present invention is more remarkably obtained. From the viewpoint of the desired effect of the invention, it is preferably 50 mass % or less, more preferably 30 mass % or less, particularly preferably 20 mass % or less, and the lower limit thereof is, for example, 0 mass % or more, 0.1 mass % or more, preferably 1 mass % or more, more preferably 3 mass % or more, particularly preferably 5 mass % or more.

The content (% by mass) of the (C) radically polymerizable compound in the second resin composition is not particularly limited, but when the nonvolatile component in the second resin composition is set to 100% by mass, the present invention is more remarkably obtained. From the viewpoint of the desired effect of the invention, it is preferably 30 mass % or less, more preferably 10 mass % or less, still more preferably 5 mass % or less, particularly preferably 1 mass % or less, and the lower limit may be, for example, 0 mass % above etc.

From the viewpoint of obtaining the desired effect of the present invention more significantly, when compared with the content rate (mass %) of the (C) radical polymerizable compound in the first resin composition, (C) in the second resin composition ) The content (% by mass) of the radically polymerizable compound is preferably as small as possible. Ratio of the content (% by mass) of the (C) radical polymer compound in the second resin composition to the content (% by mass) of the (C) radical polymerizable compound in the first resin composition (second The resin composition/first resin composition) is usually 0 or more, preferably 0.6 or less, more preferably 0.2 or less, and particularly preferably 0.1 or less.

<(D) Radical Polymerization Initiator> Each of the first resin composition and the second resin composition may contain (D) a radical polymerization initiator. The (D) radical polymerization initiator may be, for example, a thermal polymerization initiator that generates free radicals when heated. (D) A radical polymerization initiator may be the polymerization initiator containing the radically polymerizable component of (C) component demonstrated above. (D) A radical polymerization initiator may be used individually by 1 type, and may be used in arbitrary combination of 2 or more types.

(D) A radical polymerization initiator, for example, a peroxide type radical polymerization initiator, an azo type radical polymerization initiator, etc. are mentioned. Among them, peroxide-based radical polymerization initiators are preferred.

Peroxide-based radical polymerization initiators include, for example, hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; tert-butylcumyl peroxide, di-tert -Butyl peroxide, di-tert-hexyl peroxide, dicumyl peroxide, 1,4-bis(1-tert-butylperoxy-1-methylethyl)benzene, 2,5 - Dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexyne, etc. Alkyl peroxide compounds; Dilauroyl peroxide, Didecanoyl peroxide, Dicyclohexyl peroxide dicarbonate, Bis(4-tert-butylcyclohexyl) peroxide Diacyl peroxide based compounds such as carbonates; tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl monocarbonate, tert-butylperoxy-2-ethyl tert-butyl peroxyneodecanoate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxylaurate, (1,1-dimethylpropyl)peroxide 2 -Ethylhexanoate, tert-butyl 2-ethyl peroxyhexanoate, tert-butyl peroxy 3,5,5-trimethylhexanoate, tert-butyl peroxy-2-ethyl Peroxyester compounds of ylhexyl monocarbonate, tert-butyl peroxymaleic acid, etc.; etc.

Azo-based radical polymerization initiators include, for example, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2, 4-Dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane -1-carbonitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, 2-phenylazo-4-methoxy-2,4-dimethyl - Azonitrile compounds such as valeronitrile; 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], 2 ,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide], 2,2'-azobis[2-methyl-N- [2-(1-Hydroxybutyl)]-propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2' -Azobis(2-methylpropanamide) dihydrate, 2,2'-azobis[N-(2-propenyl)-2-methylpropanamide], 2,2 Azoamide compounds such as '-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide), etc.; Alkyl azo compounds of 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), etc.; etc.

(D) Commercial products of radical polymerization initiators include, for example, "Perbutyl C", "Perbutyl A", "Perbutyl P", "Perbutyl L", "Perbutyl O", and "Perbutyl ND" manufactured by NOF Corporation. ", "Perbutyl Z", "Perbutyl I", "Percumyl P", "Percumyl D", "perhexyl D", "perhexyl A", "perhexyl I", "perhexyl Z", "perhexyl ND", "perhexyl O" ", "perhexyl PV", "perhexyl O", "PERHEXYN 25B", etc.

The content (% by mass) of the (D) radical polymerization initiator in the first resin composition is not particularly limited, but when the non-volatile component in the first resin composition is set to 100% by mass, the From the viewpoint of the desired effect of the present invention, it is preferably 5 mass % or less, more preferably 2 mass % or less, particularly preferably 1 mass % or less, and the lower limit thereof is, for example, 0 mass % or more, 0.001 mass % or more, preferably It is 0.01 mass % or more, More preferably, it is 0.05 mass % or more, Especially preferably, it is 0.1 mass % or more.

The content (% by mass) of the (D) radical polymerization initiator in the second resin composition is not particularly limited, but when the non-volatile component in the second resin composition is set to 100% by mass, the From the viewpoint of the desired effect of the present invention, it is preferably 5 mass % or less, more preferably 2 mass % or less, particularly preferably 1 mass % or less, and the lower limit may be, for example, 0 mass % or more.

<(E) Thermoplastic resin> The first resin composition and the second resin composition each contain (E) a thermoplastic resin. The (E) thermoplastic resin described here is a component other than the (C) radically polymerizable compound described above.

(E) Thermoplastic resin, for example, polyimide resin, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyetherimide resin Amine resin, polyether resin, polyether resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. (E) Thermoplastic resin In one Embodiment, it is preferable to contain the thermoplastic resin selected from the group which consists of a polyimide resin and a phenoxy resin. Moreover, a thermoplastic resin may be used individually by 1 type, and may be used in arbitrary combination of 2 or more types.

Specific examples of the polyimide resin include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., "Rikacoat SN20" and "Rikacoat PN20" manufactured by Nippon Chemical Co., Ltd., and the like.

For example, the phenoxy resin has a structure selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, perylene skeleton, and dicyclopentadiene skeleton. A phenoxy resin having one or more skeletons selected from the group consisting of a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group.

Specific examples of phenoxy resins include "1256" and "4250" (both are phenoxy resins containing bisphenol A skeleton) manufactured by Mitsubishi Chemical Co., Ltd.; "YX8100" (containing bisphenol S) manufactured by Mitsubishi Chemical Co., Ltd. Phenoxy resin with skeleton); "YX6954" (a phenoxy resin containing bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Co., Ltd.; "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.; Mitsubishi Chemical Co., Ltd. "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30", etc.

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", and "Denka Butyral 6000-EP" manufactured by Denki Chemical Industry Co., Ltd. ; S-Lec BH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series made by Sekisui Chemical Industry Co., Ltd.; and so on.

Examples of polyolefin resins include low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl acrylate copolymers and other vinyl-based resins. Copolymer resins; polyolefin-based polymers such as polypropylene, ethylene-propylene block copolymers, etc.

Examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxyl group-containing polybutadiene resins, phenolic hydroxyl group-containing polybutadiene resins, carboxyl group-containing polybutadiene resins, and acid anhydride-containing resins. Polybutadiene resin containing epoxy group, polybutadiene resin containing epoxy group, polybutadiene resin containing isocyanate group, polybutadiene resin containing urethane group, polyphenylene ether-polybutadiene olefin resin, etc.

Specific examples of the polyamide imide resin include "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamide imide resin include modified polyamide imide such as "KS9100" and "KS9300" (polyamide imide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd. .

Specific examples of the polyether resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Specific examples of the polymer resin include "P1700" and "P3500" made by Solvay Advanced Polymers.

Specific examples of the polyphenylene ether resin include "NORYL SA90" manufactured by SABIC. Specific examples of the polyetherimide resin include "ULTEM" manufactured by GE Corporation.

The polycarbonate resins include hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, and urethane resins Ester-based carbonate resin, etc. Specific examples of polycarbonate resins include "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals Corporation, "C-1090" manufactured by Kuraray Corporation, "C-2090", "C-3090" (polycarbonate diol), etc. Specific examples of the polyether ether ketone resin include "Sumiploy K" manufactured by Sumitomo Chemical Corporation.

Polyester resin, for example, polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene terephthalate resin, polyethylene terephthalate resin Propylene formate resin, polypropylene naphthalate resin, polyethylene terephthalate resin, etc.

(E) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, particularly preferably 20,000 or more, from the viewpoint of remarkably obtaining the effects of the present invention. 100,000 or less, more preferably 70,000 or less, still more preferably 60,000 or less, and particularly preferably 50,000 or less.

The content (% by mass) of the thermoplastic resin (E) in the first resin composition is not particularly limited, but when the non-volatile component in the first resin composition is set to 100% by mass, the results of the present invention are more remarkably obtained. From the viewpoint of the desired effect, preferably 40 mass % or less, more preferably 20 mass % or less, particularly preferably 15 mass % or less, and the lower limit thereof is, for example, 0 mass % or more, 0.1 mass % or more, 0.5 mass % or more, 1 mass % or more is preferable, 2 mass % or more is more preferable, and 3 mass % or more is especially preferable.

The content (% by mass) of the thermoplastic resin (E) in the second resin composition is not particularly limited, but when the non-volatile component in the second resin composition is set to 100% by mass, the results of the present invention are more remarkably obtained. From the viewpoint of the desired effect, it is preferably 40 mass % or less, more preferably 30 mass % or less, particularly preferably 20 mass % or less, and the lower limit thereof is, for example, 0 mass % or more, 0.1 mass % or more, 0.5 mass % or more, 1 % by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more.

<(F) Hardening accelerator> When each of the first resin composition and the second resin composition contains an epoxy resin (A-1) as a thermosetting resin (A), and further, a case where a curing accelerator (F) is contained as an optional component . (F) The hardening accelerator has a function of promoting the hardening of the (A-1) epoxy resin.

Examples of the curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. Among them, an imidazole-based hardening accelerator is preferable from the viewpoint of improving the crosslinking property. (F) A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

Phosphorus-based curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium caprate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium laurate) Butylphosphonium) pyromellitic acid ester, tetrabutylphosphonium hydrogen phthalate (Tetrabutylphosphonium hydrogen phthalate), tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl Aliphatic phosphonium salts such as ]-4-methylphenate ( Phenolate ) , di-tert-butyldimethylphosphonium tetraphenyl borate, etc.; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide Phosphonium, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolyl borate, tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium tetra-p-tolyl borate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetra Phenyl borate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate Aromatic phosphonium salts such as salts, butyltriphenylphosphonium thiocyanate, etc.; aromatic phosphine-borane complexes such as triphenylphosphine and triphenylborane; triphenylphosphine and p-benzoquinone Aromatic phosphine and quinone addition reactants such as addition reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butylphosphine, di- Aliphatic phosphines such as -tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine, etc.; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenyl Phosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tris-p-toluene phosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-isopropylphenyl)phosphine 4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl) ) phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl) ) phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl) ) phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphine) Aromatic phosphines such as phosphino)butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino)diphenyl ether, and the like.

Urea-based hardening accelerators include, for example, 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1, Aliphatic dimethyl urea such as 1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chloro Phenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)- 1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3 -(3,4-Dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxy phenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)benzene base]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)benzene base]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4-methyl-1 , 3-phenylene) bis(N', N'-dimethylurea) [toluene bis-dimethylurea] and other aromatic dimethylureas, etc.

The guanidine-based hardening accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, and dimethylguanidine. Guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5 ,7-Triazabicyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1 -Dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc.

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole. , 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl- 4-Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-benzene Imidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino- 6-[2'-Undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazole yl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isotriazine Polycyanic acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl Imidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methyl Imidazoline, 2-phenylimidazoline and other imidazole compounds and adducts of imidazole compounds and epoxy resins.

As the imidazole-based hardening accelerator, commercially available products can also be used, for example, "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Chemical Co., Ltd., "P200-H50" manufactured by Mitsubishi Chemical Co., Ltd., etc. .

The metal-based hardening accelerators include, for example, 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 acetylacetonate (II), cobalt acetylacetonate (III), etc., organocopper complexes such as copper acetylacetonate (II), etc. Organozinc complexes such as zinc (II) acetylacetonate, organoiron complexes such as iron (III) acetylacetonate, organonickel complexes such as nickel (II) acetylacetonate, manganese (II) acetylacetonate ) and other organic manganese complexes, etc. The organic metal salts include, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-tri( Dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc.

As the amine-based hardening accelerator, a commercially available product may be used, for example, "MY-25" manufactured by Ajinomoto-fine-techno, Inc., and the like are exemplified.

The content (% by mass) of the (F) hardening accelerator in the first resin composition is not particularly limited, but when the non-volatile component in the first resin composition is set to 100% by mass, the present invention is more remarkably obtained. From the viewpoint of the desired effect, it is preferably 5 mass % or less, more preferably 3 mass % or less, particularly preferably 1 mass % or less, and the lower limit thereof may be, for example, 0 mass % or more.

The content (% by mass) of the (F) hardening accelerator in the second resin composition is not particularly limited, but when the non-volatile component in the second resin composition is set to 100% by mass, the present invention is more remarkably obtained. From the viewpoint of the desired effect, preferably 5 mass % or less, more preferably 3 mass % or less, particularly preferably 1 mass % or less, and the lower limit thereof is, for example, 0 mass % or more, 0.001 mass % or more, 0.01 mass % or more, Preferably it is 0.1 mass % or more.

<(G) Other additives> Each of the first resin composition and the second resin composition may further contain optional additives as nonvolatile components. Examples of such additives include organic fillers such as rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, Colorants for titanium oxide, carbon black, etc.; polymerization inhibitors for hydroquinone, catechol, pyrogallol, phenothiazine, etc.; ;Tackifiers such as Benton and microcrystalline kaolinite; Defoamers such as polysiloxane defoamer, acrylic defoamer, fluorine defoamer, vinyl resin defoamer, etc.; Benzotriazole UV absorbers such as UV absorbers; Adhesion enhancers such as urea silanes; Endowment agents; antioxidants such as hindered phenol-based antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants, polysiloxane-based surfactants, etc.; phosphorus-based flame retardants (such as , phosphate compounds, phosphazene compounds, phosphonic acid compounds, red phosphorus), nitrogen-based flame retardants (such as melamine sulfate), halogen-based flame retardants, inorganic flame retardants (such as antimony trioxide) and other flame retardants ; Phosphate-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, polysiloxane-based dispersants, anionic dispersants, cationic dispersants, etc.; borate-based stabilizers, titanate-based dispersants Stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, carboxylic acid anhydride stabilizers, and other stabilizers. (G) Other additives may be used alone or in combination of two or more at an arbitrary ratio. (G) The content of other additives can be appropriately set as long as those skilled in the art are familiar with it.

<(H) Organic solvent> Each of the first resin composition and the second resin composition may further contain an arbitrary organic solvent as a volatile component in addition to the above-mentioned nonvolatile component. (H) As the organic solvent, as long as it can dissolve at least a part of the nonvolatile components, a known one can be used appropriately, and the type thereof is not particularly limited. (H) Organic solvent, for example, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, acetic acid Ester solvents such as isopentyl, methyl propionate, ethyl propionate, γ-butyrolactone, etc.; tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl Ether, diphenyl ether and other ether solvents; methanol, ethanol, propanol, butanol, ethylene glycol and other alcohol solvents; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol Alcohol monoethyl ether acetate, ethyl diethylene glycol acetate, γ-butyrolactone, methyl methoxypropionate and other ether ester solvents; methyl lactate, ethyl lactate, 2-hydroxyisobutyl Ester alcohol solvents such as methyl acid; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol) ) and other ether alcohol-based solvents; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other amide-based solvents; dimethylsulfoxide Nitrile-based solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon-based solvents such as hexane, cyclopentane, cyclohexane, methylcyclohexane, etc.; benzene, toluene, xylene, ethyl Aromatic hydrocarbon solvents such as benzene, trimethylbenzene, etc. (H) An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types in arbitrary ratios. When the (H) organic solvent is used, one type may be used alone, or two or more types may be used in combination in an arbitrary ratio.

<Manufacturing method of resin composition> The first resin composition and the second resin composition are individually prepared in arbitrary preparation containers, and (A) thermosetting resin, (B) inorganic filler, (C) radical polymerizable compound, (D) Radical polymerization initiator, (E) thermoplastic resin, (F) hardening accelerator, (G) other additives, and (H) organic solvent, if necessary, in any order, and/or a part or All are added at the same time and mixed to make. In addition, in the process of adding and mixing each component, the temperature may be appropriately set, and heating and/or cooling may be performed temporarily or all the time. In addition, in the process of adding and mixing, or after that, the resin composition may be uniformly dispersed by stirring or shaking using, for example, a stirring device such as a mixer or a shaking device. In addition, defoaming can be performed under low pressure conditions such as under vacuum while stirring or shaking.

＜Support body＞ The support in the resin sheet with a support includes, for example, a film made of a plastic material, a metal foil, and a release paper, preferably a film and a metal foil made of a plastic material.

When a film made of a plastic material is used as the support, for example, the plastic material includes polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter sometimes abbreviated as "PET"). Polyester such as "PEN"), polycarbonate (hereinafter sometimes referred to as "PC"), polymethyl methacrylate (PMMA) and other acryl groups, cyclic polyolefins, triacetyl cellulose ( TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When using a metal foil as a support body, a copper foil, an aluminum foil, etc. are mentioned, for example, a copper foil is preferable. As the copper foil, a foil composed of a single metal of copper can be used, and a foil composed of an alloy of copper and other metals (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

A matt treatment, corona treatment and antistatic treatment can be applied to the surface of the support which is joined to the resin sheet layer.

Moreover, as a support body, the support body with a mold release layer which has a mold release layer on the surface joined to the resin sheet layer can be used. The release agent used for the release layer of the support with the release layer can be, for example, one selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and polysiloxane resins. more than one release agent. As the support with a release layer, commercially available products can be used, for example, "SK-1", "SK-1", "" AL-5", "AL-7", "lumirror T60" manufactured by Toray Corporation, "Purex" manufactured by Teijin Corporation, "unipeel" manufactured by Unitika Corporation, etc.

The thickness of the support body is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. Moreover, when the support body with a mold release layer is used, the thickness of the whole support body with a mold release layer is preferably within the above-mentioned range.

The resin sheet with the support may further contain a protective film on the surface not joined to the support of the resin sheet layer. The protective film contributes to the adhesion of dirt and the like on the surface of the resin sheet layer or prevents injury. As the material of the protective film, the same materials as those described in the column of <Support body> can be used. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. The resin sheet with the support can be used by peeling off the protective film when manufacturing a printed wiring board or the like. The thickness of the protective film is preferably thinner than the thickness of the support.

<Manufacturing method of resin sheet with support> A preferred embodiment of the method for producing a resin sheet with a support uses a first resin sheet provided with a first resin composition layer on a first support, and a second support provided with a second resin composition The second resin sheet of the material layer is a method of laminating the second resin composition layer and the first resin composition layer by bonding to form a resin sheet with a support. In this method, by removing the second support first compared to the first support, the first support becomes the support described above in the resin sheet with the support.

For the first and second resin sheets, for example, the liquid first resin composition and the second resin composition are directly prepared, or the first resin composition and the second resin composition are dissolved in an organic solvent to prepare a resin varnish. It is manufactured by coating on the 1st support body and the 2nd support body using a die coater etc., respectively, and further drying to form a 1st resin composition layer or a 2nd resin composition layer. As the organic solvent, the same ones as those described as components of the resin composition can be exemplified. An organic solvent can be used individually by 1 type. Two or more types can also be used in combination.

Drying of the resin composition can be carried out by conventional methods such as heating and blowing hot air. The drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the first and second resin composition layers is 10 mass % or less, preferably 5 mass % or less. Depending on the boiling point of the organic solvent in the resin composition, for example, in the case of using a resin composition containing an organic solvent of 30% by mass to 60% by mass, it can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes. The first and second resin composition layers.

As another embodiment, after coating the first resin composition on the support, drying the coating film to form the first resin composition layer, and then coating the second resin composition on the first resin composition layer, The method of drying the coating film and providing the second resin composition layer can produce a resin sheet with a support.

In this method, for the first resin composition layer, the liquid first resin composition may be directly prepared, or the first resin composition may be dissolved in the same organic solvent as above to prepare a resin varnish, and a die coater or the like may be used for this. , coated on the support, and produced by drying the resin composition. For the second resin composition layer, the liquid second resin composition may be directly prepared, or the second resin composition may be dissolved in the same organic solvent as above to prepare a resin varnish, and this may be coated with a die coater or the like. The cloth is placed on the first resin composition layer, and is produced by drying the resin composition. The drying method of the resin composition can be dried by the same method as the above-mentioned conditions.

In addition, the resin sheet with a support can be formed by a tandem coating method in which two types of resin compositions (resin varnishes) are sequentially coated on one coating line in addition to the above-described manufacturing method.

The resin sheet with the support can be wound into a roll for storage. When the resin sheet with the support has a protective film, the protective film can be peeled off and used.

<Characteristics of resin sheet with support> By curing the resin sheet layer of the resin sheet with a support of the present invention, an insulating layer formed of a cured product of the resin sheet layer can be obtained. This insulating layer forms a via hole, and when roughening treatment is applied, the white fringing phenomenon can be suppressed. Hereinafter, these effects will be described with reference to the drawings.

2 is a cross-sectional view schematically showing an insulating layer 100 obtained by curing the resin sheet layer of the resin sheet with a support according to one embodiment of the present invention together with an inner layer substrate 200 . FIG. 2 is a plane passing through the center 120C of the bottom 120 of the via hole 110 and parallel to the thickness direction of the insulating layer 100 , showing a section of cutting the insulating layer 100 .

As shown in FIG. 2 , the insulating layer 100 includes a layer obtained by curing the resin sheet layer formed on the inner layer substrate 200 including the conductor layer 210 , and a second resin composition layer in order from the conductor layer 210 side 20. The second cured layer 20' that is thermally cured, and the first cured layer 10' that thermally cures the first resin composition layer 10. In addition, the insulating layer 100 forms the via hole 110 . The via hole 110 is generally formed in a forward-taper shape with a diameter closer to the surface 100U of the insulating layer 100 on the opposite side of the conductor layer 210 . The larger the diameter, the closer to the conductor layer 210 and the smaller the diameter. A column with a certain diameter is formed. The via hole 110 is usually formed by irradiating the surface 100U of the insulating layer 100 on the opposite side of the conductor layer 210 with laser light to remove a part of the insulating layer 100 .

The bottom of the conductive layer 210 side of the aforementioned via hole 110 is conveniently referred to as "the bottom of the via hole", and is denoted by the symbol 120 . In addition, the diameter of the via bottom 120 is referred to as the via bottom diameter Lb. In addition, the opening formed on the opposite side of the conductive layer 210 of the via hole 110 is conveniently referred to as "the top of the via hole", and is denoted by the reference numeral 130 . In addition, the diameter of the guide hole top 130 is called the guide hole top diameter Lt. Generally, the via bottom 120 and the via top 130 form a circular shape from the planar shape seen in the thickness direction of the insulating layer 100, but may also be an elliptical shape. When the planar shapes of the via bottom 120 and the via top 130 are elliptical shapes, the via bottom diameter Lb and via top diameter Lt respectively represent the long diameter of the aforementioned elliptical shape.

At this time, the taper rate Lb/Lt obtained by dividing the via bottom diameter Lb by the via top diameter Lt is closer to 100%, the better the shape of the via 110 is.

The taper ratio Lb/Lt of the guide hole 110 can be calculated from the guide hole bottom diameter Lb and the guide hole top diameter Lt of the guide hole 110 . In addition, the diameter Lb of the bottom of the guide hole and the diameter of the top of the guide hole Lt of the guide hole 110 use FIB (Focused Ion Beam), so that the insulating layer 100 is parallel to the thickness direction of the insulating layer 100 and passes through the center 120C of the bottom 120 of the guide hole. After cutting in the form of cross-section, the cross-section can be observed and measured with an electron microscope.

3 is a plan view schematically showing a surface 100U on the opposite side to the conductor layer 210 (in FIG. 3 , not shown) of the insulating layer 100 obtained by curing the resin sheet layer of the resin sheet with a support according to one embodiment of the present invention .

As shown in FIG. 3 , when viewing the insulating layer 100 formed with the via hole 110 , around the via hole 110 , from the edge 180 of the top 130 of the via hole to the edge 190 on the peripheral side of the discolored portion 140 , insulation is observed. The discolored portion 140 of the layer 100 is discolored. The discolored portion 140 is formed by resin deterioration when the guide hole 110 is formed, and is usually formed continuously from the guide hole 110 . In addition, in many cases, the discolored part 140 becomes a whitened part.

4 is a cross-sectional view schematically showing a roughened insulating layer 100 together with an inner layer substrate 200 obtained by hardening the resin sheet layer of the resin sheet with a support according to one embodiment of the present invention. In this FIG. 4 , the cross section of the insulating layer 100 is cut through a plane parallel to the thickness direction of the insulating layer 100 passing through the center 120C of the guide hole bottom 120 of the guide hole 110 .

As shown in FIG. 4 , when the insulating layer 100 formed with the via holes 110 is subjected to roughening treatment, a white fringing phenomenon occurs, and the insulating layer 100 of the discolored portion 140 is peeled off from the conductor layer 210 , sometimes forming the edge of the bottom portion 120 of the via hole. 150 continuous gap portion 160 .

By using the resin sheet layer in the present invention, the aforementioned haloing phenomenon can be suppressed. Therefore, peeling of the insulating layer 100 from the conductor layer 210 can be suppressed, so that the size of the gap portion 160 can be reduced.

The edge 150 of the bottom 120 of the guide hole corresponds to the edge of the inner peripheral side of the gap portion 160 . Therefore, the distance Wb from the edge 150 of the guide hole bottom 120 to the end portion on the peripheral side of the gap portion 160 (that is, from the center 120C of the guide hole bottom 120 to the distal end) 170 corresponds to the gap portion 160 The size of the in-plane direction. Here, the in-plane direction refers to a direction perpendicular to the thickness direction of the insulating layer 100 . In addition, in the following description, the aforementioned distance Wb may refer to the white edge distance Wb from the edge 150 of the guide hole bottom 120 of the guide hole 110 . Therefore, the white edge distance Wb of the edge 150 of the bottom 120 of the via hole can be used to evaluate the degree of suppression of the white edge phenomenon. Specifically, the smaller the margin distance Wb of the edge 150 of the via bottom 120 is, the more effectively the margin phenomenon can be suppressed.

For example, the insulating layer 100 obtained by heating the resin sheet layer formed on the copper foil at 100° C. for 30 minutes and then curing it at 180° C. for 30 minutes is irradiated with CO ₂ laser light, and the top diameter Lt of the via hole forms a via hole with a diameter of about 40 μm 110. Then, it was immersed in the swelling solution at 60°C for 10 minutes, then immersed in the oxidizing agent solution at 80°C for 20 minutes, then immersed in the neutralizing solution at 40°C for 5 minutes, and then dried at 80°C for 15 minutes. . When using the resin sheet with a support of the present invention, the white edge distance Wb of the edge 150 of the bottom 120 of the guide hole 110 of the insulating layer 100 obtained in this way is preferably 10 μm or less, more preferably 8 μm or less, Still more preferably, it is 5.5 μm or less, and particularly preferably 5 μm or less.

The irradiation conditions of the aforementioned CO ₂ laser light were mask diameter of 1 mm, pulse width of 16 μs, energy of 0.2 mJ/shot, irradiation number of 2, and pulse mode (10 kHz).

From the white edge distance Wb of the edge 150 of the bottom 120 of the via hole, FIB (Focused Ion Beam) can be used to make the insulating layer 100 parallel in the thickness direction of the insulating layer 100 and cut through the cross-section of the center 120C of the bottom 120 of the via hole. Then, the cross section was observed and measured with an electron microscope.

In addition, by using the resin sheet layer, the shape of the via hole 110 in the insulating layer 100 before roughening can be easily controlled. Therefore, the shape of the via hole 110 can be easily controlled even after the insulating layer 100 is generally roughened. Therefore, even after the roughening process, the shape of the guide hole 110 can be made good as before the roughening process.

The taper ratio Lb/Lt of the guide hole 110 after the roughening process can be calculated from the guide hole bottom diameter Lb and the guide hole top diameter Lt of the guide hole 110 . In addition, the diameter Lb of the bottom of the guide hole and the diameter of the top of the guide hole Lt of the guide hole 110 are made by using FIB (Focused Ion Beam). After the section appears to be cut, the section can be observed with an electron microscope for measurement.

Further, according to the review of the present inventors, it is found that the larger the diameter of the guide hole is, the larger the size of the gap portion 160 tends to be. Therefore, the ratio of the size of the gap portion 160 to the diameter of the guide hole 110 can be used to evaluate the degree of suppression of the white fringing phenomenon. For example, it can be evaluated by the white edge ratio Hb with respect to the bottom radius Lb/2 of the guide hole 110 . Here, the bottom radius Lb/2 of the guide hole 110 is the radius of the guide hole bottom 120 of the guide hole 110 . Also, the white edge ratio Hb relative to the bottom radius Lb/2 of the via hole 110 refers to the ratio obtained by dividing the white edge distance Wb of the edge 150 of the via bottom 120 by the bottom radius Lb/2 of the via hole 110 . The smaller the white edge ratio Hb relative to the bottom radius Lb/2 of the guide hole 110, the more effective the suppression of the white edge phenomenon.

For example, the insulating layer 100 obtained by heating the resin sheet layer formed on the copper foil at 100° C. for 30 minutes and then curing it at 180° C. for 30 minutes is irradiated with CO ₂ laser light, and the top diameter Lt of the via hole forms a via hole with a diameter of about 40 μm 110. Then, it was immersed in the swelling solution at 60°C for 10 minutes, then immersed in the oxidizing agent solution at 80°C for 20 minutes, then immersed in the neutralizing solution at 40°C for 5 minutes, and then dried at 80°C for 15 minutes. . The white edge ratio Hb formed by the insulating layer 100 thus obtained relative to the bottom radius Lb/2 of the via hole 110 is preferably 35% or less, more preferably 30% or less, and still more preferably 25% or less.

The irradiation conditions of the aforementioned CO ₂ laser light were mask diameter of 1 mm, pulse width of 16 μs, energy of 0.2 mJ/shot, irradiation number of 2, and pulse mode (10 kHz).

The white edge ratio Hb relative to the bottom radius Lb/2 of the guide hole 110 can be calculated from the guide hole bottom diameter Lb of the guide hole 110 and the white edge distance Wb of the edge 150 of the guide hole bottom 120 of the guide hole 110 .

Further, generally by using the resin sheet layer in the present invention, the formation of the discolored portion 140 during the formation of the via hole 110 can be suppressed. Therefore, as shown in FIG. 3 , the size of the discolored portion 140 can be reduced, and it is desirable to make the discolored portion 140 disappear. The size of the discolored portion 140 can be evaluated by the white edge distance Wt of the edge 180 of the guide hole top 130 of the guide hole 110 .

The edge 180 of the top 130 of the guide hole corresponds to the edge of the inner peripheral side of the discoloration portion 140 . The white edge distance Wt from the edge 180 of the guide hole top 130 refers to the distance from the edge 180 of the guide hole top 130 to the edge 190 on the peripheral side of the discoloration portion 140 . The smaller the white edge distance Wt of the edge 180 of the guide hole top 130 is, the more effectively the formation of the discoloration portion 140 can be suppressed.

For example, the insulating layer 100 obtained by heating the resin sheet layer formed on the copper foil at 100° C. for 30 minutes and then curing it at 180° C. for 30 minutes is irradiated with CO ₂ laser light, and the top diameter Lt of the via hole forms a via hole with a diameter of about 40 μm 110. Then, it was immersed in the swelling solution at 60°C for 10 minutes, then immersed in the oxidizing agent solution at 80°C for 20 minutes, then immersed in the neutralizing solution at 40°C for 5 minutes, and then dried at 80°C for 15 minutes. . The white edge distance Wt from the edge 180 of the via top 130 of the insulating layer 100 obtained in this way is preferably 15 μm or less, more preferably 10 μm or less, and still more preferably 8 μm or less.

The irradiation conditions of the aforementioned CO ₂ laser light were mask diameter of 1 mm, pulse width of 16 μs, energy of 0.2 mJ/shot, irradiation number of 2, and pulse mode (10 kHz).

The white edge distance Wt from the edge 180 of the top 130 of the guide hole can be determined by observation with an optical microscope.

In addition, according to the review of the present inventors, it is found that generally, the larger the diameter of the guide hole 110 is, the larger the size of the discolored portion 140 tends to be. Therefore, the ratio of the size of the discolored portion 140 to the diameter of the guide hole 110 can evaluate the degree of suppression of the formation of the discolored portion 140 . For example, it can be evaluated by the white edge ratio Ht relative to the top radius Lt/2 of the guide hole 110 . Here, the top radius Lt/2 of the guide hole 110 is the radius of the guide hole top 130 of the guide hole 110 . Also, the white edge ratio Ht relative to the top radius Lt/2 of the via hole 110 refers to the ratio obtained by dividing the white edge distance Wt of the edge 180 of the via top 130 by the top radius Lt/2 of the via hole 110 . The smaller the white edge ratio Ht relative to the top radius Lt/2 of the guide hole 110 is, the more effective it is to suppress the formation of the discolored portion 140 .

For example, the insulating layer 100 obtained by heating the resin sheet layer formed on the copper foil at 100° C. for 30 minutes and then curing it at 180° C. for 30 minutes is irradiated with CO ₂ laser light, and the top diameter Lt of the via hole forms a via hole with a diameter of about 40 μm 110. Then, it was immersed in the swelling solution at 60°C for 10 minutes, then immersed in the oxidizing agent solution at 80°C for 20 minutes, then immersed in the neutralizing solution at 40°C for 5 minutes, and then dried at 80°C for 15 minutes. . The white-to-edge ratio Ht formed by the insulating layer 100 thus obtained relative to the top radius Lt/2 of the via hole 110 is preferably 35% or less, more preferably 30% or less, and still more preferably 28% or less.

The irradiation conditions of the aforementioned CO ₂ laser light were: mask diameter of 1 mm, pulse width of 16 μs, energy of 0.2 mJ/shot, irradiation number of 2, and pulse mode (10 kHz).

The white edge ratio Ht relative to the top radius Lt/2 of the guide hole 110 can be calculated from the guide hole top diameter Lt of the guide hole 110 and the white edge distance Wt of the edge 180 of the guide hole top 130 of the guide hole 110 .

In the manufacturing process of the printed wiring board, the via hole 110 is usually formed in a state where no other conductor layer (not shown) is provided on the surface 100U of the insulating layer 100 on the opposite side of the conductor layer 210 . Therefore, when the manufacturing process of the printed wiring board is known, the bottom portion 120 of the via hole is located on the side of the conductor layer 210, and the structure of the top portion 130 of the via hole opening on the opposite side of the conductor layer 210 can be clearly recognized. However, in the completed printed wiring board, conductor layers may be provided on both sides of the insulating layer 100 . At this time, due to the positional relationship with the conductor layer, it may be difficult to distinguish the bottom portion 120 of the via hole from the top portion 130 of the via hole. However, generally, the diameter Lt of the top of the guide hole 130 is greater than the diameter Lb of the bottom of the guide hole 120 . Therefore, in the aforementioned situation, the bottom portion 120 of the via hole and the top portion 130 of the via hole can be distinguished by the size of the diameter.

By using the resin sheet with the support of the present invention, in addition to suppressing the white fringing phenomenon, the dielectric tangent d _all of the entire hardened layer (insulating layer) can be lowered.

。 For example, the dielectric tangent _{dall of} the entire hardened layer (insulating layer) composed of two layers of the first hardened layer and the second hardened layer 2 The thickness of the resin composition layer is set to t ₂ (μm), and the dielectric tangent of the first cured layer formed by curing the first resin composition layer at 190° C. for 90 minutes (measurement frequency 5.8 GHz, measurement temperature 23° C.) is set to As d ₁ , when the dielectric tangent (measurement frequency 5.8 GHz, measurement temperature 23° C.) of the second cured layer formed by curing the second resin composition layer at 190° C. for 90 minutes is set as d ₂ , the following Equation (5) is calculated.

.

The dielectric tangent d _all of the entire hardened layer (insulating layer) calculated in this way is preferably 0.020 or less, 0.010 or less, more preferably 0.009 or less, 0.008 or less, 0.007 or less, still more preferably 0.006 or less, 0.0058 or less, 0.0056 or less, particularly preferably 0.0055 or less, 0.005 or less, 0.0045 or less, and 0.004 or less.

<Application of resin sheet with support> The resin sheet with a support of the present invention is suitable for use as a resin sheet with a support for forming an insulating layer that forms a conductor layer (including a rewiring layer) formed on the insulating layer.

In addition, in the multilayer printed wiring board described later, it is suitable for use as a resin sheet with a support for forming an insulating layer of a multilayer printed wiring board, and a resin sheet with a support for forming an interlayer insulating layer of a printed wiring board.

Further, for example, in the case of manufacturing a semiconductor chip package through the following steps (1) to (6), the resin sheet with a support of the present invention is also suitable as an insulating layer for rewiring layer formation and rewiring formation layer formation. Resin sheet with support, and resin sheet with support for semiconductor chip packaging. When the semiconductor chip package is manufactured, a redistribution layer can be formed on the sealing layer. (1) the step of laminating the temporary fixing film on the base material, (2) the step of temporarily fixing the semiconductor wafer on the temporary fixing film, (3) the step of forming the sealing layer on the semiconductor wafer, (4) the step of peeling off the base material and the temporary fixing film from the semiconductor wafer, (5) a step of forming a rewiring formation layer as an insulating layer on the substrate of the semiconductor wafer and the surface after the peeling of the temporary fixing film, and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

In addition, the resin sheet layer in the resin sheet with a support of the present invention provides an insulating layer with good parts embeddability, so that the printed wiring board can also be suitably used when the parts embed circuit board.

。 [Cured product] The cured product of the present invention is a cured product formed by curing the resin sheet layer in the resin sheet with a support of the present invention. Therefore, the cured product of the present invention has a first cured layer formed of the cured product of the first resin composition and a second resin composition formed on the first cured layer with a different composition from the first resin composition For the second hardened layer formed by the hardened material, let the thickness of the first hardened layer be t _1' (μm), the thickness of the second hardened layer be t _2' (μm), and the thickness of the first hardened layer The elastic modulus (measurement temperature at 23°C) is set as y ₁ (GPa), the elastic modulus of the second hardened layer (measurement temperature at 23° C.) is set as y ₂ (GPa), and the dielectric tangent of the first hardened layer ( When the measurement frequency is 5.8 GHz, the measurement temperature is 23° C.) as d ₁ , and the dielectric tangent of the second hardened layer (the measurement frequency is 5.8 GHz and the measurement temperature is 23° C.) is set as d ₂ , all of the following formulas (1′) are satisfied. , (2) and (3).

.

The thickness t1 _' (μm) of the first hardened layer is the same as the thickness t1 (μm) of the first resin composition layer, and the thickness _{t2' (} μm) of the second hardened layer is the same as the thickness t1 (μm) of the second resin composition layer. The thickness t ₂ (μm) is the same. Therefore, the range of t1 _' /t2 _' is the same as the range of _t1 / _t2 .

[Printed Wiring Board] The printed wiring board of this invention is equipped with the insulating layer (insulation layer which consists of hardened|cured material) formed of the resin sheet layer of the resin sheet with a support body of this invention.

A printed wiring board can be manufactured by the method including the steps of the following (I) and (II), using, for example, the above-mentioned resin sheet with a support. (1) On the inner layer substrate, the lamination step is performed so that the second resin composition layer of the resin sheet with the support is bonded to the inner layer substrate (II) Step of thermosetting the resin sheet layer to form an insulating layer

The "inner layer substrate" used in the step (I) refers to a member that becomes a substrate of a printed wiring board, and examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting type Polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one side or both sides, and the conductor layer may be patterned. An inner layer substrate in which a conductor layer (circuit) is formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit substrate". Moreover, when manufacturing a printed wiring board, the intermediate product which forms an insulating layer and/or a conductor layer is also included in the "inner-layer board|substrate" of this invention. When the printed wiring board is a component-embedded circuit board, a component-embedded inner-layer substrate can also be used.

The lamination of the inner layer substrate and the resin sheet with the support is performed by, for example, from the support side, by thermocompression bonding of the second resin composition layer of the resin sheet layer to the inner substrate. The member for thermocompression bonding of the resin sheet with the support to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") includes, for example, a heated metal plate (SUS mirror plate, etc.) or a metal roll (SUS roll), etc. . Also, instead of pressing the thermocompression-bonding member directly on the resin sheet with the support, the resin sheet with the support sufficiently follows the surface unevenness of the inner layer substrate, interposed between an elastic material such as heat-resistant rubber, etc. Better compression.

The lamination of the inner layer substrate and the resin sheet with the support can be carried out by a vacuum lamination method. In the vacuum lamination method, the heating and crimping temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heating and crimping pressure is preferably 0.098MPa to 1.77MPa, more preferably 0.29MPa~ In the range of 1.47 MPa, the heating and crimping time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure at a pressure of 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurization laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum coater by Nikko-Materials Co., Ltd., and a batch-type vacuum pressurization laminator.

After lamination, under normal pressure (atmospheric pressure), for example, by pressing the thermocompression-bonding member from the support side, the laminated resin sheet with the support may be smoothed. The pressing conditions of the smoothing treatment may be the same as those of the thermocompression bonding conditions of the above-mentioned build-up. The smoothing process can be performed by a commercially available laminator. In addition, the lamination and the smoothing process can be performed continuously using the above-mentioned commercially available vacuum lamination machine.

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

In step (II), the resin sheet layer is thermally cured to form an insulating layer. The thermosetting conditions of the resin sheet layer are not particularly limited, and conditions generally employed when forming an insulating layer of a printed wiring board can be used.

For example, the thermal curing conditions of the resin sheet layer vary depending on the types of the first and second resin compositions, and the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and more preferably 170°C. ℃~210℃. The hardening time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and still more preferably 15 minutes to 100 minutes.

Before thermosetting the resin sheet layer, the resin sheet layer is preliminarily heated at a temperature lower than the curing temperature. For example, before thermosetting the resin sheet layer, the resin sheet layer is pre-heated at a temperature of 50°C or more but not 120°C (preferably 60°C or more and 115°C or less, more preferably 70°C or more and 110°C or less). minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and still more preferably 15 minutes to 100 minutes).

When manufacturing a printed wiring board, (III) the step of opening a hole in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming the conductor layer can be further carried out. These steps (III) to (V), which can be used in the manufacture of printed wiring boards, can be implemented in accordance with various known methods for those skilled in the art. In addition, when removing the support after step (II), the removal of the support may be between step (II) and step (III), between step (III) and step (IV), or between step (IV) between step (V). In addition, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) can be repeated to form a multilayer wiring board.

The step (III) is a step of opening holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. The step (III) can be implemented using, for example, a drill, a laser, a plasma, or the like, depending on the composition of the first and second resin compositions used for forming the insulating layer, and the like. The size or shape of the holes can be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smear removal is also carried out. The order and conditions of the roughening treatment are not particularly limited, and when the insulating layer of the printed wiring board is formed, well-known procedures and conditions generally used can be adopted. For example, the insulating layer can be roughened by performing swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling liquid used in the roughening step is not particularly limited, and examples thereof include alkali solutions, surfactant solutions, etc., preferably alkali solutions, and more preferably sodium hydroxide solutions and potassium hydroxide solutions. Commercially available swelling liquids include, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. The swelling treatment by the swelling liquid is not particularly limited, but for example, the insulating layer is immersed in the swelling liquid at 30° C. to 90° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid of 40° C. to 80° C. for 5 minutes to 15 minutes. The oxidizing agent used for the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. By the roughening treatment of an oxidizing agent such as an alkaline permanganic acid solution, the insulating layer is preferably immersed in an oxidizing agent solution heated to 60° C. to 100° C. for 10 minutes to 30 minutes. In addition, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan. In addition, the neutralization liquid used for the roughening treatment is preferably an acidic aqueous solution, and as a commercial product, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan can be mentioned. The treatment with the neutralizing solution is performed by immersing the treated surface roughened by the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 1 minute to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object to be roughened by the oxidizing agent in a neutralizing liquid at 40° C. to 70° C. for 5 minutes to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 120 nm or less, more preferably 110 nm or less, and still more preferably 100 nm or less. The lower limit is not particularly limited, but is preferably 30 nm or more, more preferably 40 nm or more, and still more preferably 50 nm or more. The arithmetic mean roughness (Ra) of the insulating layer surface can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains at least one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, a metal alloy (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy) selected from the group consisting of two or more kinds of metal alloys. formed layer. Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or a single metal layer of nickel, is preferred from the viewpoints of versatility, cost, easiness of patterning, etc. of the formation of the conductor layer. ･Alloy layer of chromium alloy, copper-nickel alloy, copper-titanium alloy, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy , and more preferably a single metal layer of copper.

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

The thickness of the conductor layer varies with the desired design of the printed wiring board, and is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductor layer can be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method, which is preferable from the viewpoint of easiness of manufacture. to be formed by the semi-additive method. Hereinafter, an example in which the conductor layer is formed by the semi-additive method is shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern for exposing a part of the plating seed layer corresponding to a desired wiring pattern is formed. On the exposed electroplating seed layer, after forming a metal layer by electroplating, the mask pattern is removed. Then, by removing the unnecessary plating seed layer by etching or the like, a conductor layer having a desired wiring pattern can be formed.

[semiconductor device] The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

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

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. "Conduction place" refers to "the place where the electrical signal is conducted in the printed wiring board", and the place can be the surface or the place where it is buried. In addition, when a semiconductor wafer is an electric circuit element using a semiconductor as a material, it does not specifically limit.

There is no particular limitation on the mounting method of a semiconductor chip in the manufacture of a semiconductor device, as long as the semiconductor chip can effectively function. Specifically, there are wire bonding mounting method, flip chip mounting method, bumpless build-up layer (BBUL) method. installation method, installation method by anisotropic conductive film (ACF), installation method by non-conductive film (NCF), etc. Here, "the mounting method by bumpless build-up layer (BBUL)" refers to "the mounting method in which the semiconductor chip is directly embedded in the concave portion of the printed wiring board, and the semiconductor chip is connected to the wiring on the printed wiring board". [Example]

Hereinafter, an Example is shown and this invention is demonstrated concretely. However, the present invention is not limited by the following examples. In the following description, "parts" and "%" indicating the amount respectively indicate "parts by mass" and "% by mass" unless otherwise specified. In addition, the operations described below are performed in an environment of normal temperature and normal pressure unless otherwise specified.

<Inorganic filler used> Inorganic filler 1: 100 parts of spherical silica (“SC2500SQ” manufactured by admatechs, average particle size 0.63 μm, specific surface area 11.2 m ² /g), N-phenyl-3 - One part of aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573) surface-treated. Inorganic filler 2: With respect to 100 parts of spherical silica (“UFP-30” manufactured by Denki Chemical Industry Co., Ltd., average particle size 0.078 μm, specific surface area 30.7 m ² /g), N-phenyl-3-amine 2 parts of propyl trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573) were surface-treated.

<Synthesis Example 1: Synthesis of Polyimide Resin 1> Into a 500 ml separable flask equipped with a nitrogen introduction tube and a stirring device, put the compound of 4-aminobenzoic acid 5-amino-1,1'-biphenyl-2-yl (formula (B-3)) ) 9.13g (30 mmol), 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride 15.61g (30 mmol), N-methyl- 94.64 g of 2-pyrrolidone, 0.47 g (6 mmol) of pyridine, and 10 g of toluene were subjected to an imidization reaction for 4 hours at 180° C. in a nitrogen atmosphere while removing toluene from the system on the way to obtain a polyamide Polyimide solution of imine resin 1 (non-volatile content 20 mass %). In the polyimide solution, no precipitation of the synthesized polyimide resin 1 was observed. The weight average molecular weight of the polyimide resin 1 was 45,000.

<Synthesis Example 2: Synthesis of Polyimide Resin 2> Aromatic tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan, 4,4'-(4,4'-isophthalic acid) was put into a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube. Propyldiphenoxy)bisphthalic anhydride) 65.0g, cyclohexanone 266.5g, and methylcyclohexane 44.4g, and the solution was heated to 60 degreeC. Next, after dropping 43.7 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) and 5.4 g of 1,3-bis(aminomethyl)cyclohexane, imidization was carried out at 140° C. for 1 hour. chemical reaction. Thereby, the polyimide solution (non-volatile matter 30 mass %) containing the polyimide resin 2 was obtained. Moreover, the weight average molecular weight of the polyimide resin 2 was 25,000.

<Preparation Example 1: Preparation of Resin Composition 1> 6 parts of bis-xylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 185), naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation, epoxy equivalent about 332) 4 parts, cyclohexane type epoxy resin ("ZX1658GS" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 135) 2 parts, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, cyclohexanone with a solid content of 30% by mass) : 1:1 solution of methyl ethyl ketone (MEK), Mw=35000) 10 parts in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone, heated and dissolved while stirring. After cooling to room temperature, 4.5 parts of active ester-based hardener ("EXB-8000L-65TM" manufactured by DIC Corporation, active group equivalent of about 220, toluene solution of 65% by mass of non-volatile components), maleimide 5 parts of a compound (“BMI-689” manufactured by Designer Molecules), 1 (55 parts) of an inorganic filler, and 0.1 part of a polymerization initiator (“Perhexyne 25B” manufactured by NOF Corporation) were uniformly dispersed using a high-speed rotary mixer , and filtered with a cartridge filter (“SHP020” manufactured by ROKITECHNO) to prepare a resin composition 1.

<Preparation Example 2: Preparation of Resin Composition 2> Preparation Example 1 was the same as Preparation Example 1, except that the amount of active ester-based hardener (“EXB-8000L-65TM” manufactured by DIC Corporation) was changed from 4.5 parts to 5 parts, and inorganic filler 2 (40 parts) was used instead of inorganic filler 1. Resin composition 2 was prepared in the same manner.

<Preparation Example 3: Preparation of Resin Composition 3> In addition to using 4.5 parts of an active ester-based hardener ("EXB-8151-62T" manufactured by DIC Corporation, a toluene solution with a solid content of 62% by mass) in place of the active ester-based hardener ("EXB-8000L-65TM" manufactured by DIC Corporation) , and resin composition 3 was prepared in the same manner as in Preparation Example 1.

<Preparation Example 4: Preparation of Resin Composition 4> Except using 10 parts of styrene-modified polyphenylene ether resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., Mn=1200, toluene solution of 65 mass % solid content), instead of maleimide compound (Designer molecules Co., Ltd.) Resin composition 4 was prepared in the same manner as in Preparation Example 1 except that "BMI-689" was prepared.

<Preparation Example 5: Preparation of Resin Composition 5> Prepared with 4 parts of a bifunctional acrylate compound (“NK ester A-DOG” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight 326) in place of the maleimide compound (“BMI-689” manufactured by Designer Molecules Co., Ltd.). Example 1 Resin composition 5 was prepared in the same manner.

<Preparation Example 6: Preparation of Resin Composition 6> Except for using 4 parts of a bifunctional allyl compound having a benzoxazine ring (“ALP-d” manufactured by Shikoku Chemical Industry Co., Ltd.) instead of a maleimide compound (“BMI-689” manufactured by Designer Molecules Co., Ltd.) , and resin composition 6 was prepared in the same manner as in Preparation Example 1.

<Preparation Example 7: Preparation of Resin Composition 7> Except not using bis-xylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation), naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation), cyclohexane type epoxy resin (Mitsubishi Chemical Corporation "ZX1658GS") and an active ester-based hardener ("EXB-8000L-65TM" manufactured by DIC Corporation), and the amount of maleimide compound ("BMI-689" manufactured by Designer molecules) was changed from 5 parts Resin composition 7 was prepared in the same manner as in Preparation Example 1, except that the phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation) was replaced with 15 parts of polyimide resin 1 (9 parts) synthesized in Synthesis Example 1.

<Preparation Example 8: Preparation of Resin Composition 8> Resin Composition 8 was prepared in the same manner as in Preparation Example 7, except that Polyimide Resin 2 (9 parts) synthesized in Synthesis Example 2 was used instead of Polyimide Resin 1 synthesized in Synthesis Example 1.

<Preparation Example 9: Preparation of Resin Composition 10> 6 parts of bisphenol epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent about 169, 1:1 mixture of bisphenol A type and bisphenol F type), biphenyl aralkyl Type epoxy resin ("NC3000" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 276) 2 parts, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, cyclohexanone with a solid content of 30% by mass: methyl ethyl ketone) (MEK) 1:1 solution, Mw=35000) 10 parts, in the mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone, heat and dissolve while stirring. After cooling to room temperature, 2 parts of active ester-based hardener ("EXB-8000L-65TM" manufactured by DIC Corporation, active group equivalent of about 220, 65% by mass of non-volatile components in toluene:MEK: 1:1 solution) was mixed. , 2 parts of a cresol novolak-based hardener containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation, 2-methoxypropanol solution with a hydroxyl equivalent of about 151 and a solid content of 50%), 1 inorganic filler (3 parts) and 0.1 part of a hardening accelerator ("1B2PZ" manufactured by Shikoku Chemical Co., Ltd.), which were uniformly dispersed using a high-speed rotary mixer, and then filtered with a cartridge filter ("SHP020" manufactured by ROKITECHNO Corporation) to prepare a resin composition 10.

<Preparation Example 10: Preparation of Resin Composition 11> In addition to using 4 parts of a triazine-containing phenol novolak-based hardener ("LA7054" manufactured by DIC Corporation, a methyl ethyl ketone solution with a hydroxyl equivalent of 125, and a solid content of 60% by mass) in place of an active ester-based hardener (manufactured by DIC Corporation) Resin composition 11 was prepared in the same manner as in Preparation Example 9, except for "EXB-8000L-65TM") and a triazine skeleton-containing cresol novolak-based hardener ("LA-3018-50P" manufactured by DIC Corporation).

<Preparation Example 11: Preparation of Resin Composition 12> In addition to using 4 parts of a triazine-containing phenol novolak-based hardener ("LA7054" manufactured by DIC Corporation, a methyl ethyl ketone solution with a hydroxyl equivalent of 125, and a solid content of 60% by mass) in place of an active ester-based hardener (manufactured by DIC Corporation) Resin composition 12 was prepared in the same manner as in Preparation Example 1 except for "EXB-8000L-65TM").

<Preparation Example 12: Preparation of Resin Composition 13> Except that the usage amount of the active ester-based hardener (“EXB-8000L-65TM” manufactured by DIC Corporation) was changed from 4.5 parts to 4 parts, and the maleimide compound (“BMI-689” manufactured by Designer molecules Corporation) was not used , and the resin composition 13 was prepared in the same manner as in Preparation Example 1.

<Preparation Example 13: Preparation of Resin Composition 14> A resin composition 14 was prepared in the same manner as in Preparation Example 10, except that the usage amount of the inorganic filler 1 was changed from 3 parts to 25 parts.

<Example 1: Production of Resin Sheet 1 with Support> A PET film with a thickness of 38 μm (“AL5” manufactured by Lintec Co., Ltd.) was prepared as a support. On the support, the varnish-like resin composition 1 prepared in Preparation Example 1 was uniformly coated with a die coater, and the coated film was dried at 80 to 120° C. (average 100° C.) for 3 minutes. A first resin composition layer (thickness 25 μm) formed of the resin composition 1 was formed thereon. Next, the resin composition 10 in the form of varnish prepared in Preparation Example 9 was uniformly coated on the first resin composition layer with a die coater so that the total thickness of the resin composition layer after drying was 30 μm. The film was dried at 80° C. for 1 minute to form a second resin composition layer, and the smooth surface side of a polypropylene cover film (“alphan MA-411” manufactured by Oji F-Tex Co., Ltd.) with a thickness of 15 μm was bonded to the resin surface to prepare a support Resin sheet 1 with support body (38 μm PET film)/1st resin composition layer/2nd resin composition layer/protective film (MA-411). In addition, the thickness was measured using a contact-type film thickness meter (Mitutoyo company make, MCD-25MJ).

<Example 2: Production of resin sheet 2 with support> A resin sheet 2 with a support was produced in the same manner as in Example 1, except that the resin composition 2 prepared in Preparation Example 2 was used instead of the resin composition 1 prepared in Preparation Example 1.

<Example 3: Production of resin sheet 3 with support> A resin sheet 3 with a support was produced in the same manner as in Example 1, except that the resin composition 3 prepared in Preparation Example 3 was used instead of the resin composition 1 prepared in Preparation Example 1.

<Example 4: Production of resin sheet 4 with support> A resin sheet 4 with a support was produced in the same manner as in Example 1, except that the resin composition 4 prepared in Preparation Example 4 was used instead of the resin composition 1 prepared in Preparation Example 1.

<Example 5: Production of resin sheet 5 with support> A resin sheet 5 with a support was produced in the same manner as in Example 1, except that the resin composition 5 prepared in Preparation Example 5 was used instead of the resin composition 1 prepared in Preparation Example 1.

<Example 6: Production of resin sheet 6 with support> A resin sheet 6 with a support was produced in the same manner as in Example 1, except that the resin composition 6 prepared in Preparation Example 6 was used instead of the resin composition 1 prepared in Preparation Example 1.

<Example 7: Production of resin sheet 7 with support> A resin sheet 7 with a support was produced in the same manner as in Example 1, except that the resin composition 7 prepared in Preparation Example 7 was used instead of the resin composition 1 prepared in Preparation Example 1.

<Example 8: Production of resin sheet 8 with support> A resin sheet 8 with a support was produced in the same manner as in Example 1, except that the resin composition 8 prepared in Preparation Example 8 was used instead of the resin composition 1 prepared in Preparation Example 1.

<Example 9: Production of resin sheet 9 with support> A resin sheet 9 with a support was produced in the same manner as in Example 1, except that the resin composition 11 prepared in Preparation Example 10 was used instead of the resin composition 10 prepared in Preparation Example 9.

<Example 10: Production of Resin Sheet 10 with Support> A resin sheet 10 with a support was produced in the same manner as in Example 1, except that the resin composition 13 prepared in Preparation Example 12 was used instead of the resin composition 1 prepared in Preparation Example 1.

<Comparative Example 1: Production of Resin Sheet 1' with Support> A PET film with a thickness of 38 μm (“AL5” manufactured by Lintec Co., Ltd.) was prepared as a support. On this support, the varnish-like resin composition 1 prepared in Preparation Example 1 was uniformly coated with a die coater so that the thickness of the resin composition layer after drying was 30 μm, and the coating film was heated at 80 to 120° C. After drying for 3 minutes (average 100°C), the smooth surface side of a polypropylene cover film with a thickness of 15 μm (“alphan MA-411” manufactured by Oji F-Tex Co., Ltd.) was attached to the resin surface to prepare a support (38 μm PET film)/resin composition Resin sheet 1' with a support composed of a material layer/protective film (MA-411).

<Comparative Example 2: Production of Resin Sheet 2' with Support> A resin sheet 2' with a support was produced in the same manner as in Comparative Example 1, except that the resin composition 10 prepared in Preparation Example 9 was used instead of the resin composition 1 prepared in Preparation Example 1.

<Comparative Example 3: Production of Resin Sheet 3' with Support> A resin sheet 3' with a support was produced in the same manner as in Example 1, except that the resin composition 12 prepared in Preparation Example 11 was used instead of the resin composition 1 prepared in Preparation Example 1.

<Comparative Example 4: Production of Resin Sheet 4' with Support> Resin sheet 4' with a support was produced in the same manner as in Example 1, except that the resin composition 14 prepared in Preparation Example 13 and the resin composition 10 prepared in Preparation Example 9 were used.

<Comparative Example 5: Production of Resin Sheet 5' with Support> Resin sheet 5' with a support was produced in the same manner as in Example 1, except that the thickness of the first resin composition layer formed with the resin composition 1 was changed from 25 μm to 10 μm (the total thickness was 30 μm).

<Test example 1: Evaluation of white border suppression> (1) Copper laminated board Prepare a glass cloth base epoxy resin laminated board with copper foil layers on both sides and copper-clad laminates on both sides (copper foil thickness 3μm, substrate thickness 0.15mm, "HL832NSF LCA" manufactured by Mitsubishi Gas Chemical Co., Ltd., 255 × 340mm size), as Paste copper laminate.

(2) Lamination of resin sheets The protective film was peeled off from the resin sheet with each support produced in the Examples and Comparative Examples, and the resin composition was prepared using a batch vacuum pressure laminator (manufactured by Nikko-materials, 2-stage multi-layer laminator, CVP700). The material layer is in contact with the copper-clad laminate, and is laminated on both sides of the copper-clad laminate. The lamination system was depressurized for 30 seconds, the air pressure was set to 13 hPa or less, and the pressure-bonding was performed at 130° C. and a pressure of 0.74 MPa for 45 seconds. Next, at 120° C. and a pressure of 0.5 MPa, a hot press (Hot Press) was performed for 75 seconds.

(3) Thermosetting of the resin composition layer 30 minutes after the copper-clad laminate laminated with resin sheets was put into an oven at 100°C, then moved to an oven at 180°C for 30 minutes, thermally hardened to form an insulating layer, and the mold release PET was peeled off. This is the hardened substrate A.

(4) CO ₂ laser guide hole processing Using a CO ₂ laser processing machine (“605GTWIII (-P)” manufactured by Mitsubishi Electric Corporation), the insulating layer is irradiated with laser light through the thin film with the metal layer to form a guide hole on the insulating layer. The hole top diameter (diameter) is a plurality of guide holes of about 40 μm. The irradiation conditions of laser light are: mask diameter 1mm, pulse width 16μs, energy 0.2mJ/irradiation, number of irradiation 2, pulse mode (10kHz).

(5) Coarsening treatment The via hole processing substrate with the laser via hole formed in the insulating layer is subjected to desmear treatment as a roughening treatment. In addition, the desmear treatment was performed by the following wet desmear treatment.

Wet degreaser treatment: In a swelling solution (“Swelling Dip Securiganth P” manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60° C. for 10 minutes, and then immersed in an oxidizing agent solution (“Concentrate” manufactured by Atotech Japan) Compact CP", an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%), immersed at 80°C for 20 minutes, and finally immersed in a neutralizing solution ("Reduction solution Securiganth P" manufactured by Atotech Japan, sulfuric acid) water solution), immersed at 40°C for 5 minutes, and then dried at 80°C for 15 minutes. This serves as the roughened substrate A.

(6) Dimensional measurement of guide hole after roughening treatment The roughened substrate A was used as a sample. About this roughened board|substrate A, the cross-sectional observation was performed using the FIB-SEM composite apparatus ("SMI3050SE" by SII NanoTechnology company). In detail, using FIB (Focused Ion Beam), the insulating layer is cut in parallel in the thickness direction of the insulating layer and in such a way that a cross-section passing through the center of the bottom of the guide hole of the guide hole occurs. The cross section was observed by SEM (Scanning Electron Microscope), and the diameter of the top of the guide hole and the diameter of the bottom of the guide hole were measured from the observed image.

Five pilot holes were selected unintentionally for the aforementioned measurement. Then, use the average of the measured values of the top diameters of the guide holes at 5 places as the top diameter Lt of the guide holes of the sample, and use the measured values of the bottom diameters of the guide holes at the 5 places. The average is used as the bottom diameter Lb of the guide hole of the sample.

(7) Dimensional measurement of white edge distance after roughening treatment About the roughened board|substrate A, cross-sectional observation was performed using the FIB-SEM composite apparatus (SII NanoTechnology company make "SMI3050SE"). In detail, using FIB (Focused Ion Beam), the insulating layer is cut in parallel in the thickness direction of the insulating layer and in such a manner that a cross-section passing through the center of the bottom of the guide hole of the guide hole occurs. This cross-section was observed by SEM (scanning electron microscope), and as a result of the observation, the edge of the bottom of the via hole was continuous, and a gap formed by peeling off the insulating layer from the copper foil layer of the inner substrate was observed. From the observed image, determine the distance from the center of the bottom of the guide hole to the edge of the bottom of the guide hole (equivalent to the inner circumference radius of the white edge) r3, and the distance from the center of the bottom of the guide hole to the far side of the gap. The distance to the end (equivalent to the surrounding radius of the white edge) r4, the difference r4-r3 between the distance r3 and the distance r4 is calculated from the white edge distance of the edge of the bottom of the pilot hole at the measurement point.

Five pilot holes were not deliberately selected for the aforementioned measurement. Then, the average of the measured values of the white edge distances of the five guide holes measured is used as the white edge distance Wb of the edge of the bottom of the guide hole of the sample.

Using the values of the via bottom diameter Lb and the margin distance Wb, the margin ratio Hb is calculated. The white edge ratio Hb after roughening treatment is the ratio "Wb" between the white edge distance Wb of the edge of the bottom of the guide hole after the roughening treatment and the radius (Lb/2) of the bottom of the guide hole after the roughening treatment /(Lb/2)”. When the white border ratio Hb was 35% or less, the evaluation of the white border suppression was "○", and when the white border ratio Hb was more than 35%, the evaluation of the white border suppression was "x".

<Reference Example 1: Production of Resin Sheet a with Support> Using the resin composition 1 prepared in Preparation Example 1, in the same manner as in Comparative Example 1, a resin sheet a with a support having one resin composition layer was produced.

<Reference example 2: Production of resin sheet b with support> A resin sheet b with a support was produced in the same manner as in Reference Example 1, except that the resin composition 2 prepared in Preparation Example 2 was used instead of the resin composition 1 prepared in Preparation Example 1.

<Reference example 3: Production of resin sheet c with support> A resin sheet c with a support was produced in the same manner as in Reference Example 1, except that the resin composition 3 prepared in Preparation Example 3 was used in place of the resin composition 1 prepared in Preparation Example 1.

<Reference Example 4: Production of Resin Sheet d with Support> A resin sheet d with a support was produced in the same manner as in Reference Example 1, except that the resin composition 4 prepared in Preparation Example 4 was used in place of the resin composition 1 prepared in Preparation Example 1.

<Reference Example 5: Production of Resin Sheet e with Support> A resin sheet e with a support was produced in the same manner as in Reference Example 1, except that the resin composition 5 prepared in Preparation Example 5 was used in place of the resin composition 1 prepared in Preparation Example 1.

<Reference Example 6: Production of Resin Sheet f with Support> A resin sheet f with a support was produced in the same manner as in Reference Example 1, except that the resin composition 6 prepared in Preparation Example 6 was used in place of the resin composition 1 prepared in Preparation Example 1.

<Reference Example 7: Production of Resin Sheet g with Support> A resin sheet g with a support was produced in the same manner as in Reference Example 1, except that the resin composition 7 prepared in Preparation Example 7 was used instead of the resin composition 1 prepared in Preparation Example 1.

<Reference Example 8: Production of Resin Sheet h with Support> A resin sheet h with a support was produced in the same manner as in Reference Example 1, except that the resin composition 8 prepared in Preparation Example 8 was used instead of the resin composition 1 prepared in Preparation Example 1.

<Reference Example 9: Production of Resin Sheet i with Support> A resin sheet i with a support was produced in the same manner as in Reference Example 1, except that the resin composition 10 prepared in Preparation Example 9 was used instead of the resin composition 1 prepared in Preparation Example 1.

<Reference Example 10: Production of Resin Sheet j with Support> A resin sheet j with a support was produced in the same manner as in Reference Example 1, except that the resin composition 11 prepared in Preparation Example 10 was used instead of the resin composition 1 prepared in Preparation Example 1.

<Reference Example 11: Production of Resin Sheet k with Support> A resin sheet k with a support was produced in the same manner as in Reference Example 1, except that the resin composition 12 prepared in Preparation Example 11 was used instead of the resin composition 1 prepared in Preparation Example 1.

<Reference Example 12: Production of Resin Sheet 1 with Support> A resin sheet 1 with a support was produced in the same manner as in Reference Example 1, except that the resin composition 13 prepared in Preparation Example 12 was used instead of the resin composition 1 prepared in Preparation Example 1.

<Reference Example 13: Production of Resin Sheet m with Support> A resin sheet m with a support was produced in the same manner as in Reference Example 1, except that the resin composition 14 prepared in Preparation Example 13 was used instead of the resin composition 1 prepared in Preparation Example 1.

<Reference Test Example 1: Measurement of Elastic Modulus> The untreated surface of the mold-releasing PET film ("501010" manufactured by Lintec Co., Ltd., thickness 38 μm, 240 mm corner) was contacted with a glass cloth base epoxy resin double-sided copper-clad laminate ("R5715ES" manufactured by Matsushita Electric Co., Ltd., thickness 0.7 mm) , 255mm angle), set on the glass cloth base epoxy resin double-sided copper laminated board, and the four sides of the mold release PET film are fixed with polyimide adhesive tape (width 10mm).

Using a batch-type vacuum pressure laminator (manufactured by Nikko-materials, 2-stage build-up laminator, CVP700), the resin sheet (167×107 mm angle) with a support prepared in each reference example was used to make the second resin composition. The material layer is in contact with the release surface of the release PET film, and the lamination process is performed in the center. The lamination process was carried out by pressure-bonding at 100° C. and a pressure of 0.74 MPa for 30 seconds after reducing the pressure for 30 seconds to make the air pressure 13 hPa or less.

Next, the support was peeled off, and the resin sheet layer was thermally cured under curing conditions of 190° C. for 90 minutes.

After thermal hardening, the polyimide adhesive tape was peeled off, and the epoxy resin on both sides of the glass cloth substrate was pasted with a copper laminate to remove the hardened layer. Furthermore, from the hardened layer, the mold release PET film was peeled off to obtain a sheet-like hardened product (hardened product for evaluation).

The cured product for evaluation was cut into a dumbbell-shaped No. 1 shape to obtain a test piece. This test piece was subjected to a tensile test of the cured product for evaluation using a Tensilon universal testing machine (manufactured by A&D Corporation) in accordance with Japanese Industrial Standards (JIS K7127), and the elastic modulus at 23°C was measured. This operation was performed three times, and the respective average values were calculated and shown in Table 1.

<Reference Test Example 2: Measurement of Specific Capacitance and Dielectric Tangent> Using a batch vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.), the resin sheets with supports produced in each reference example were laminated on a laminate plate (MCL-E-700G manufactured by Hitachi Chemical Co., Ltd.). copper foil etching). The lamination system was decompressed for 30 seconds, the air pressure was set to 13 hPa or less, and pressure-bonding was performed at 120° C. for 30 seconds and a pressure of 0.74 MPa. Then, the PET film was peeled off, and the resin composition layer was cured under curing conditions of 190° C. and 90 minutes to obtain a cured product sample.

The cured product sample was cut into test pieces having a width of 2 mm and a length of 80 mm. For this test piece, the specific capacitance and the dielectric tangent were measured by the resonance cavity perturbation method using "HP8362B" manufactured by Agilent Technologies, at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Three test pieces were measured, and the average value was calculated and shown in Table 1.

式(5)中，t ₁係第1樹脂組成物層之厚度(μm)，t ₂係第2樹脂組成物層之厚度(μm)，d ₁係由第1樹脂組成物層所形成之第1硬化層之介電正切，d ₂係由第2樹脂組成物層所形成之第2硬化層之介電正切。 <Test Example 2: Evaluation of the dielectric tangent of the entire hardened layer (insulating layer)> The dielectric tangent of the hardened layer calculated in Reference Test Example 2 obtained from the hardening of each resin composition layer used in Examples and Comparative Examples and Examples And the thickness of each resin composition layer in a comparative example, the dielectric tangent _dall of the whole hardened layer (insulation layer) which consists of two layers of a 1st hardened layer and a 2nd hardened layer was calculated according to the following formula.

In formula (5), _t1 is the thickness (μm) of the first resin composition layer, _t2 is the thickness (μm) of the second resin composition layer, and d1 is the thickness of the _first resin composition layer formed by the first resin composition layer. 1 is the dielectric tangent of the hardened layer, and d ₂ is the dielectric tangent of the second hardened layer formed by the second resin composition layer.

When the dielectric tangent d _all of the entire hardened layer (insulating layer) is 0.0055 or less, the evaluation of low dielectric tangent is judged as "○", and when the dielectric tangent d _all of the entire hardened layer (insulating layer) is greater than 0.0055, low dielectric tangent The evaluation of the dielectric tangent was judged as "X".

The usage amount of the raw materials of the resin compositions of the Examples and Comparative Examples, the thickness of the resin composition layer, the measurement results, calculation results and evaluation results of the test examples and reference test examples are shown in Table 1 below.

As shown in Table 1, in Comparative Example 2 of the hardened layer monolayer which can suppress the white fringing phenomenon, there is a problem of high dielectric tangent, while in Comparative Example 1 of the hardened layer monolayer with low dielectric tangent, white fringing occurs. obvious. In addition, in Comparative Example 3 which does not satisfy the condition (3) with two hardened layers, and Comparative Example 5 which does not satisfy the condition (1) with two hardened layers, the occurrence of white fringing can be suppressed, but there are two hardened layers. The problem of the overall high dielectric tangent is that in Comparative Example 4 of the second hardened layer which does not satisfy the condition (2), the dielectric tangent of the entire second hardened layer is low, but the occurrence of white edges is remarkable. On the other hand, when the resin composition of this invention which satisfies all conditions (1)-(3) is used, it turns out that these problems can be overcome.

1: Resin sheet with support 2: resin sheet layer 3: Support body 10: First resin composition layer 10': 1st hardened layer 20: Second resin composition layer 20': 2nd hardened layer 100: Insulation layer 100U: The surface of the insulating layer on the opposite side of the conductor layer 110: Pilot hole 120: Bottom of guide hole 120C: The center of the bottom of the guide hole 130: top of guide hole 140: Discoloration Department 150: The edge of the bottom of the guide hole of the guide hole 160: Clearance Department 170: End of the peripheral side of the gap 180: The edge of the top of the guide hole 190: The edge part of the surrounding side of the discolored part 200: Inner substrate 210: Conductor layer Lb: The bottom diameter of the guide hole Lt: The top diameter of the guide hole of the guide hole Wb: White edge distance from the bottom edge of the via hole Wt: White edge distance from the top edge of the via hole

1 is a cross-sectional view schematically showing a resin sheet with a support according to an embodiment of the present invention. [ Fig. 2] Fig. 2 is a cross-sectional view schematically showing an insulating layer obtained by curing a resin sheet layer of the resin sheet with a support according to one embodiment of the present invention together with an inner layer substrate. 3 is a plan view schematically showing the surface opposite to the conductor layer of the insulating layer obtained by curing the resin sheet layer of the support-attached resin sheet according to one embodiment of the present invention. 4 is a cross-sectional view schematically showing an insulating layer after a roughening treatment obtained by curing a resin sheet layer of a resin sheet with a support according to an embodiment of the present invention together with an inner layer substrate.

Claims (20)

A resin sheet with a support, which is provided with a support, and a resin sheet with a support provided on a resin sheet layer on the support, wherein the resin sheet layer is composed of a first resin in order from the side of the support The first resin composition layer formed by the material and the second resin composition layer formed by the second resin composition having a different composition from the first resin composition, the thickness of the first resin composition layer is set as t ₁ ( μm), the thickness of the second resin composition layer is set to t ₂ (μm), and the elastic modulus (measurement temperature 23° C.) of the first hardened layer formed by curing the first resin composition layer at 190° C. for 90 minutes is set to is y ₁ (GPa), the elastic modulus (measurement temperature 23° C.) of the second hardened layer formed by curing the second resin composition layer at 190° C. for 90 minutes is set to y ₂ (GPa), and the first hardened layer is When the dielectric tangent (measurement frequency of 5.8 GHz, measurement temperature of 23° C.) is set as d ₁ and the dielectric tangent of the second hardened layer (measurement frequency of 5.8 GHz, measurement temperature of 23° C.) is set to d ₂ , all of the following formulas are satisfied ( 1), (2) and (3) conditions,

. The resin sheet with a support according to claim 1, wherein the second resin composition contains (A) a thermosetting resin. The resin sheet with a support according to claim 1, wherein the first resin composition and the second resin composition each contain (B) an inorganic filler. The resin sheet with a support according to claim 3, wherein the content rate (mass %) of the (B) inorganic filler in the second resin composition is relative to the content rate (B) of the inorganic filler in the first resin composition The ratio (2nd resin composition/1st resin composition) of (mass %) is 0.30 or less. The resin sheet with a support according to claim 3, wherein the content rate (mass %) of the (B) inorganic filler in the second resin composition is relative to the content rate (B) of the inorganic filler in the first resin composition The ratio (mass %) (2nd resin composition/1st resin composition) is 0.25 or more. The resin sheet with a support according to claim 1, wherein the first resin composition contains (C) a radically polymerizable compound. The resin sheet with a support according to claim 1, wherein in the condition of formula (2), y ₂ /y ₁ is 0.28 or more. The resin sheet with a support according to claim 1, wherein in the condition of formula (3), d ₂ /d ₁ is 4 or less. The resin sheet with a support according to claim 1, wherein in the condition of formula (3), d ₂ /d ₁ is 2 or more. The resin sheet with a support according to claim 9, wherein in the condition of formula (3), d ₂ /d ₁ is 2.5 or more. The resin sheet with a support according to claim 1, wherein the elastic modulus _y1 of the first hardened layer is 11.5GPa or less. The resin sheet with a support according to claim 1, wherein the elastic modulus _y1 of the first hardened layer is 8.5GPa or more. The resin sheet with a support according to claim 1, wherein the elastic modulus y ₂ of the second hardened layer is 3.3 GPa or less. The resin sheet with a support according to claim 1, wherein the dielectric tangent d1 of the _first hardened layer is 0.004 or less. The resin sheet with a support according to claim 1, wherein the dielectric tangent d ₂ of the second hardened layer is 0.008 or less. The resin sheet with support as claimed in claim 1, wherein the specific capacitance of the first hardened layer (measurement frequency 5.8GHz, measurement temperature 23°C) is set as p ₁ , and the specific capacitance of the second hardened layer (measurement frequency 5.8GHz) , when the measurement temperature is 23°C) as p ₂ , further, the conditions of the following formula (4) are satisfied,

. The resin sheet with a support according to claim 1, wherein the dielectric tangent d _all of the entire hardened layer composed of two layers of the first hardened layer and the second hardened layer calculated by the following formula (5) is 0.005 the following,

. A hardened product comprising a first hardened layer formed of a hardened product of a first resin composition, and formed on the first hardened layer and formed of a second resin having a composition different from that of the first resin composition For the second hardened layer formed by the hardened product, let the thickness of the first hardened layer be t _1' (μm), the thickness of the second hardened layer be t _2' (μm), and the thickness of the first hardened layer The elastic modulus (measurement temperature at 23°C) is set as y ₁ (GPa), the elastic modulus of the second hardened layer (measurement temperature at 23° C.) is set as y ₂ (GPa), and the dielectric tangent of the first hardened layer ( When the measurement frequency is 5.8 GHz, the measurement temperature is 23° C.) as d ₁ , and the dielectric tangent of the second hardened layer (the measurement frequency is 5.8 GHz and the measurement temperature is 23° C.) is set as d ₂ , all of the following formulas (1′) are satisfied. , (2) and (3) conditions,

. A printed wiring board provided with an insulating layer composed of the cured product of claim 18. A semiconductor device comprising the printed wiring board as claimed in claim 19.

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