Resin sheet with support

Abstract

The objective of this invention is to provide a resin sheet with a support and a cured product capable of suppressing the overall dielectric loss tangent of the cured layer to a low level and suppressing halo phenomena. The solution of this invention is a resin sheet with a support, comprising a support and a resin sheet layer disposed on the support, wherein the resin sheet layer, from the support side, sequentially comprises: a first resin composition layer formed of a first resin composition, and a second resin composition layer formed of a second resin composition different from the first resin composition, and the resin sheet with the support satisfies predetermined conditions.

Description

Technical Field

[0001] This invention relates to resin sheets with supports. It further relates to cured resin sheet layers of the resin sheet with supports, printed wiring boards, and semiconductor devices. Background Technology

[0002] In recent years, the demand for small, high-performance electronic devices such as smartphones and tablets has increased. Consequently, the insulating materials (insulating layers) used in semiconductor packaging in these small electronic devices also require further enhancement in functionality. Such insulating layers are known to include insulating layers formed by curing resin compositions (see, for example, Patent Document 1).

[0003] In recent years, the trend towards thinner and smaller electronic devices has led to a demand for insulating layers with lower dielectric loss tangents. However, when materials with lower dielectric loss tangents are used, the seal is compromised, curing stress tends to accumulate, and the halo effect that occurs after through-holes becomes more pronounced.

[0004] The halo effect refers to the peeling phenomenon that occurs between the insulating layer and the inner substrate around a via. This halo effect typically occurs when the resin around the via deteriorates, and this deteriorated portion is eroded during the roughening process. It should be noted that the aforementioned deteriorated portion is usually observed as a discolored area.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent document 1: Japanese Patent Application Publication No. 2017-008312. Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] The objective of this invention is to provide a resin sheet with a support and a cured product that can suppress the overall dielectric loss tangent of the cured layer to a low level and suppress the halo phenomenon.

[0010] Methods for solving problems

[0011] To solve the aforementioned problems, the inventors conducted in-depth research and discovered that, in a resin sheet with a support having a first resin composition layer and a second resin composition layer, when the ratio of the thickness of each layer, the ratio of the elastic modulus, and the ratio of the dielectric loss tangent are set to meet specified conditions, it is unexpectedly possible to suppress the overall dielectric loss tangent of the cured layer to a low level and to suppress the halo phenomenon, thereby completing the present invention. That is, the present invention includes the following contents.

[0012] [1] A resin sheet with a support body, comprising a support body and a resin sheet layer disposed on the support body, wherein the resin sheet layer sequentially comprises, from the support body side: a first resin composition layer formed of a first resin composition, and a second resin composition layer formed of a second resin composition different from the first resin composition.

[0013] When the thickness of the first resin composition layer is set as t1 (μm), the thickness of the second resin composition layer is set as t2 (μm), 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 y1 (GPa), the elastic modulus of the second cured layer formed by curing the second resin composition layer at 190°C for 90 minutes (measurement temperature 23°C) is set as y2 (GPa), the dielectric loss tangent of the first cured layer (measurement frequency 5.8 GHz, measurement temperature 23°C) is set as d1, and the dielectric loss tangent of the second cured layer (measurement frequency 5.8 GHz, measurement temperature 23°C) is set as d2, all conditions of the following equations (1), (2), and (3) are satisfied.

[0014] 1≤t1 / t2≤10···(1)

[0015] y2 / y1≤0.70···(2)

[0016] 1<d2 / d1···(3)

[0017] [2] The resin sheet with a support body described in [1] above, wherein the second resin composition contains (A) a thermosetting resin;

[0018] [3] The resin sheet with a support body described in [1] or [2] above, wherein the first resin composition and the second resin composition respectively contain (B) inorganic filler material;

[0019] [4] The resin sheet with support described in [3] above, wherein the ratio of the content (mass%) of the inorganic filler material (B) in the second resin composition to the content (mass%) of the inorganic filler material (B) in the first resin composition (second resin composition / first resin composition) is 0.30 or less;

[0020] [5] The resin sheet with support described in [3] or [4] above, wherein the ratio of the content (mass%) of the inorganic filler material (B) in the second resin composition to the content (mass%) of the inorganic filler material (B) in the first resin composition (second resin composition / first resin composition) is 0.25 or more;

[0021] [6] The resin sheet with a support body as described in any one of [1] to [5] above, wherein the first resin composition contains a (C) free radical polymerizable compound;

[0022] [7] The resin sheet with a support body as described in any one of [1] to [6] above, wherein, under the conditions of formula (2), y2 / y1 is 0.28 or more;

[0023] [8] The resin sheet with a support body described in any one of [1] to [7] above, wherein, under the conditions of formula (3), d2 / d1 is 4 or less;

[0024] [9] The resin sheet with a support body as described in any one of [1] to [8] above, wherein, under the conditions of formula (3), d2 / d1 is 2 or more;

[0025]

[10] The resin sheet with a support body described in [9] above, wherein, under the conditions of formula (3), d2 / d1 is 2.5 or more;

[0026]

[11] The resin sheet with a support body as described in any one of [1] to

[10] above, wherein the elastic modulus y1 of the first cured layer is 11.5 GPa or less;

[0027]

[12] The resin sheet with a support body as described in any one of [1] to

[11] above, wherein the elastic modulus y1 of the first cured layer is 8.5 GPa or more;

[0028]

[13] The resin sheet with a support body as described in any one of [1] to

[12] above, wherein the elastic modulus y2 of the second cured layer is 3.3 GPa or less;

[0029]

[14] The resin sheet with a support body as described in any one of [1] to

[13] above, wherein the dielectric loss tangent d1 of the first cured layer is 0.004 or less;

[0030]

[15] The resin sheet with a support body as described in any one of [1] to

[14] above, wherein the dielectric loss tangent d2 of the second cured layer is 0.008 or less;

[0031]

[16] The resin sheet with a support body described in any one of [1] to

[15] above, wherein when the relative permittivity of the first cured layer (measurement frequency 5.8 GHz, measurement temperature 23 °C) is set to p1 and the relative permittivity of the second cured layer (measurement frequency 5.8 GHz, measurement temperature 23 °C) is set to p2, further satisfies the condition of the following formula (4).

[0032] p2 / p1<1···(4)

[0033]

[17] The resin sheet with a support body described in any one of [1] to

[16] above, wherein the dielectric loss tangent d of the entire curing layer consisting of the first curing layer and the second curing layer is calculated by the following formula (5). all Below 0.005

[0034] d all =d1×t1 / (t1+t2)+d2×t2 / (t1+t2)···(5)

[0035]

[18] A cured material having:

[0036] The first cured layer formed by the cured product of the first resin composition, and

[0037] A second cured layer is formed on the first cured layer by a cured product of a second resin composition having a different composition from the first resin composition.

[0038] Let the thickness of the first cured layer be t. 1' (μm), set the thickness of the second curing layer to t. 2' When the elastic modulus of the first cured layer (measurement temperature 23℃) is set as y1 (GPa), the elastic modulus of the second cured layer (measurement temperature 23℃) is set as y2 (GPa), the dielectric loss tangent of the first cured layer (measurement frequency 5.8GHz, measurement temperature 23℃) is set as d1, and the dielectric loss tangent of the second cured layer (measurement frequency 5.8GHz, measurement temperature 23℃) is set as d2, all conditions of the following equations (1'), (2) and (3) are satisfied.

[0039] 1≤t 1' / t 2' ≤10···(1')

[0040] y2 / y1≤0.70···(2)

[0041] 1<d2 / d1···(3)

[0042]

[19] A printed wiring board having an insulating layer formed from the cured material described above

[18] ;

[0043]

[20] A semiconductor device comprising the printed wiring board described above

[19] .

[0044] Invention Effects

[0045] According to the present invention, a resin sheet with a support and a cured product can be provided that can suppress the overall dielectric loss tangent of the cured layer to a low level and suppress the halo phenomenon. Attached Figure Description

[0046] Figure 1 This is a schematic cross-sectional view of a resin sheet with a support body according to one embodiment of the present invention;

[0047] Figure 2 This is a schematic cross-sectional view showing an insulating layer and an inner substrate obtained by curing a resin sheet with a support, according to one embodiment of the present invention.

[0048] Figure 3 This is a schematic plan view of the side opposite to the conductor layer of an insulating layer obtained by curing a resin sheet with a support, according to an embodiment of the present invention.

[0049] Figure 4 This is a schematic cross-sectional view showing both the roughened insulating layer and the inner substrate of a resin sheet with a support, obtained by curing the resin sheet layer, according to one embodiment of the present invention. Detailed Implementation

[0050] The present invention will now be described in detail with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples listed below, and may be implemented with optional modifications without departing from the scope of the claims and their equivalents.

[0051] [Resin sheet with support]

[0052] The resin sheet with a support of the present invention comprises a support and a resin sheet layer disposed on the support. The resin sheet layer, from the support side, sequentially comprises: a first resin composition layer formed of a first resin composition, and a second resin composition layer formed of a second resin composition different from the first resin composition.

[0053] Hereinafter, the first resin composition and the second resin composition will sometimes be referred to collectively as the "resin composition", and the first resin composition layer and the second resin composition layer will sometimes be referred to collectively as the "resin composition layer".

[0054] Figure 1 The diagram shows a schematic cross-sectional view of an example of a resin sheet with a support according to the present invention. The resin sheet 1 with a support 1 of the present invention includes a support 3 and a resin sheet layer 2. The resin sheet layer 2 sequentially includes a first resin composition layer 10 and a second resin composition layer 20 from the support 3 side. The resin sheet layer 2 may include additional layers between the first resin composition layer 10 and the second resin composition layer 20, but preferably only includes the first resin composition layer and the second resin composition layer.

[0055] <Resin Composition Layer>

[0056] The types and / or proportions of the components of the first resin composition layer formed by the first resin composition and the second resin composition layer formed by the second resin composition are different, thereby satisfying all the conditions (1), (2) and (3) described below.

[0057] As condition (1), when the thickness of the first resin composition layer is set to t1 (μm) and the thickness of the second resin composition layer is set to t2 (μm), the resin composition layer satisfies the following condition (1):

[0058] 1≤t1 / t2≤10···(1).

[0059] In the conditions of formula (1), from the viewpoint of obtaining the desired effect of the present invention more significantly, t1 / t2 is preferably 2 or more, more preferably 3 or more, particularly preferably 4 or more, and the upper limit is preferably 9 or less, more preferably 8 or less, further preferably 7 or less, particularly preferably 6 or less.

[0060] As condition (2), when the elastic modulus (measured at 23°C) of the first cured layer formed by curing the first resin composition layer at 190°C for 90 minutes is set as y1 (GPa), and the elastic modulus (measured at 23°C) of the second cured layer formed by curing the second resin composition layer at 190°C for 90 minutes is set as y2 (GPa), the resin composition layer satisfies the following condition (2):

[0061] y2 / y1≤0.70···(2).

[0062] In the conditions of formula (2), from the viewpoint of obtaining the desired effect of the present invention more significantly, y2 / y1 is preferably 0.60 or less, more preferably 0.50 or less, further preferably 0.45 or less, particularly preferably 0.40 or less, and the lower limit is preferably 0.10 or more, more preferably 0.20 or more, further preferably 0.25 or more, particularly preferably 0.28 or more.

[0063] It should be noted that the elastic modulus y1 of the first cured layer and the elastic modulus y2 of the second cured layer can be determined, for example, by the method described in the following reference test example 1.

[0064] As condition (3), when the dielectric loss 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 as d1, and the dielectric loss tangent of the second cured layer formed by curing the second resin composition layer at 190°C for 90 minutes (measurement frequency 5.8 GHz, measurement temperature 23°C) is set as d2, the resin composition layer satisfies the following condition (3):

[0065] 1<d2 / d1···(3).

[0066] In the conditions of formula (3), from the viewpoint of obtaining the desired effect of the present invention more significantly, d2 / d1 is preferably 1.5 or more, more preferably 2 or more, further preferably 2.5 or more, particularly preferably 3 or more, and the upper limit is preferably 10 or less, more preferably 7 or less, further preferably 5 or less, particularly preferably 4 or less.

[0067] It should be noted that the dielectric loss tangent d1 of the first cured layer and the dielectric loss tangent d2 of the second cured layer can be determined, for example, by the method described in the following reference test example 2.

[0068] From the viewpoint of achieving the desired effect of the present invention more significantly, the thickness t1 of the first resin composition layer is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less, with the lower limit preferably being 1 μm or more, more preferably 10 μm or more, and even more preferably 20 μm or more.

[0069] From the viewpoint of achieving the desired effect of the present invention more significantly, the thickness t2 of the second resin composition layer is preferably 50 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less, with the lower limit preferably being 0.1 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more.

[0070] From the viewpoint of achieving the desired effect of the present invention more significantly, the total 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, and even more preferably 40 μm or less, with the lower limit preferably being 1 μm or more, more preferably 10 μm or more, and even more preferably 20 μm or more.

[0071] From the viewpoint of achieving the desired effect of the present invention more significantly, the elastic modulus y1 (measured at 23°C) of the first cured layer formed by curing the first resin composition layer at 190°C for 90 minutes is preferably 5.0 GPa or more, more preferably 7.0 GPa or more, further preferably 8.0 GPa or more, particularly preferably 8.5 GPa or more, and the upper limit is preferably 20.0 GPa or less, 17.0 GPa or less, more preferably 15.0 GPa or less, 14.0 GPa or less, further preferably 13.0 GPa or less, 12.0 GPa or less, and particularly preferably 11.5 GPa or less.

[0072] From the viewpoint of achieving the desired effect of the present invention more significantly, the elastic modulus y2 (measured at 23°C) of the second cured layer formed by curing the second resin composition layer at 190°C for 90 minutes is preferably 1.0 GPa or more, more preferably 2.0 GPa or more, further preferably 2.5 GPa or more, particularly preferably 3.0 GPa or more, and the upper limit is preferably 10.0 GPa or less, more preferably 7.0 GPa or less, 5.0 GPa or less, further preferably 4.0 GPa or less, 3.7 GPa or less, particularly preferably 3.5 GPa or less, or 3.3 GPa or less.

[0073] From the viewpoint of achieving the desired effect of the present invention more significantly, the dielectric loss tangent d1 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 preferably 0.010 or less, 0.009 or less, more preferably 0.008 or less, 0.007 or less, even more preferably 0.006 or less, 0.005 or less, even more preferably 0.004 or less, and particularly preferably 0.003 or less.

[0074] From the viewpoint of achieving the desired effect of the present invention more significantly, the dielectric loss tangent d2 of the second cured layer formed by curing the second resin composition layer at 190°C for 90 minutes (measurement frequency 5.8 GHz, measurement temperature 23°C) is preferably 0.030 or less, 0.020 or less, more preferably 0.018 or less, 0.016 or less, even more preferably 0.014 or less, 0.012 or less, even more preferably 0.010 or less, and particularly preferably 0.008 or less.

[0075] 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 overall dielectric loss tangent of the cured layer can be suppressed to a low level, and the halo phenomenon can be suppressed.

[0076] When the relative permittivity (measurement frequency 5.8 GHz, measurement temperature 23 ℃) of the first cured layer formed by curing the first resin composition layer at 190 ℃ for 90 minutes is set as p1, and the relative permittivity (measurement frequency 5.8 GHz, measurement temperature 23 ℃) of the second cured layer formed by curing the second resin composition layer at 190 ℃ for 90 minutes is set as p2, the first resin composition layer formed from the first resin composition and the second resin composition layer formed from the second resin composition preferably satisfy, in addition to satisfying the above conditions (1), (2) and (3), the condition of formula (4) is further satisfied:

[0077] p2 / p1<1···(4).

[0078] In the conditions of formula (4), the lower limit of p2 / p1 is preferably 0.7 or more, more preferably 0.8 or more, further preferably 0.85 or more, and particularly preferably 0.9 or more. The upper limit of p2 / p1 is preferably 0.98 or less, and particularly preferably 0.95 or less.

[0079] It should be noted that the relative permittivity p1 of the first cured layer and the relative permittivity p2 of the second cured layer can be determined, for example, by the method described in the following reference test example 2.

[0080] From the viewpoint of achieving the desired effect of the present invention more significantly, the relative permittivity p1 (measured at a frequency of 5.8 GHz and a measurement temperature of 23 °C) of the first cured layer formed by curing the first resin composition layer at 190 °C for 90 minutes is preferably 4.0 or less, 3.9 or less, more preferably 3.8 or less, 3.7 or less, even more preferably 3.6 or less, 3.5 or less, even more preferably 3.4 or less, and particularly preferably 3.3 or less.

[0081] From the viewpoint of achieving the desired effect of the present invention more significantly, the relative permittivity p2 of the second cured layer formed by curing the second resin composition layer at 190°C for 90 minutes (measurement frequency 5.8 GHz, measurement temperature 23°C) is preferably 4.0 or less, 3.8 or less, more preferably 3.7 or less, 3.5 or less, further preferably 3.4 or less, 3.3 or less, further more preferably 3.2 or less, 3.1 or less, and particularly preferably 3.0 or less.

[0082] 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 component selected from (A) thermosetting resin, (B) inorganic filler, (C) free radical polymerizable compound, (D) free radical polymerization initiator, (E) thermoplastic resin, (F) curing accelerator, (G) other additives, and (H) organic solvent. Those skilled in the art can appropriately adjust the ratio of the elastic modulus and the ratio of the dielectric loss tangent (and optionally the ratio of the relative permittivity) of the two cured layers formed by each resin composition layer by selecting and changing the content of these components, and can set them within the range of conditions (2) and (3) above (and optionally within the range of condition (4) above). The components contained in the resin composition will be described in detail below.

[0083] <(A) Thermosetting Resins>

[0084] Both 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 capable of being used as an insulating layer or other insulating component when the cured layer of the resin composition is cured can be used. Examples of (A) thermosetting resins include, for example, epoxy resins, epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate ester resins, polyimide resins, benzoxazine resins, unsaturated polyester resins, phenolic resins, melamine resins, and silicone resins.

[0085] <(A-1) Epoxy Resin>

[0086] The first resin composition and the second resin composition may each 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 epoxy groups.

[0087] Examples of (A-1) epoxy resins include, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, and naphthol phenolic varnish. Epoxy resins include novolac type, phenolnovolac type, tert-butylcatechol type, naphthalene type, naphthol type, anthracene type, glycidylamine type, glycidyl ester type, cresolnovolac type, biphenyl type, linear aliphatic epoxy resin, butadiene-based epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spirocyclic epoxy resin, cyclohexane type, cyclohexanediol type, naphthylene ether type, tris(hydroxymethyl) type, and tetraphenylethane type, etc. Epoxy resins can be used alone or in combination of two or more.

[0088] The first resin composition and the second resin composition preferably each contain an epoxy resin having two or more epoxy groups in one molecule as the (A-1) epoxy resin. From the viewpoint of significantly obtaining the desired effect of the present invention, the proportion of epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, relative to 100% by mass of the non-volatile component of the (A-1) epoxy resin.

[0089] (A-1) The epoxy resin includes an epoxy resin that is liquid at 25°C (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at 25°C (hereinafter sometimes referred to as "solid epoxy resin"). In the first resin composition and the second resin composition, the epoxy resin (A-1) may consist only of solid epoxy resin, may consist only of liquid epoxy resin, or may consist of a combination of liquid epoxy resin and solid epoxy resin.

[0090] As a liquid epoxy resin, it is preferred to be a liquid epoxy resin having two or more epoxy groups in one molecule.

[0091] As liquid epoxy resins, preferred types include GLYCIROL 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, phenolic varnish type epoxy resin, alicyclic epoxy resin with an ester skeleton, cyclohexanediol type epoxy resin, cyclic aliphatic glycidyl ether, and epoxy resin with a butadiene structure. More preferred types include GLYCIROL type epoxy resin, cyclic aliphatic glycidyl ether, bisphenol A type epoxy resin, and bisphenol F type epoxy resin.

[0092] Specific examples of liquid epoxy resins include: DIC's "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin); Mitsubishi Chemical's "828US", "jER828EL" (bisphenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), and "jER152" (phenolic varnish type epoxy resin); Mitsubishi Chemical's "630" and "630LSD"; ADEKA's "ED-523T" (GLYCIROL type epoxy resin (ADEKA GLYCIROL)), "EP-3980S" (glycidylamine type epoxy resin), and "EP-4088S" (dicyclopentadiene type epoxy resin); Nippon Steel Chemical Materials Co., Ltd.'s "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase... ChemteX's "EX-721" (glycidyl ester type epoxy resin); Daicel's "Celloxide 2021P" (alicyclic epoxy resin with ester skeleton) and "PB-3600" (epoxy resin with butadiene structure); Nippon Steel Chemical Materials' "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane); and Nagase ChemteX's "EX-201" (cyclic aliphatic glycidyl ether), etc.

[0093] As a solid epoxy resin, it is preferred to be a solid epoxy resin having three or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule.

[0094] As solid epoxy resins, the preferred types are xylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, naphthol phenolic varnish-type epoxy resins, cresol phenolic varnish-type epoxy resins, dicyclopentadiene-type epoxy resins, triphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthyl ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, phenol aralkyl-type epoxy resins, tetraphenylethane-type epoxy resins, phenol benzopyrrolidone (phenolphthalimidine)-type epoxy resins, and phenolphthalein-type epoxy resins.

[0095] Specific examples of solid epoxy resins include: DIC's "HP4032H" (naphthalene-type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins); DIC's "N-690" (cresol phenolic varnish type epoxy resin); DIC's "N-695" (cresol phenolic varnish type epoxy resin); DIC's "HP-7200," "HP-7200HH," "HP-7200H," and "HP-7200L" (dicyclopentadiene type epoxy resin); D IC Corporation's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", and "HP6000" (naphthalene ether type epoxy resin); Nippon Kayaku Co., Ltd.'s "EPPN-502H" (triphenol type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC7000L" (naphthalene phenolic varnish type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC3000H", "NC3000", "NC3000L", "NC3000FH", and "NC3100" (biphenyl type epoxy resin) Resins); JITAC Chemical Materials Co., Ltd.'s "ESN475V" (naphthalene-type epoxy resin); JITAC Chemical Materials Co., Ltd.'s "ESN485" (naphthol-type epoxy resin); JITAC Chemical Materials Co., Ltd.'s "ESN375" (dihydroxynaphthalene-type epoxy resin); Mitsubishi Chemical Corporation's "YX4000H", "YX4000", "YX4000HK", "YL7890" (bi-xylenol-type epoxy resin); Mitsubishi Chemical Corporation's "YL6121" (biphenyl-type epoxy resin); Mitsubishi Chemical Corporation's "YX8800" (anthracite-type epoxy resin); The following epoxy resins are used: Mitsubishi Chemical Co., Ltd.'s "YX7700" (phenolic aralkyl type epoxy resin); Osaka Gas Chemical Co., Ltd.'s "PG-100" and "CG-500"; Mitsubishi Chemical Co., Ltd.'s "YL7760" (bisphenol AF type epoxy resin); Mitsubishi Chemical Co., Ltd.'s "YL7800" (fluorene type epoxy resin); Mitsubishi Chemical Co., Ltd.'s "jER1010" (bisphenol A type epoxy resin); Mitsubishi Chemical Co., Ltd.'s "jER1031S" (tetraphenylethane type epoxy resin); and Nippon Kayaku Co., Ltd.'s "WHR991S" (phenolic benzopyrrolidone type epoxy resin), etc. They can be used individually or in combination of two or more.

[0096] When liquid epoxy resin and solid epoxy resin are used in combination as (A-1) epoxy resin, their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 20:1 to 1:20, more preferably 10:1 to 1:10, and particularly preferably 7:1 to 1:7.

[0097] (A-1) The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., even more preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. The epoxy equivalent is the mass of resin per equivalent of epoxy groups. This epoxy equivalent can be determined according to JIS K7236.

[0098] From the viewpoint of significantly achieving the desired effects of the present invention, the weight-average molecular weight (Mw) of the epoxy resin (A-1) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. The weight-average molecular weight of the resin can be determined by gel permeation chromatography (GPC) in the form of a polystyrene equivalent.

[0099] The content (mass%) of (A-1) epoxy resin in the first resin composition is not particularly limited. When the non-volatile component in the first resin composition is set to 100% by mass, from the viewpoint of obtaining the desired effect of the present invention more significantly, it is preferably 50% by mass or less, more preferably 30% by mass or less, particularly preferably 20% by mass or less, and the lower limit is, for example, 0% by mass or more, 0.1% by mass or more, preferably 1% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more.

[0100] The content (mass%) of (A-1) epoxy resin in the second resin composition is not particularly limited. When the non-volatile component in the second resin composition is set to 100% by mass, from the viewpoint of obtaining the desired effect of the present invention more significantly, it is preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less. The lower limit is, for example, 0% by mass or more, 0.1% by mass or more, 1% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more, and particularly preferably 40% by mass or more.

[0101] <(A-2) Epoxy Curing Agent>

[0102] When the first resin composition and the second resin composition each comprise (A-1) epoxy resin as (A) thermosetting resin, they may further comprise (A-2) epoxy curing agent as an optional component. In one embodiment, the first resin composition preferably contains (A-2) epoxy curing agent. In one embodiment, the second resin composition preferably contains (A-2) epoxy curing agent. The (A-2) epoxy curing agent has the function of reacting with the (A-1) epoxy resin to cure the resin composition.

[0103] The epoxy curing agent (A-2) is not particularly limited, and examples include: reactive ester-based curing agents, phenolic curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and thiol-based curing agents. The epoxy curing agent (A-2) can be used alone or in combination of two or more. Preferably, the epoxy curing agent (A-2) includes an epoxy curing agent selected from reactive ester-based curing agents and phenolic curing agents.

[0104] As an active ester-based curing agent, compounds with two or more highly reactive ester groups in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxyamine esters, and heterocyclic hydroxyl compounds, are generally preferred.

[0105] The reactive ester-based curing agent is preferably an reactive ester-based curing agent obtained by the condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxyl compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, reactive ester-based curing agents obtained by reacting a carboxylic acid compound with a hydroxyl compound are preferred, and reactive ester-based curing agents obtained by reacting a carboxylic acid compound with a phenol compound and / or a naphthol compound are more preferred.

[0106] Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenolic or naphthol compounds 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-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, trihydroxybenzene, dicyclopentadiene-type diphenol compounds, and linear phenolic resins. Here, "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by the condensation of 2 phenol molecules and 1 dicyclopentadiene molecule.

[0107] Specifically, the preferred active ester-based curing agent is a dicyclopentadiene-type active ester-based curing agent, a naphthalene-type active ester-based curing agent containing a naphthalene structure, an active ester-based curing agent containing an acetylated linear phenolic resin, or an active ester-based curing agent containing a benzoylated linear phenolic resin. More preferably, it is selected from at least one of dicyclopentadiene-type and naphthalene-type active ester-based curing agents. As a dicyclopentadiene-type active ester-based curing agent, an active ester-based curing agent containing a dicyclopentadiene-type diphenol structure is preferred.

[0108] Commercially available reactive ester-based curing agents include those containing a dicyclopentadiene-type diphenol structure such as "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", and "HPC-8000H-65TM" (manufactured by DIC Corporation); and those containing a naphthalene structure such as "EXB-8151-62T", "EXB-8100L-65T", and "EXB-8150-60T". Examples of active ester curing agents include: “EXB-8150-62T”, “EXB-9416-70BK”, “HPC-8150-60T”, and “HPC-8150-62T” (manufactured by DIC Corporation); examples of phosphorus-containing active ester curing agents include “EXB9401” (manufactured by DIC Corporation); examples of active ester curing agents as acetylated linear phenolic resins include “DC808” (manufactured by Mitsubishi Chemical Corporation); examples of active ester curing agents as benzoylated linear phenolic resins include “YLH1026”, “YLH1030”, and “YLH1048” (manufactured by Mitsubishi Chemical Corporation); and examples of active ester curing agents containing styrene and naphthalene structures include “PC1300-02-65MA” (manufactured by AIRWATER Corporation).

[0109] There are no particular restrictions on phenolic curing agents, but biphenyl-type curing agents, naphthalene-type curing agents, phenolic varnish curing agents, naphthalene ether curing agents, and phenolic curing agents containing a triazine skeleton are preferred. Specific examples include: biphenyl-type curing agents “MEH-7700”, “MEH-7810”, “MEH-7851” (manufactured by Meiwa Kasei Corporation); naphthalene-type curing agents “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); phenolic varnish curing agent “TD2090” (manufactured by DIC Corporation); and naphthalene ether curing agent “EXB-6000” (manufactured by DIC Corporation). Specific examples of phenolic curing agents containing a triazine skeleton include "LA3018", "LA7052", "LA7054", and "LA1356" (manufactured by DIC). In particular, naphthalene-type curing agents and phenolic curing agents containing a triazine skeleton are more suitable.

[0110] As a carbodiimide-based curing agent, examples include curing agents having one or more, preferably two or more, carbodiimide structures in one molecule. Examples include aliphatic bis(tert-butylcarbodiimide) and cyclohexanebis(methylene-tert-butylcarbodiimide); aromatic bis(xylylcarbodiimide) and other bis(carbodiimide); and aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylcarbodiimide, poly(methylene biscyclohexylcarbodiimide), and poly(isophoronecarbodiimide). Imines; poly(phenylene carbodiimide), poly(naphthylcarbodiimide), poly(tolylcarbodiimide), poly(methyldiisopropylphenylene carbodiimide), poly(triethylphenylene carbodiimide), poly(diethylphenylene carbodiimide), poly(triisopropylphenylene carbodiimide), poly(diisopropylphenylene carbodiimide), poly(xylylene carbodiimide), poly(tetramethylxylylene carbodiimide), poly(methylene diphenylene carbodiimide), poly[methylene bis(methylphenylene)carbodiimide] and other aromatic polycarbodiimides and other polycarbodiimides.

[0111] Commercially available carbodiimide-based curing agents include, for example, "CARBODILITE V-02B", "CARBODILITE V-03", "CARBODILITE V-04K", "CARBODILITE V-07" and "CARBODILITE V-09" manufactured by Nisshinbo Chemical Co., Ltd.; and "Stabaxol P", "Stabaxol P400" and "Hycasyl 510" manufactured by Rhein-Chemie Co., Ltd.

[0112] As an anhydride-based curing agent, examples include curing agents having one or more anhydride groups per molecule, preferably curing agents having two or more anhydride groups per molecule. Specific examples of anhydride-based curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic 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, and diphenyltrioxide. Anhydrides such as benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(dehydrated trimellitate), and styrene-maleic acid resin copolymerized from styrene and maleic acid are examples of polymeric anhydrides. Commercially available anhydride-based curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by Shin Nippon Rikka Co., Ltd.; "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Co., Ltd.; and "HN-2200" and "HN-5500" manufactured by Hitachi Chemical Co., Ltd.

[0113] As amine-based curing agents, examples include curing agents having one or more, preferably two or more, amino groups in one molecule. Examples include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. From the viewpoint of achieving the desired effect of the present invention, aromatic amines are preferred. The amine-based curing agent is preferably a primary or secondary amine, more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybiphenylamine, and 2,2-bis(3-amino-4-hydroxy) 2,2-bis(4-aminophenyl)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, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. Amine-based curing agents can be commercially available, such as SEIKA's "SEIKACURE-S", Nippon Kayaku Co.'s "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", "KAYAHARD AS", and Mitsubishi Chemical's "Epicure W".

[0114] Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0115] Examples of cyanate ester curing agents include, for instance, bisphenol A dicyanate, polyphenol cyanates (oligomeric (3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), 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., difunctional cyanate ester resins, multifunctional cyanate ester resins derived from phenolic varnish resins and cresol varnish resins, and some triazine-modified prepolymers of these cyanate ester resins. Specific examples of cyanate ester-based curing agents include Lonza Japan's "PT30" and "PT60" (both phenolic varnish-type multifunctional cyanate ester resins), "BA230", and "BA230S75" (prepolymers of bisphenol A dicyanate that have been partially or completely triazinized to become trimers).

[0116] Examples of thiol-based curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate.

[0117] (A-2) The reactive base equivalent of the epoxy curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., further preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The reactive base equivalent is the mass of the curing agent per 1 equivalent of reactive base.

[0118] The content (mass%) of the (A-2) epoxy curing agent in the first resin composition is not particularly limited. When the non-volatile component in the first resin composition is set to 100% by mass, from the viewpoint of obtaining the desired effect of the present invention more significantly, it is preferably 40% by mass or less, more preferably 20% by mass or less, particularly preferably 10% by mass or less, and the lower limit is, for example, 0% by mass or more, 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, particularly preferably 3% by mass or more.

[0119] The content (mass%) of (A-2) epoxy curing agent in the second resin composition is not particularly limited. When the non-volatile component in the second resin composition is set to 100% by mass, from the viewpoint of obtaining the desired effect of the present invention more significantly, it is preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less. The lower limit is, for example, 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more.

[0120] <(B) Inorganic filler materials>

[0121] The first resin composition and the second resin composition preferably contain (B) inorganic filler. In one embodiment where the first resin composition or the second resin composition contains (B) inorganic filler, adjusting the content of (B) inorganic filler in the resin composition can be one of the methods for adjusting the elastic modulus of the cured layer.

[0122] Inorganic compounds are used as the inorganic filler material in (B). Examples of inorganic filler materials include: silica, alumina, glass, cordierite, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Silica is particularly suitable. Examples of silica include, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Furthermore, spherical silica is preferred as silica. (B) One type of inorganic filler material can be used alone, or two or more types can be used in combination.

[0123] Commercially available products as (B) inorganic filler materials include, for example: Nippon Steel & Sumitomo Metal Materials Co., Ltd.’s “SP60-05” and “SP507-05”; Admatechs Co., Ltd.’s “YC100C”, “YA050C”, “YA050C-MJE”, and “YA010C”; Denka Co., Ltd.’s “UFP-30”; Tokuyama Co., Ltd.’s “Silfil NSS-3N”, “Silfil NSS-4N”, and “Silfil NSS-5N”; Admatechs Co., Ltd.’s “SC2500SQ”, “SO-C4”, “SO-C2”, and “SO-C1”; etc.

[0124] From the viewpoint of significantly achieving the desired effect of the present invention, (B) the average particle size of the inorganic filler material is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less.

[0125] The average particle size of (B) inorganic filler material can be determined using laser diffraction-scattering based on the Mie scattering theory. Specifically, a laser diffraction-scattering particle size distribution measuring device can be used to prepare a volume-based particle size distribution of the (B) inorganic filler material, and the median diameter can be set as the average particle size for measurement. The sample used for measurement can be prepared by weighing 100 mg of (B) inorganic filler material and 10 g of methyl ethyl ketone into a vial and dispersing it ultrasonically for 10 minutes. Using a laser diffraction-scattering particle size distribution measuring device, the sample is measured with the light source wavelength set to blue and red, and the volume-based particle size distribution of the (B) inorganic filler material is measured in a flow cell. The average particle size, as the median diameter, is calculated from the obtained particle size distribution. Examples of laser diffraction-scattering particle size distribution measuring devices include the "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

[0126] From the viewpoint of significantly achieving the desired effects of the present invention, (B) the specific surface area of ​​the inorganic filler material is preferably 1 m². 2 / g or more, preferably 2m 2 / g or more, preferably 3m 2 / g or more. There is no specific upper limit, but 60mg is preferred. 2 / g or less, 50m 2 / g or less or 40m 2 / g or less. The specific surface area can be obtained according to the BET method, using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech), to adsorb nitrogen gas onto the sample surface, and then calculate the specific surface area using the BET multi-point method.

[0127] From the viewpoint of improving moisture resistance and dispersibility, (B) the inorganic filler material is preferably treated with a surface treatment agent. Examples of surface treatment agents include fluorinated silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. Furthermore, a single surface treatment agent can be used, or two or more can be used in any combination.

[0128] Commercially available surface treatment agents include, for example, "KBM403" (3-epoxypropoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM-4803" (long-chain epoxy silane coupling agent) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0129] From the viewpoint of improving the dispersibility of the inorganic filler material (B), the degree of surface treatment using the surface treatment agent is preferably controlled within a specified range. Specifically, 0.2 to 5 parts by mass of the surface treatment agent is preferably used to surface treat 100 parts by mass of the inorganic filler material (B), preferably 0.2 to 3 parts by mass, and preferably 0.3 to 2 parts by mass.

[0130] The degree of surface treatment using the surface treatment agent can be evaluated by the carbon content per unit surface area of ​​the inorganic filler material (B). From the viewpoint of improving the dispersibility of the inorganic filler material (B), the carbon content per unit surface area of ​​the inorganic filler material (B) is preferably 0.02 mg / m³. 2 The above, and more preferably, is 0.1 mg / m³ 2 The above, and more preferably, is 0.2 mg / m³ 2 That's all. On the other hand, from the viewpoint of suppressing the increase in melt viscosity of the resin varnish and the melt viscosity in the resin sheet layer, 1 mg / m³ is preferred. 2 The following, more preferably, is 0.8 mg / m 2 The following, and more preferably, is 0.5 mg / m². 2 the following.

[0131] The carbon content per unit surface area of ​​the (B) inorganic filler material can be determined after washing the surface-treated (B) inorganic filler material with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the (B) inorganic filler material that has been surface-treated with a surface treatment agent, and ultrasonic washing is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid components, the carbon content per unit surface area of ​​the (B) inorganic filler material can be determined using a carbon analyzer. A carbon analyzer such as the "EMIA-320V" manufactured by Horiba Seisakusho Co., Ltd. can be used.

[0132] The content (mass%) of inorganic filler material (B) in the first resin composition is not particularly limited. When the non-volatile component in the first resin composition is set to 100% by mass, from the viewpoint of obtaining the desired effect of the present invention more significantly, it is preferably 90% by mass or less, more preferably 80% by mass or less, particularly preferably 75% by mass or less, and 73% by mass or less. The lower limits are, for example, 0% by mass or more, 1% by mass or more, 10% by mass or more, 30% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, particularly preferably 60% by mass or more, and 65% by mass or more.

[0133] The content (mass%) of inorganic filler material (B) in the second resin composition is not particularly limited. When the non-volatile component in the second resin composition is set to 100% by mass, from the viewpoint of obtaining the desired effect of the present invention more significantly, it is preferably 80% by mass or less, more preferably 50% by mass or less, particularly preferably 30% by mass or less, and the lower limit is, for example, 0% by 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.

[0134] From the viewpoint of achieving the desired effect of the present invention more significantly, the ratio of the content (mass%) of the inorganic filler (B) in the second resin composition to the content (mass%) of the inorganic filler (B) in the first resin composition (second resin composition / first resin composition) is preferably 1.00 or less, more preferably 0.70 or less, further preferably 0.50 or less, further more preferably 0.40 or less, particularly preferably 0.30 or less, and the lower limit is preferably 0.10 or more, more preferably 0.15 or more, further preferably 0.20 or more, particularly preferably 0.25 or more.

[0135] <(C) Free radical polymerizable compounds>

[0136] The first resin composition and the second resin composition may each contain a (C) radical polymerizable compound. In one embodiment, the first resin composition preferably contains a (C) radical polymerizable compound. One type of (C) radical polymerizable compound may be used alone, or two or more may be used in any combination.

[0137] In one embodiment, (C) the free radical polymerizable compound is a free radical polymerizable compound having an olefinically unsaturated bond. (C) the free radical polymerizable compound is not particularly limited and may have, for example, unsaturated hydrocarbon groups such as allyl, 3-cyclohexenyl, 3-cyclopentenyl, p-vinylphenyl, m-vinylphenyl, o-vinylphenyl; and α,β-unsaturated carbonyl groups such as acryloyl, methacryloyl, and maleimide (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl). Preferably, (C) the free radical polymerizable compound has two or more free radical polymerizable groups in one molecule.

[0138] As (C) radical polymerizable compounds, examples include (meth)acrylic acid-based radical polymerizable compounds, styrene-based radical polymerizable compounds, allyl-based radical polymerizable compounds, maleimide-based radical polymerizable compounds, etc. In one embodiment, the (C) radical polymerizable compound preferably comprises a (meth)acrylic acid-based radical polymerizable compound, a styrene-based radical polymerizable compound, or a maleimide-based radical polymerizable compound.

[0139] (Meth)acrylic acid-based free radical polymerizable compounds are compounds having two or more acryloyl groups and / or methacryloyl groups. Examples of (meth)acrylate free radical polymerizable compounds include: cyclohexane-1,4-diethanol di(meth)acrylate, cyclohexane-1,3-diethanol di(meth)acrylate, tricyclodecane-diethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and other low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylate compounds; dioxanediol di(meth)acrylate, 3,6-dioxane-1,8-dioxanediol di(meth)acrylate, etc. Low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylate compounds such as 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-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, etc.; low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylate compounds such as tri(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, etc.; high molecular weight (molecular weight greater than 1000) acrylate compounds such as (meth)acrylate-modified polyphenylene ether resin, etc. Commercially available (meth)acrylic acid-based free radical polymerizable compounds include, for example: "A-DOG" (dioxanediol diacrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; "DCP-A" (tricyclodecanediethanol diacrylate) and "DCP" (tricyclodecanediethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd.; "KAYARAD R-684" (tricyclodecanediethanol diacrylate) and "KAYARAD R-604" (dioxanediol diacrylate) manufactured by Nippon Kayaku Co., Ltd.; and "SA9000" and "SA9000-111" (methacrylic acid modified polyphenylene ether) manufactured by SABIC Innovative Plastics.

[0140] Styrene-based free radical polymerizable compounds are compounds having two or more vinyl groups directly bonded to aromatic carbon atoms. Examples of styrene-based free radical polymerizable compounds include: low molecular weight (molecular weight less than 1000) styrene-based compounds such as divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl) ether; and high molecular weight (molecular weight greater than 1000) styrene-based compounds such as vinylbenzyl-modified polyphenylene ether resin and styrene-divinylbenzene copolymer. Commercially available styrene-based free radical polymerizable compounds include, for example: "ODV-XET(X03)", "ODV-XET(X04)", and "ODV-XET(X05)" (styrene-divinylbenzene copolymer) manufactured by Nippon Steel Chemical Materials Co., Ltd., and "OPE-2St 1200" and "OPE-2St 2200" (vinyl benzyl modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0141] Allyl-based free radical polymerizable compounds are compounds having two or more allyl groups. Examples of allyl-based free radical polymerizable compounds include: diallyl biphenylate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, and diallyl 2,3-naphthalenedicarboxylate, etc., aromatic carboxylic acid allyl ester compounds; 1,3,5-triallyl isocyanurate, 1,3-diallyl-5-glycidyl isocyanurate, etc., allyl isocyanurate compounds; 2,2- Aromatic allyl compounds containing epoxy groups, such as bis[3-allyl-4-(glycidoxy)phenyl]propane; aromatic allyl compounds containing benzoxazine, such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazine-3-yl)phenyl]methane; ether-containing aromatic allyl compounds, such as 1,3,5-triallyl ether benzene; allyl silane compounds, such as diallyl diphenylsilane, etc. Commercially available allyl-based free radical polymerizable compounds include TAIC (1,3,5-triallyl isocyanurate) manufactured by Nippon Chemical Co., Ltd., DAD (dallyl biphenyl dicarboxylate) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., TRIAM-705 (triallyl trimellitate) manufactured by Wako Pure Chemical Industries Co., Ltd., DAND (dallyl 2,3-naphthocarboxylate) manufactured by Nippon Distillation Industries Co., Ltd., ALP-d (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) manufactured by Shikoku Chemical Co., Ltd., RE-810NM (2,2-bis[3-allyl-4-(glycidoxy)phenyl]propane) manufactured by Nippon Chemical Co., Ltd., and DA-MGIC (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Chemical Co., Ltd.

[0142] Maleimide-based free radical polymerizable compounds are compounds having two or more maleimide groups. These compounds can be aliphatic maleimide compounds containing an aliphatic amine skeleton or aromatic maleimide compounds containing an aromatic amine skeleton. Commercially available examples include Shin-Etsu Chemical Co., Ltd.'s "SLK-2600" and Designer. The following are examples of maleimide compounds manufactured by Molecules: "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", and "BMI-2500" (maleimide compounds containing a dimer diamine structure); "BMI-6100" (aromatic maleimide compound) manufactured by Designer Molecules; "MIR-5000-60T" and "MIR-3000-70MT" (biphenyl aryl maleimide compounds) manufactured by Nippon Kayaku Co., Ltd.; "BMI-70" and "BMI-80" manufactured by KI Chemical Co., Ltd.; and "BMI-2300" and "BMI-TMH" manufactured by Yamato Chemical Industries Co., Ltd. Furthermore, maleimide resins (maleimide compounds containing an indane ring skeleton) disclosed in Japanese Invention Publication No. 2020-500211 can also be used as maleimide-based free radical polymerizable compounds.

[0143] (C) The equivalent amount of the olefinic unsaturated bond in the free radical polymerizable compound is preferably 20 g / eq. to 3000 g / eq., more preferably 50 g / eq. to 2500 g / eq., further preferably 70 g / eq. to 2000 g / eq., and particularly preferably 90 g / eq. to 1500 g / eq. The equivalent amount of the olefinic unsaturated bond is the mass of the free radical polymerizable compound per 1 equivalent of olefinic unsaturated bond.

[0144] (C) The weight-average molecular weight (Mw) of the free radical polymerizable compound is preferably 40,000 or less, more preferably 10,000 or less, even more preferably 5,000 or less, and particularly preferably 3,000 or less. The lower limit is not particularly limited, for example, it can be set to 150 or more.

[0145] The content (mass%) of the (C) free radical polymerizable compound in the first resin composition is not particularly limited. When the non-volatile component in the first resin composition is set to 100% by mass, from the viewpoint of obtaining the desired effect of the present invention more significantly, it is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less. The lower limit is, for example, 0% by mass or more, 0.1% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more.

[0146] The content (mass%) of the (C) free radical polymerizable compound in the second resin composition is not particularly limited. When the non-volatile component in the second resin composition is set to 100% by mass, from the viewpoint of obtaining the desired effect of the present invention more significantly, it is preferably 30% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 1% by mass or less. The lower limit can be set to 0% by mass or more, for example.

[0147] From the viewpoint of achieving the desired effect of the present invention more significantly, it is preferable that the content (mass%) of the (C) radical polymerizable compound in the second resin composition is less than the content (mass%) of the (C) radical polymerizable compound in the first resin composition. The ratio (second resin composition / first resin composition) of the content (mass%) of the (C) radical polymerizable compound in the second resin composition to the content (mass%) of the (C) radical polymerizable compound in the first resin composition is generally 0 or more, preferably 0.6 or less, more preferably 0.2 or less, and particularly preferably 0.1 or less.

[0148] <(D) Free Radical Polymerization Initiator>

[0149] Both the first resin composition and the second resin composition may contain (D) a free radical polymerization initiator. (D) The free radical polymerization initiator may be, for example, a thermal polymerization initiator that generates free radicals upon heating. (D) The free radical polymerization initiator may be a polymerization initiator comprising a free radical polymerizable component as described above (C). One type of (D) free radical polymerization initiator may be used alone, or two or more may be used in any combination.

[0150] Examples of (D) radical polymerization initiators include peroxide-based radical polymerization initiators and azo-based radical polymerization initiators. Among these, peroxide-based radical polymerization initiators are preferred.

[0151] Examples of peroxide-based free radical polymerization initiators include: hydrogen peroxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; dialkyl peroxide compounds such as tert-butyl cumene peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, dicumyl peroxide, 1,4-bis(1-tert-butylperoxy-1-methylethyl)benzene, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; and dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl percarbonate, and bis(4-tert-butylcyclohexyl)peroxide. Peroxide diacyl compounds such as oxidized dicarbonates; peroxide ester compounds such as tert-butyl peracetate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxylaurate, 1,1-dimethylpropyl 2-ethylperoxyhexanoate, tert-butyl 2-ethylperoxyhexanoate, tert-butyl 3,5,5-trimethylperoxyhexanoate, tert-butyl peroxy-2-ethylhexyl monocarbonate, and tert-butyl peroxymaleate; etc.

[0152] Examples of azo nitrile compounds that serve as initiators for azo radical polymerization include: 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carboxynitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, 2-phenylazo-4-methoxy-2,4-dimethylpentanonitrile, etc.; 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], 2,2'-azobis[2-methyl-N-[1,1-bis( Azoamide compounds such as [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-methylpropionamide) dihydrate, 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); alkylazo compounds such as 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane); etc.

[0153] Commercially available products that serve as (D) radical polymerization initiators include, for example, those manufactured by Nippon Oil Company such as "PERBUTYL C", "PERBUTYL A", "PERBUTYL P", "PERBUTYL L", "PERBUTYL O", "PERBUTYL ND", "PERBUTYL Z", "PERBUTYL I", "PERCUMYL P", "PERCUMYL D", "PERHEXYL D", "PERHEXYL A", "PERHEXYL LI", "PERHEXYL Z", "PERHEXYL ND", "PERHEXYL O", "PERHEXYL LPV", "PERHEXYL O", and "PERHEXYNE 25B".

[0154] The content (mass%) of the (D) free radical polymerization initiator in the first resin composition is not particularly limited. When the non-volatile component in the first resin composition is set to 100% by mass, from the viewpoint of obtaining the desired effect of the present invention more significantly, it is preferably 5% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less. The lower limit is, for example, 0% by mass or more, 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more.

[0155] The content (mass%) of (D) free radical polymerization initiator in the second resin composition is not particularly limited. When the non-volatile component in the second resin composition is set to 100% by mass, from the viewpoint of obtaining the desired effect of the present invention more significantly, it is preferably 5% by mass or less, more preferably 2% by mass or less, particularly preferably 1% by mass or less, and the lower limit may be set to 0% by mass or more, for example.

[0156] <(E) Thermoplastic Resins>

[0157] The first resin composition and the second resin composition sometimes each contain (E) a thermoplastic resin. The (E) thermoplastic resin described herein refers to any substance other than the (C) free radical polymerizable compounds described above.

[0158] Examples of the (E) thermoplastic resin include: polyimide resin, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamide-imide resin, polyether-imide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin, etc. In one embodiment, the (E) thermoplastic resin preferably comprises a thermoplastic resin selected from polyimide resin and phenoxy resin. Furthermore, one type of thermoplastic resin may be used alone, or two or more types may be used in combination.

[0159] Specific examples of polyimide resins include Shin-Etsu Chemical Co., Ltd.'s "SLK-6100", Shin Nippon Rikka Co., Ltd.'s "RIKACOAT SN20" and "RIKACOAT PN20".

[0160] Examples of phenoxy resins include those having one or more skeletons selected from the following: bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, phenolic skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal end of the phenoxy resin may have any functional group such as a phenolic hydroxyl group or an epoxy group.

[0161] Specific examples of phenoxy resins include: Mitsubishi Chemical's "1256" and "4250" (both phenoxy resins containing a bisphenol A backbone); Mitsubishi Chemical's "YX8100" (phenoxy resin containing a bisphenol S backbone); Mitsubishi Chemical's "YX6954" (phenoxy resin containing a bisphenol acetophenone backbone); Nippon Steel & Sumitomo Chemical's "FX280" and "FX293"; and Mitsubishi Chemical's "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", and "YL7891BH30", etc.

[0162] Examples of polyvinyl alcohol acetal resins include, for example, polyvinyl alcohol formaldehyde resin and polyvinyl alcohol butyral resin, with polyvinyl alcohol butyral resin being preferred. Specific examples of polyvinyl alcohol acetal resins include: "Electrochemical Butyral 4000-2", "Electrochemical Butyral 5000-A", "Electrochemical Butyral 6000-C", and "Electrochemical Butyral 6000-EP" manufactured by Denki Kagaku Kogyo Co., Ltd.; and the S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemicals Co., Ltd., etc.

[0163] Examples of polyolefin resins include low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, and other ethylene-based copolymers; as well as polyolefin polymers such as polypropylene and ethylene-propylene block copolymers.

[0164] Examples of polybutadiene resins include: resins containing a hydrogenated polybutadiene backbone, hydroxyl-containing polybutadiene resins, phenolic hydroxyl-containing polybutadiene resins, carboxyl-containing polybutadiene resins, acid anhydride-containing polybutadiene resins, epoxy-containing polybutadiene resins, isocyanate-containing polybutadiene resins, urethane-containing polybutadiene resins, and polyphenylene ether-polybutadiene resins.

[0165] Specific examples of polyamide-imide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Other specific examples of polyamide-imide resins include modified polyamide-imides such as "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane backbone) manufactured by Hitachi Chemical Co., Ltd.

[0166] Specific examples of polyethersulfone resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0167] Specific examples of polysulfone resins include polysulfones such as "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0168] Specific examples of polyphenylene ether resins include SABIC's "NORYL SA90". Specific examples of polyetherimide resins include GE's "ULTEM".

[0169] Examples of polycarbonate resins include: hydroxyl-containing carbonate resins, phenolic hydroxyl-containing carbonate resins, carboxyl-containing carbonate resins, anhydride-containing carbonate resins, isocyanate-containing carbonate resins, and urethane-containing carbonate resins. Specific examples of polycarbonate resins include "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemical Co., Ltd., and "C-1090," "C-2090," and "C-3090" (polycarbonate diol) manufactured by Kuraray Co., Ltd. Specific examples of polyetheretherketone (PEEK) resins include "SUMIPLOYK" manufactured by Sumitomo Chemical Co., Ltd.

[0170] Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polypropylene terephthalate resin, polypropylene naphthalate resin, and polycyclohexanedimethyl terephthalate resin.

[0171] From the viewpoint of achieving significant effects of the present invention, the weight-average molecular weight (Mw) of the thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, further preferably 10,000 or more, particularly preferably 20,000 or more, preferably 100,000 or less, more preferably 70,000 or less, further preferably 60,000 or less, and particularly preferably 50,000 or less.

[0172] The content (mass%) of thermoplastic resin (E) in the first resin composition is not particularly limited. When the non-volatile component in the first resin composition is set to 100% by mass, from the viewpoint of obtaining the desired effect of the present invention more significantly, it is preferably 40% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less. The lower limit is, for example, 0% by mass or more, 0.1% by mass or more, 0.5% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 3% by mass or more.

[0173] The content (mass%) of thermoplastic resin (E) in the second resin composition is not particularly limited. When the non-volatile component in the second resin composition is set to 100% by mass, from the viewpoint of obtaining the desired effect of the present invention more significantly, it is preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less. The lower limit is, for example, 0% by mass or more, 0.1% by mass or more, 0.5% by 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.

[0174] <(F) Curing Accelerator>

[0175] When the first resin composition and the second resin composition each comprise (A-1) epoxy resin as (A) thermosetting resin, they sometimes further comprise (F) curing accelerator as an optional component. The (F) curing accelerator has the function of promoting the curing of the (A-1) epoxy resin.

[0176] Examples of curing accelerators 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 these, imidazole-based curing accelerators are preferred from the viewpoint of improving crosslinking properties. (F) A single curing accelerator may be used alone, or two or more may be used in combination.

[0177] Examples of phosphorus-based curing accelerators include: tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitic acid tetraphosphate, tetrabutylphosphonium hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate, and other aliphatic phosphonium salts; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, and p-tolyltriphenylphosphonium tetrap-methylphosphonium bromide. Aromatic phosphonium salts such as phenyl borates, tetraphenylphosphonium tetraphenyl borates, tetraphenylphosphonium tetratolyl borates, triphenylethylphosphonium tetraphenyl borates, tri(3-methylphenyl)ethylphosphonium tetraphenyl borates, tri(2-methoxyphenyl)ethylphosphonium tetraphenyl borates, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-benzoquinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, and di-tert-butyl(2-butylphosphine) Aliphatic phosphines such as tricyclohexylphosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine; and tributylphenylphosphine, tri-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(4-tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,5-dimethylphenyl)phosphine, and tri(2,6-dimethylphenyl)phosphine. Aromatic phosphines include 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(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether.

[0178] Examples of urea-based curing accelerators include: 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-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, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. Aromatic dimethylureas include 1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea)[toluenebisdimethylurea], etc.

[0179] Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine.

[0180] Examples of imidazole-based curing accelerators include, for example, 2-methylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, and 2,4-diamino-6-[2'-methylimidazolium-(1')] [Ethyl-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine isocyanuric acid adduct, 2-phenylimidazolyl isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds and adducts of imidazole compounds with epoxy resins.

[0181] As an imidazole-based curing accelerator, commercially available products can be used, such as "1B2PZ", "2MZA-PW", and "2PHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Co., Ltd.

[0182] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) and cobalt(III) acetylacetone, organocopper complexes such as copper(II) acetylacetone, organozinc complexes such as zinc(II) acetylacetone, organoiron complexes such as iron(III) acetylacetone, organonickel complexes such as nickel(II) acetylacetone, and organomanganese complexes such as manganese(II) acetylacetone. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0183] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene.

[0184] As an amine-based curing accelerator, commercially available products can be used, such as "MY-25" manufactured by Ajinomoto Fine-Techno.

[0185] The content (mass%) of the curing accelerator (F) in the first resin composition is not particularly limited. From the viewpoint of obtaining the desired effect of the present invention more significantly, when the non-volatile component in the first resin composition is set to 100% by mass, it is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less. The lower limit can be set to 0% by mass or more, for example.

[0186] The content (mass%) of the curing accelerator (F) in the second resin composition is not particularly limited. When the non-volatile component in the second resin composition is set to 100% by mass, from the viewpoint of obtaining the desired effect of the present invention more significantly, it is preferably 5% by mass or less, more preferably 3% by mass or less, particularly preferably 1% by mass or less, and the lower limit is, for example, 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, and preferably 0.1% by mass or more.

[0187] <(G) Other Additives>

[0188] Both the first resin composition and the second resin composition may further comprise optional additives as non-volatile components. Examples of such additives include, for instance, organic fillers such as rubber particles; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentonite and montmorillonite; defoamers such as silicone-based defoamers, acrylic-based defoamers, fluorinated defoamers, and vinyl resin-based defoamers; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion enhancers such as ureasilanes; and adhesion promoters such as triazole-based, tetraazole-based, and triazine-based adhesion promoters. Antioxidants such as hindered phenolic antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorinated surfactants and organosilicon surfactants; flame retardants such as phosphorus-based (e.g., phosphate ester compounds, phosphazene compounds, phosphonic acid compounds, red phosphorus), nitrogen-based (e.g., melamine sulfate), halogen-based, and inorganic flame retardants such as antimony trioxide; dispersants such as phosphate ester-based, polyoxyethylene-based, acetylene-based, organosilicon-based, anionic, and cationic dispersants; stabilizers such as borate / ester-based, titanate / ester-based, aluminate / ester-based, zirconate / ester-based, isocyanate-based, carboxylic acid-based, and carboxylic anhydride-based stabilizers, etc. (G) Other additives may be used alone or in combination of two or more in any ratio. (G) The content of other additives can be appropriately set by those skilled in the art.

[0189] <(H) organic solvent>

[0190] In addition to the aforementioned non-volatile components, the first resin composition and the second resin composition sometimes further contain an optional organic solvent as a volatile component. As the (H) organic solvent, any known organic solvent capable of dissolving at least a portion of the non-volatile component can be used, and its type is not particularly limited. Examples of (H) organic solvents include, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; and 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol ethyl ether acetate. Ether ester solvents such as acetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (H) Organic solvents can be used alone or in combination of two or more in any ratio.

[0191] <Method for manufacturing resin composition>

[0192] The first and second resin compositions can be manufactured by independently adding (A) a thermosetting resin, (B) an inorganic filler, (C) a free radical polymerizable compound, (D) a free radical polymerization initiator, (E) a thermoplastic resin, (F) a curing accelerator, (G) other additives, and (H) an organic solvent simultaneously and in any preparation container, as needed, in any order and / or in any order. Furthermore, during the addition and mixing of the components, the temperature can be appropriately set, and heating and / or cooling can be performed temporarily or continuously. Additionally, during or after the addition and mixing, the resin composition can be stirred or agitated using a stirring or shaking device, such as a mixer, to ensure uniform dispersion. Furthermore, degassing can be performed under low-pressure conditions such as vacuum while stirring or agitating.

[0193] <Support Body>

[0194] Examples of supports for resin sheets with supports include films made of plastic materials, metal foils, and release paper, with films and metal foils made of plastic materials being more preferred.

[0195] When a film formed of a plastic material is used as a support, examples of plastic materials include, for example, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), acrylic polymers such as polycarbonate (hereinafter sometimes abbreviated as "PC") and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0196] When using metal foil as a support, examples of metal foil include copper foil and aluminum foil, with copper foil being preferred. Copper foil can be used as the support, either as a single metal such as copper or as an alloy of copper with other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0197] The surface of the support body that is bonded to the resin sheet layer can be treated with matte finish, corona treatment, and antistatic treatment.

[0198] Furthermore, as a support, a support with a release layer can be used on the surface bonded to the resin sheet layer. Examples of release agents used in the release layer of the support with a release layer include, for example, one or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. Commercially available products can be used as the support with a release layer, such as PET films having a release layer with an alkyd resin-based release agent as the main component, namely, Lintec's "SK-1", "AL-5", and "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and UNITIKA's "Unipeel".

[0199] The thickness of the support is not particularly limited, but is preferably in the range of 5μm to 75μm, more preferably in the range of 10μm to 60μm. It should be noted that when using a support with a release layer, the overall thickness of the support with the release layer is preferably within the above range.

[0200] A protective film can be further included on the surface of the resin sheet layer that is not bonded to the support. The protective film helps prevent the adhesion of dust, etc., or scratches on the surface of the resin sheet layer. The same material as described in the <Support> section can be used as the material for the protective film. The thickness of the protective film is not particularly limited, for example, from 1 μm to 40 μm. When manufacturing printed wiring boards, etc., the resin sheet with the support can be used by peeling off the protective film. The thickness of the protective film is preferably thinner than the thickness of the support.

[0201] <Method for manufacturing resin sheets with supports>

[0202] A suitable embodiment of the method for manufacturing a resin sheet with a support is as follows: a first resin sheet having a first resin composition layer disposed on a first support and a second resin sheet having a second resin composition layer disposed on a second support are laminated in such a manner that the second resin composition layer is bonded to the first resin composition layer to form a resin sheet with a support. In this method, the second support is removed before the first support, thereby the first support becomes the support described above in the resin sheet with a support.

[0203] The first resin sheet and the second resin sheet can be manufactured, for example, by preparing a resin varnish by directly dissolving the first resin composition and the second resin composition in a liquid state or by dissolving the first resin composition and the second resin composition in an organic solvent, applying them respectively onto a first support and a second support using a die coater or the like, and then drying them to form a first resin composition layer or a second resin composition layer. Examples of organic solvents include those described as components of the resin composition. One organic solvent can be used alone, or two or more can be used in combination.

[0204] The drying of the resin composition can be carried out by known methods such as heating or blowing hot air. The drying conditions are not particularly limited, but drying is carried out such that the content of organic solvent in the first resin composition layer and the second resin composition layer is 10% by mass or less, preferably 5% by mass or less. The drying method also varies depending on the boiling point of the organic solvent in the resin composition. For example, when using a resin composition containing 30% to 60% by mass of organic solvent, the first resin composition layer and the second resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0205] As another embodiment, the resin sheet with the support can also be manufactured by the following method: coating a first resin composition onto the support and drying the coating to form a first resin composition layer, and then coating a second resin composition onto the first resin composition layer and drying the coating to form a second resin composition layer.

[0206] In this method, the first resin composition layer can be prepared by directly dissolving the liquid first resin composition or dissolving it in the same organic solvent as described above to prepare a resin varnish, applying it to a support using a die coater or the like, and then drying the resin composition. Furthermore, the second resin composition layer can be prepared by directly dissolving the liquid second resin composition or dissolving it in the same organic solvent as described above to prepare a resin varnish, applying it to the first resin composition layer using a die coater or the like, and then drying the resin composition. The resin composition can be dried using the same methods described above.

[0207] In addition to the manufacturing methods described above, resin sheets with supports can also be formed by a series coating method in which two resin compositions (resin varnishes) are sequentially coated on a coating production line.

[0208] Resin sheets with supports can be rolled up for storage. When resin sheets with supports have a protective film, they can be used by peeling off the protective film.

[0209] <Characteristics of Resin Sheets with Supports>

[0210] By curing the resin sheet layer of the resin sheet material with the support of the present invention, an insulating layer formed from the cured resin sheet layer can be obtained. When through-holes are formed in this insulating layer and a roughening treatment is performed, halo phenomena can be suppressed. Hereinafter, these effects will be explained with reference to the accompanying drawings.

[0211] Figure 2 This is a schematic cross-sectional view illustrating both an insulating layer 100 and an inner substrate 200 obtained by curing a resin sheet layer with a support, according to one embodiment of the present invention. Figure 2 The cross-section of the insulating layer 100 is shown by cutting it through the center 120C of the bottom 120 of the through hole 110 and parallel to the thickness direction of the insulating layer 100.

[0212] like Figure 2As shown, the insulating layer 100 is a layer obtained by curing a resin sheet layer formed on the inner layer substrate 200 containing the conductor layer 210. Starting from the conductor layer 210 side, it sequentially comprises a second cured layer 20' formed by thermally curing a second resin composition layer 20 and a first cured layer 10' formed by thermally curing a first resin composition layer 10. Furthermore, a through-hole 110 is formed on the insulating layer 100. The through-hole 110 is typically formed in a forward-tapered shape, with a larger diameter closer to the surface 100U of the insulating layer 100 opposite to the conductor layer 210 and a smaller diameter closer to the conductor layer 210. Ideally, it is formed as a column with a constant diameter in the thickness direction of the insulating layer 100. The through-hole 110 is typically formed by irradiating the surface 100U of the insulating layer 100 opposite to the conductor layer 210 with a laser to remove a portion of the insulating layer 100.

[0213] The bottom of the via 110 on the conductor layer 210 side is suitably referred to as the "via bottom" and denoted by the symbol 120. The diameter of the via bottom 120 is then referred to as the via bottom diameter Lb. Furthermore, the opening of the via 110 formed on the opposite side of the conductor layer 210 is suitably referred to as the "via top" and denoted by the symbol 130. The diameter of the via top 130 is then referred to as the via top diameter Lt. Typically, the planar shape of the via bottom 120 and via top 130, as viewed from the thickness direction of the insulating layer 100, is circular, but it can also be elliptical. When the planar shape of the via bottom 120 and via top 130 is elliptical, the via bottom diameter Lb and via top diameter Lt respectively represent the major axis of the aforementioned ellipse.

[0214] At this point, the closer the taper (tap ratio) Lb / Lt obtained by dividing the bottom diameter Lb of the through hole by the top diameter Lt of the through hole is to 100%, the better the shape of the through hole 110.

[0215] The taper Lb / Lt of the through-hole 110 can be calculated from the bottom diameter Lb and the top diameter Lt of the through-hole 110. Furthermore, the bottom diameter Lb and the top diameter Lt of the through-hole 110 can be determined by cutting the insulating layer 100 using a FIB (Focused Ion Beam) to create a cross-section parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the bottom 120 of the through-hole, and then observing this cross-section using an electron microscope.

[0216] Figure 3 This schematically illustrates an embodiment of the invention involving an insulating layer 100 obtained by curing a resin sheet layer with a support and a conductor layer 210. Figure 3 (Not shown in the figure) is a top view of the opposite side surface 100U.

[0217] like Figure 3 As shown, when observing the insulating layer 100 with the through-hole 110, a discolored portion 140 is sometimes observed around the through-hole 110, extending from the edge 180 of the top 130 of the through-hole to the outer periphery edge 190 of the discolored portion 140, where the insulating layer 100 changes color. This discolored portion 140 may be formed due to resin degradation during the formation of the through-hole 110, and therefore is usually formed continuously from the through-hole 110. Furthermore, in most cases, the discolored portion 140 becomes a whitened portion.

[0218] Figure 4 This is a schematic cross-sectional view showing both the roughened insulating layer 100 and the inner substrate 200 obtained by curing a resin sheet layer with a support, according to one embodiment of the present invention. Figure 4 The diagram shows a cross-section of the insulating layer 100 cut off by a plane that passes through the center 120C of the bottom 120 of the through hole 110 and is parallel to the thickness direction of the insulating layer 100.

[0219] like Figure 4 As shown, if the insulating layer 100 with through hole 110 is roughened, a halo effect is produced, the insulating layer 100 of the discolored portion 140 is peeled off from the conductor layer 210, and sometimes a continuous gap portion 160 is formed from the edge 150 of the bottom 120 of the through hole.

[0220] By using the resin sheet layer of the present invention, the aforementioned halo phenomenon can be suppressed. Therefore, the peeling of the insulating layer 100 from the conductor layer 210 can be suppressed, thereby reducing the size of the gap 160.

[0221] The edge 150 of the bottom 120 of the through hole corresponds to the inner peripheral edge of the gap 160. Therefore, the distance Wb from the edge 150 of the bottom 120 of the through hole to the end of the outer peripheral side of the gap 160 (i.e., the end on the side away from the center 120C of the bottom 120 of the through hole) is equivalent to the in-plane dimension of the gap 160. Here, the in-plane direction refers to the direction perpendicular to the thickness direction of the insulating layer 100. Furthermore, in the following description, the aforementioned distance Wb is sometimes referred to as the halo distance Wb from the edge 150 of the bottom 120 of the through hole 110. The degree of suppression of the halo phenomenon can be evaluated by this halo distance Wb from the edge 150 of the bottom 120 of the through hole. Specifically, the smaller the halo distance Wb from the edge 150 of the bottom 120 of the through hole, the more effectively the halo phenomenon can be suppressed.

[0222] For example, an insulating layer 100 is obtained by heating a resin sheet layer formed on a copper foil at 100°C for 30 minutes and then at 180°C for 30 minutes to cure it. The insulating layer 100 is then irradiated with a CO2 laser to form a through-hole 110 with a top diameter Lt of approximately 40 μm. The through-hole is then immersed in a swelling solution at 60°C for 10 minutes, followed by immersion in an oxidizing agent solution at 80°C for 20 minutes, then immersion in a neutralizing solution at 40°C for 5 minutes, and finally dried at 80°C for 15 minutes. If the resin sheet with a support of the present invention is used, the halo distance Wb of the insulating layer 100 thus obtained from the edge 150 of the through-hole bottom 120 of the through-hole 110 is preferably 10 μm or less, more preferably 8 μm or less, further preferably 5.5 μm or less, and particularly preferably 5 μm or less.

[0223] The aforementioned CO2 laser irradiation conditions were set as follows: mask diameter 1 mm, pulse width 16 μs, energy 0.2 mJ / emission, emission number 2, burst mode (10 kHz).

[0224] The halo distance Wb from the edge 150 of the bottom 120 of the via can be determined by cutting the insulating layer 100 using FIB (Focused Ion Beam) to present a cross section parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the bottom 120 of the via, and then observing the cross section with an electron microscope.

[0225] Furthermore, by using a resin sheet layer, the shape of the through-hole 110 in the insulating layer 100 before roughening treatment can be easily controlled. Therefore, even in the insulating layer 100 after roughening treatment, the shape of the through-hole 110 can usually be easily controlled. Thus, even after roughening treatment, the shape of the through-hole 110 can be made as good as before roughening treatment.

[0226] The taper Lb / Lt of the roughened via 110 can be calculated from the bottom diameter Lb and top diameter Lt of the via 110. Furthermore, the bottom diameter Lb and top diameter Lt of the via 110 can be determined by cutting the insulating layer 100 using a FIB (Focused Ion Beam) to create a cross-section parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the bottom 120 of the via, and then observing this cross-section using an electron microscope.

[0227] Furthermore, according to the inventors' research, it has been shown that the larger the diameter of the through-hole, the larger the size of the gap 160 tends to be. Therefore, the degree of suppression of the halo phenomenon can be evaluated based on the ratio of the size of the gap 160 to the diameter of the through-hole 110. For example, it can be evaluated by the halo ratio Hb relative to the bottom radius Lb / 2 of the through-hole 110. Here, the bottom radius Lb / 2 of the through-hole 110 refers to the radius of the bottom 120 of the through-hole 110. In addition, the halo ratio Hb relative to the bottom radius Lb / 2 of the through-hole 110 is the ratio obtained by dividing the halo distance Wb from the edge 150 of the bottom 120 of the through-hole by the bottom radius Lb / 2 of the through-hole 110. The smaller the halo ratio Hb relative to the bottom radius Lb / 2 of the through-hole 110, the more effectively the halo phenomenon can be suppressed.

[0228] For example, a resin sheet layer formed on a copper foil is heated at 100°C for 30 minutes, followed by heating at 180°C for 30 minutes. The cured insulating layer 100 is then irradiated with a CO2 laser to form a through-hole 110 with a top diameter Lt of approximately 40 μm. Next, it is immersed in a swelling solution at 60°C for 10 minutes, followed by immersion in an oxidizing agent solution at 80°C for 20 minutes, then immersion in a neutralizing solution at 40°C for 5 minutes, and finally dried at 80°C for 15 minutes. The halo ratio Hb relative to the bottom radius Lb / 2 of the through-hole 110 formed on the insulating layer 100 thus obtained can preferably be 35% or less, more preferably 30% or less, and even more preferably 25% or less.

[0229] The aforementioned CO2 laser irradiation conditions were set as follows: mask diameter 1 mm, pulse width 16 μs, energy 0.2 mJ / emission, emission number 2, burst mode (10 kHz).

[0230] The halo ratio Hb relative to the bottom radius Lb / 2 of the through hole 110 can be calculated from the bottom diameter Lb of the through hole 110 and the halo distance Wb from the edge 150 of the bottom 120 of the through hole 110.

[0231] Furthermore, typically, by using the resin sheet layer of the present invention, the formation of the discolored portion 140 during the formation of the through-hole 110 can be suppressed. Therefore, as Figure 3 As shown, the size of the color-changing part 140 can be reduced, ideally to the point that the color-changing part 140 is non-existent. The size of the color-changing part 140 can be evaluated by the halo distance Wt from the edge 180 of the top 130 of the through hole 110.

[0232] The edge 180 of the top 130 of the through hole corresponds to the inner peripheral edge of the discoloration portion 140. The halo distance Wt from the edge 180 of the top 130 of the through hole represents the distance from the edge 180 of the top 130 of the through hole to the outer peripheral edge 190 of the discoloration portion 140. The smaller the halo distance Wt from the edge 180 of the top 130 of the through hole, the more effectively the formation of the discoloration portion 140 can be suppressed.

[0233] For example, a resin sheet layer formed on a copper foil is heated at 100°C for 30 minutes, followed by heating at 180°C for 30 minutes. The cured insulating layer 100 is then irradiated with a CO2 laser to form a through-hole 110 with a top diameter Lt of approximately 40 μm. Next, it is immersed in a swelling solution at 60°C for 10 minutes, followed by immersion in an oxidizing agent solution at 80°C for 20 minutes, then immersion in a neutralizing solution at 40°C for 5 minutes, and finally dried at 80°C for 15 minutes. The halo distance Wt of the insulating layer 100 thus obtained, starting from the edge 180 of the through-hole top 130, is preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less.

[0234] The aforementioned CO2 laser irradiation conditions were set as follows: mask diameter 1 mm, pulse width 16 μs, energy 0.2 mJ / emission, emission number 2, burst mode (10 kHz).

[0235] The halo distance Wt from the edge 180 at the top 130 of the through hole can be determined by observation using an optical microscope.

[0236] Furthermore, according to the inventors' research, it has been shown that the larger the diameter of the through-hole 110, the larger the size of the discoloration portion 140 tends to be. Therefore, the degree of suppression of the formation of the discoloration portion 140 can be evaluated based on the ratio of the size of the discoloration portion 140 to the diameter of the through-hole 110. For example, it can be evaluated by the halo ratio Ht relative to the top radius Lt / 2 of the through-hole 110. Here, the top radius Lt / 2 of the through-hole 110 refers to the radius of the top 130 of the through-hole 110. In addition, the halo ratio Ht relative to the top radius Lt / 2 of the through-hole 110 refers to the ratio obtained by dividing the halo distance Wt from the edge 180 of the top 130 of the through-hole by the top radius Lt / 2 of the through-hole 110. The smaller the halo ratio Ht relative to the top radius Lt / 2 of the through-hole 110, the more effectively the formation of the discoloration portion 140 can be suppressed.

[0237] For example, a resin sheet layer formed on a copper foil is heated at 100°C for 30 minutes, followed by heating at 180°C for 30 minutes. The cured insulating layer 100 is then irradiated with a CO2 laser to form a through-hole 110 with a top diameter Lt of approximately 40 μm. Next, it is immersed in a swelling solution at 60°C for 10 minutes, followed by immersion in an oxidizing agent solution at 80°C for 20 minutes, then immersion in a neutralizing solution at 40°C for 5 minutes, and finally dried at 80°C for 15 minutes. The halo ratio Ht relative to the top radius Lt / 2 of the through-hole 110 formed on the thus-obtained insulating layer 100 can preferably be 35% or less, more preferably 30% or less, and even more preferably 28% or less.

[0238] The aforementioned CO2 laser irradiation conditions were set as follows: mask diameter 1 mm, pulse width 16 μs, energy 0.2 mJ / emission, emission number 2, burst mode (10 kHz).

[0239] The halo ratio Ht relative to the top radius Lt / 2 of the through hole 110 can be calculated from the top diameter Lt of the through hole 110 and the halo distance Wt from the edge 180 of the top 130 of the through hole 110.

[0240] During the manufacturing process of a printed circuit board (PCB), the via 110 is typically formed on the side 100U of the insulating layer 100 opposite to the conductor layer 210 without any other conductor layer (not shown). Therefore, if the PCB manufacturing process is known, the structure with a via bottom 120 on the conductor layer 210 side and a via top 130 opening on the side opposite to the conductor layer 210 can be clearly identified. However, in the finished PCB, conductor layers are sometimes provided on both sides of the insulating layer 100. In this case, it may be difficult to distinguish the via bottom 120 from the via top 130 based on their positional relationship with the conductor layers. However, the via top diameter Lt of the via top 130 is typically larger than or equal to the via bottom diameter Lb of the via bottom 120. Therefore, in the aforementioned case, the via bottom 120 from the via top 130 can be distinguished based on their diameters.

[0241] By using the resin sheet with a support of the present invention, in addition to suppressing the halo phenomenon, the dielectric loss tangent d of the entire cured layer (insulating layer) can also be reduced. all The inhibition level is relatively low.

[0242] For example, the dielectric loss tangent d of the entire cured layer (insulating layer) formed by the first cured layer and the second cured layer. allWhen the thickness of the first resin composition layer is set as t1 (μm), the thickness of the second resin composition layer is set as t2 (μm), the dielectric loss 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 as d1, and the dielectric loss tangent of the second cured layer formed by curing the second resin composition layer at 190°C for 90 minutes (measurement frequency 5.8 GHz, measurement temperature 23°C) is set as d2, it can be calculated by the following formula (5).

[0243] d all =d1×t1 / (t1+t2)+d2×t2 / (t1+t2)···(5).

[0244] The dielectric loss tangent d of the entire cured layer (insulating layer) calculated in this way is... all Preferably, the value is 0.020 or less, 0.010 or less, more preferably 0.009 or less, 0.008 or less, 0.007 or less, even more preferably 0.006 or less, 0.0058 or less, 0.0056 or less, and particularly preferably 0.0055 or less, 0.005 or less, 0.0045 or less, or 0.004 or less.

[0245] <Applications of Resin Sheets with Supports>

[0246] The resin sheet with a support of the present invention can be suitably used as a resin sheet with a support for forming an insulating layer for forming a conductor layer (including a redistribution layer) formed on the insulating layer.

[0247] Furthermore, in the multilayer printed wiring board described later, a resin sheet with a support for forming an insulating layer of the multilayer printed wiring board and a resin sheet with a support for forming an interlayer insulating layer of the printed wiring board can be suitably used.

[0248] Furthermore, for example, when manufacturing a semiconductor chip package via steps (1) to (6) below, the resin sheet with a support of the present invention can also be suitably used as a resin sheet with a support for forming a redistribution layer (as an insulating layer for forming the redistribution layer) and as a resin sheet with a support for sealing a semiconductor chip. During the manufacturing of the semiconductor chip package, a redistribution layer can also be further formed on the sealing layer;

[0249] (1) The step of laminating a temporary fixing film on the substrate,

[0250] (2) The step of temporarily fixing the semiconductor chip onto the temporary fixing film.

[0251] (3) The step of forming a sealing layer on a semiconductor chip.

[0252] (4) The step of peeling the substrate and temporary fixing film from the semiconductor chip.

[0253] (5) The step of forming a rewiring layer as an insulating layer on the surface of the semiconductor chip where the substrate and temporary fixing film have been stripped, and

[0254] (6) The step of forming a redistribution layer as a conductor layer on the redistribution forming layer.

[0255] Furthermore, the resin sheet layer in the resin sheet with support of the present invention provides an insulating layer with good component embedding, and can therefore be suitably used in cases where the printed wiring board is a circuit board with components built in.

[0256] [cured material]

[0257] The cured product of the present invention is a cured product formed by curing a resin sheet layer in a resin sheet with a support of the present invention. Therefore, the cured product of the present invention has a first cured layer formed from a cured product of a first resin composition, and a second cured layer formed on the first cured layer from a cured product of a second resin composition different from the first resin composition; the thickness of the first cured layer is set to t. 1' (μm), set the thickness of the second curing layer to t. 2' When the elastic modulus of the first cured layer (measurement temperature 23℃) is set as y1 (GPa), the elastic modulus of the second cured layer (measurement temperature 23℃) is set as y2 (GPa), the dielectric loss tangent of the first cured layer (measurement frequency 5.8GHz, measurement temperature 23℃) is set as d1, and the dielectric loss tangent of the second cured layer (measurement frequency 5.8GHz, measurement temperature 23℃) is set as d2, all conditions of the following equations (1'), (2) and (3) are satisfied.

[0258] 1≤t 1' / t 2' ≤10···(1')

[0259] y2 / y1≤0.70···(2)

[0260] 1<d2 / d1···(3).

[0261] The thickness t of the first cured layer 1' The thickness t1 (μm) of the first resin composition layer is the same as the thickness t1 (μm) of the second cured layer. 2' The thickness t2 (μm) is the same as the thickness t2 (μm) of the second resin composition layer. Therefore, t 1' / t 2' The range is the same as the range of t1 / t2.

[0262] Printed wiring board

[0263] The printed wiring board of the present invention includes an insulating layer (an insulating layer formed by curing) formed from a resin sheet layer of a resin sheet with a support body of the present invention.

[0264] Printed wiring boards can be manufactured, for example, using the aforementioned resin sheet with a support, by a method including the steps (I) and (II) below:

[0265] (I) A step of laminating a second resin composition layer with a support sheet onto an inner substrate.

[0266] (II) The step of heat curing the resin sheet layer to form an insulating layer.

[0267] The term "inner layer substrate" used in step (I) refers to a component that serves as the substrate of a printed wiring board, such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, or a thermosetting polyphenylene ether substrate. Furthermore, this substrate may have a conductor layer on one or both sides, and this conductor layer may be patterned. An inner layer substrate with a conductor layer (circuit) formed on one or both sides of the substrate is sometimes called an "inner layer circuit substrate." Additionally, intermediate components used to further form insulating layers and / or conductor layers during the manufacture of the printed wiring board are also included in the "inner layer substrate" as used in this invention. When the printed wiring board is a component-integrated circuit board, an inner layer substrate with integrated components can be used.

[0268] The lamination of the inner substrate and the resin sheet with the support can be performed, for example, by heating and pressing a second resin composition layer of the resin sheet layer onto the inner substrate from the support side. Examples of components for heating and pressing the resin sheet with the support onto the inner substrate (hereinafter also referred to as a "heat-pressing component") include, for example, a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller). It should be noted that the heat-pressing component is not directly pressed onto the resin sheet with the support; rather, it is preferable to press it using an elastic material such as heat-resistant rubber so that the resin sheet with the support fully follows the surface irregularities of the inner substrate.

[0269] The lamination of the inner substrate and the resin sheet with the support can be performed by vacuum lamination. In vacuum lamination, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C; the heating and pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa; and the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions of 26.7 hPa or less.

[0270] Lamination can be performed using commercially available vacuum laminators. Examples of commercially available vacuum laminators include, for instance, the vacuum pressure laminator manufactured by Meiki Seisakusho, the vacuum dressing device manufactured by Nikko-Materials, and the intermittent vacuum pressure laminator.

[0271] After lamination, the heated pressing member is pressed under normal pressure (atmospheric pressure), for example from the support side, thereby smoothing the laminated resin sheet with the support. The pressing conditions for smoothing can be set to the same conditions as the heated pressing conditions for lamination described above. Smoothing can be performed using a commercially available laminating machine. It should be noted that lamination and smoothing can be performed continuously using the aforementioned commercially available vacuum laminating machine.

[0272] The support can be removed between steps (I) and (II), or after step (II).

[0273] In step (II), the resin sheet layer is thermocured to form an insulating layer. The thermocuring conditions for the resin sheet layer are not particularly limited, and conditions typically used when forming insulating layers for printed wiring boards can be used.

[0274] For example, the thermosetting conditions of the resin sheet layer vary depending on the type of the first resin composition and the second resin composition, but the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C. The curing time can be preferably set to 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0275] Before heat curing the resin sheet layer, the resin sheet layer can be preheated at a temperature lower than the curing temperature. For example, before heat curing the resin sheet layer, the resin sheet layer can be preheated for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes) at a temperature of 50°C or higher and lower than 120°C (preferably 60°C or higher and lower than 115°C, more preferably 70°C or higher and lower than 110°C).

[0276] In manufacturing a printed wiring board, steps (III) of creating holes in the insulating layer, (IV) of roughening the insulating layer, and (V) of forming a conductor layer may be further performed. These steps (III) to (V) can be performed according to various methods known to those skilled in the art in the manufacture of the printed wiring board. It should be noted that when the support is removed after step (II), the removal of the support can be performed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). Furthermore, the formation of the insulating layer and conductor layer in steps (II) to (V) can be repeated as needed to form a multilayer wiring board.

[0277] Step (III) is the step of creating holes in the insulating layer, thereby forming vias, through-holes, and other holes in the insulating layer. Step (III) can be carried out using, for example, a drill bit, a laser, or plasma, depending on the composition of the first and second resin compositions used in the formation of the insulating layer. The size and shape of the holes can be appropriately determined according to the design of the printed circuit board.

[0278] Step (IV) is a roughening treatment of the insulating layer. Typically, smear removal is also performed in this step (IV). The roughening treatment steps and conditions are not particularly limited, and known steps and conditions commonly used in forming the insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened sequentially by a swelling treatment using a swelling solution, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing solution. The swelling solution used in the roughening treatment is not particularly limited; examples include alkaline solutions and surfactant solutions, with an alkaline solution being preferred, and sodium hydroxide solution or potassium hydroxide solution being more preferred. Commercially available swelling solutions include, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by ATOTECH JAPAN. The swelling treatment using the swelling solution is not particularly limited; for example, it can be performed by immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin in the insulating layer to a moderate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 to 15 minutes. The oxidant used in the roughening treatment is not particularly limited, and examples include, for instance, an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. Roughening treatment using an oxidant such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidant solution heated to 60°C to 100°C for 10 to 30 minutes. Furthermore, the concentration of permanganate in the alkaline permanganate solution is preferably 5% to 10% by mass. Commercially available oxidants include, for example, alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Ammet Japan Co., Ltd. Furthermore, the neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and commercially available products include, for example, "Reduction Solution Securiganth P" manufactured by Ammet Japan Co., Ltd. The treatment using the neutralizing solution can be performed by immersing the roughened surface treated with an oxidant in a neutralizing solution at 30°C to 80°C for 1 minute to 30 minutes. From the viewpoint of operability, it is preferable to immerse the roughened object treated with an oxidant in a neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes.

[0279] In one embodiment, the arithmetic mean roughness (Ra) of the surface of the roughened insulating layer is preferably 120 nm or less, more preferably 110 nm or less, and even 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 even 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.

[0280] Step (V) is the step of forming a conductor layer, which is formed on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer can be a single metal layer or an alloy layer. Examples of alloy layers include layers formed from alloys of two or more metals selected from the above (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). From the viewpoints of versatility, cost, and ease of patterning in conductor layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium, copper-nickel, or copper-titanium alloys, is preferred. More preferably, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloys, is even more preferred. A single metal layer of copper is even more preferred.

[0281] The conductor layer can be a single-layer structure or a multi-layer structure obtained by stacking two or more single-metal or alloy layers of different kinds of metals or alloys. When the conductor layer is a multi-layer structure, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0282] The thickness of the conductor layer depends on the desired printed wiring board design, typically 3μm to 35μm, preferably 5μm to 30μm.

[0283] In one embodiment, the conductor layer can be formed by plating. For example, the surface of the insulating layer can be plated using conventionally known techniques such as semi-additive or fully additive methods to form a conductor layer with the desired wiring pattern. From the viewpoint of ease of manufacturing, it is preferable to form the conductor layer using the semi-additive method. Hereinafter, examples of forming the conductor layer using the semi-additive method are shown.

[0284] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer, exposing a portion of the seed layer to correspond to the desired wiring pattern. After forming a metal layer on the exposed seed layer by electrolytic plating, the mask pattern is removed. Then, the unwanted portion of the seed layer is removed by etching or the like, thus forming a conductor layer with the desired wiring pattern.

[0285] [Semiconductor Devices]

[0286] 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.

[0287] Examples of semiconductor devices include various semiconductor devices used in electrical products (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trams, ships, and airplanes).

[0288] The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. A "conductive portion" refers to a portion that transmits electrical signals in the printed wiring board, and its location can be on the surface or embedded. Furthermore, the semiconductor chip is not particularly limited to any circuit element made of semiconductor material.

[0289] There are no particular limitations on the mounting method of semiconductor chips during the manufacture of semiconductor devices, as long as the semiconductor chip can effectively perform its function. Specific examples include wire bonding mounting method, flip chip mounting method, mounting method using a built-in bumpless layer (BBUL), mounting method using anisotropic conductive film (ACF), and mounting method using non-conductive film (NCF). Here, "mounting method using a built-in bumpless layer (BBUL)" refers to "a mounting method in which the semiconductor chip is directly embedded into a recess in a printed circuit board, thereby connecting the semiconductor chip to the wiring on the printed circuit board."

[0290] Example

[0291] The following examples illustrate the present invention. However, the present invention is not limited to these examples. In the following description, unless otherwise explicitly stated, "parts" and "%" refer to "parts by mass" and "% by mass," respectively. Furthermore, the operations described below are performed at room temperature and pressure unless otherwise explicitly stated.

[0292] <Inorganic filler material used>

[0293] Inorganic filler material 1: relative to spherical silica (Yaduma Corporation "SC2500SQ"), average particle size 0.63μm, specific surface area 11.2m². 2 100 parts (g) of a substance that has been surface-treated with 1 part of N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., KBM573);

[0294] Inorganic filler material 2: Compared to spherical silica (Denki Kagaku Kogyo Co., Ltd. "UFP-30"), average particle size 0.078 μm, specific surface area 30.7 m². 2A substance consisting of 100 parts (g) of a material that has been surface-treated with 2 parts of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM573).

[0295] <Synthesis Example 1: Synthesis of Polyimide Resin 1>

[0296] In a 500 ml detachable flask equipped with a nitrogen inlet tube and a stirrer, 9.13 g (30 mmol) of 5-aminobenzoic acid 5-amino-1,1'-biphenyl-2-yl ester (a compound of formula (B-3)), 15.61 g (30 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic dianhydride, 94.64 g of N-methyl-2-pyrrolidone, 0.47 g (6 mmol) of pyridine, and 10 g of toluene were added. Under a nitrogen atmosphere, an imidization reaction was carried out at 180 °C for 4 hours, with toluene being removed from the system midway through the reaction. This yielded a polyimide solution containing polyimide resin 1 (20% by mass of non-volatile components). No precipitation of the synthesized polyimide resin 1 was observed in the polyimide solution. The weight-average molecular weight of polyimide resin 1 was 45,000.

[0297] <Synthesis Example 2: Synthesis of Polyimide Resin 2>

[0298] In a reaction vessel equipped with a stirrer, water separator, thermometer, and nitrogen inlet, 65.0 g of aromatic tetracarboxylic acid dianhydride (SABIC Japan, "BisDA-1000"), 266.5 g of cyclohexanone, and 44.4 g of methylcyclohexane were added, and the solution was heated to 60°C. Next, 43.7 g of dimer diamine (Croda Japan, "PRIAMINE 1075") and 5.4 g of 1,3-bis(aminomethyl)cyclohexane were added dropwise, and an imidization reaction was carried out at 140°C for 1 hour. This yielded a polyimide solution containing polyimide resin 2 (30% by mass of non-volatile components). Furthermore, the weight-average molecular weight of polyimide resin 2 was 25,000.

[0299] <Preparation Example 1: Preparation of Resin Composition 1>

[0300] Six parts of xylenol-type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent approximately 185), four parts of naphthalene-type epoxy resin (Nippon Steel & Sumitomo Chemical Corporation "ESN475V", epoxy equivalent approximately 332), two parts of cyclohexane-type epoxy resin (Mitsubishi Chemical Corporation "ZX1658GS", epoxy equivalent approximately 135), ten parts of phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30"), and ten parts of a 1:1 solution of cyclohexanone and methyl ethyl ketone (MEK) with a solid content of 30% by weight, Mw = 35000) were dissolved by heating while stirring in a mixed solvent of 20 parts naphtha and 10 parts cyclohexanone. After cooling to room temperature, 4.5 parts of an active ester curing agent (DIC Corporation's "EXB-8000L-65TM", an active group equivalent of approximately 220, and a toluene solution containing 65% by mass of non-volatile components), 5 parts of a maleimide compound (Designer Molecules Corporation's "BMI-689"), 55 parts of an inorganic filler 1, and 0.1 parts of a polymerization initiator (Nippon Oil Corporation's "PERHEXYNE 25B") were mixed in the mixture. After being uniformly dispersed using a high-speed rotary mixer, the mixture was filtered through a cartridge filter (ROKITECHNO Corporation's "SHP020") to prepare resin composition 1.

[0301] <Preparation Example 2: Preparation of Resin Composition 2>

[0302] The amount of active ester-based curing agent (DIC Corporation's "EXB-8000L-65TM") was changed from 4.5 parts to 5 parts, and 40 parts of inorganic filler 2 were used instead of inorganic filler 1. Otherwise, the resin composition 2 was prepared in the same manner as in Preparation Example 1.

[0303] <Preparation Example 3: Preparation of Resin Composition 3>

[0304] Resin composition 3 was prepared in the same manner as in Preparation Example 1, except that 4.5 parts of an active ester curing agent (DIC's "EXB-8000L-65TM") was used instead of an active ester curing agent (DIC's "EXB-8151-62T", a toluene solution with a solid content of 62% by mass).

[0305] <Preparation Example 4: Preparation of Resin Composition 4>

[0306] Resin composition 4 was prepared in the same manner as in Preparation Example 1, except that 10 parts of styrene-modified polyphenylene ether resin (OPE-2St 1200, Mn=1200, toluene solution with 65% by mass solids) were used instead of maleimide compound (Designer Molecules "BMI-689").

[0307] <Preparation Example 5: Preparation of Resin Composition 5>

[0308] Resin composition 5 was prepared in the same manner as in Preparation Example 1, except that 4 parts of a difunctional acrylate compound (NK ester A-DOG, molecular weight 326, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) were used instead of the maleimide compound (BMI-689 manufactured by Designer Molecules Co., Ltd.).

[0309] <Preparation Example 6: Preparation of Resin Composition 6>

[0310] Resin composition 6 was prepared in the same manner as in Preparation Example 1, except that 4 parts of a difunctional allyl compound having a benzoxazine ring (ALP-d, manufactured by Shikoku Chemical Industry Co., Ltd.) were used instead of the maleimide compound (BMI-689 manufactured by Designer Molecules Co., Ltd.).

[0311] <Preparation Example 7: Preparation of Resin Composition 7>

[0312] The polyimide resin 1 synthesized in Synthesis Example 1 was prepared in the same manner as in Preparation Example 1, except that xylenol-type epoxy resin (YX4000HK manufactured by Mitsubishi Chemical Co., Ltd.), naphthalene-type epoxy resin (ESN475V manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), cyclohexane-type epoxy resin (ZX1658GS manufactured by Mitsubishi Chemical Co., Ltd.), and reactive ester-based curing agent (EXB-8000L-65TM manufactured by DIC Co., Ltd.) were used instead of 5 parts, the amount of maleimide compound (BMI-689 manufactured by Designer Molecules Co., Ltd.) was changed from 5 parts to 15 parts, and 9 parts of phenoxy resin (YX7553BH30 manufactured by Mitsubishi Chemical Co., Ltd.) were used instead of phenoxy resin.

[0313] <Preparation Example 8: Preparation of Resin Composition 8>

[0314] The resin composition 8 was prepared in the same manner as in Preparation Example 7, except that 9 parts of polyimide resin 2 synthesized in Preparation Example 2 were used instead of polyimide resin 1 synthesized in Preparation Example 1.

[0315] <Preparation Example 9: Preparation of Resin Composition 10>

[0316] Six parts of bisphenol type epoxy resin (Nippon Steel & Sumitomo Chemical Co., Ltd. "ZX1059", epoxy equivalent approximately 169, a 1:1 mixture of bisphenol A and bisphenol F), two parts of biphenyl aryl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000", epoxy equivalent 276), and ten parts of phenoxy resin (Mitsubishi Chemical Co., Ltd. "YX7553BH30", a 1:1 solution of cyclohexanone and methyl ethyl ketone (MEK) with a solid content of 30% by weight, Mw = 35000) were dissolved by heating while stirring in a mixed solvent of 20 parts naphtha and 10 parts cyclohexanone. After cooling to room temperature, 2 parts of an active ester-based curing agent (DIC's "EXB-8000L-65TM", with an active group equivalent of approximately 220 and 65% by mass of non-volatile components in a 1:1 solution of toluene:MEK) 2 parts of a triazine-based cresol phenolic varnish curing agent (DIC's "LA-3018-50P", with a hydroxyl equivalent of approximately 151 and 50% solid components in a 2-methoxypropanol solution) 3 parts of an inorganic filler 1 part and a curing accelerator (Shikoku Kasei's "1B2PZ") 0.1 parts were mixed and evenly dispersed using a high-speed rotary mixer and then filtered through a cartridge filter (ROKITECHNO's "SHP020") to prepare resin composition 10.

[0317] <Preparation Example 10: Preparation of Resin Composition 11>

[0318] Resin composition 11 was prepared in the same manner as in Preparation Example 9, except that 4 parts of a phenolic varnish curing agent containing triazine (DIC Corporation's "EXB-8000L-65TM") was used instead of an active ester-based curing agent (DIC Corporation's "EXB-8000L-65TM") and a cresol-phenolic varnish curing agent containing a triazine skeleton (DIC Corporation's "LA-3018-50P").

[0319] <Preparation Example 11: Preparation of Resin Composition 12>

[0320] Resin composition 12 was prepared in the same manner as in Preparation Example 1, except that 4 parts of a triazine-containing phenolic varnish curing agent (DIC Corporation's "LA7054", hydroxyl equivalent 125, methyl ethyl ketone solution with 60% by mass of solids) were used instead of the reactive ester-based curing agent (DIC Corporation's "EXB-8000L-65TM").

[0321] <Preparation Example 12: Preparation of Resin Composition 13>

[0322] The amount of active ester curing agent (DIC Corporation's "EXB-8000L-65TM") was changed from 4.5 parts to 4 parts, and maleimide compound (Designer Molecules Corporation's "BMI-689") was not used. Otherwise, the resin composition 13 was prepared in the same manner as in Preparation Example 1.

[0323] <Preparation Example 13: Preparation of Resin Composition 14>

[0324] The amount of inorganic filler 1 used was changed from 3 parts to 25 parts, and the resin composition 14 was prepared in the same manner as in Preparation Example 10.

[0325] <Example 1: Fabrication of resin sheet 1 with support>

[0326] As a support, a 38 μm thick PET film (Lintec Corporation "AL5") was prepared. A varnish-like resin composition 1 prepared in Preparation Example 1 was uniformly coated onto the support using a die coater. The coating was dried at 80–120°C (average 100°C) for 3 minutes, forming a first resin composition layer (25 μm thick) on the support. Next, a varnish-like resin composition 10 prepared in Preparation Example 9 was uniformly coated onto the first resin composition layer using a die coater, with the total thickness of the dried resin composition layer reaching 30 μm. The coating was dried at 80°C for 1 minute, forming a second resin composition layer. A 15 μm thick polypropylene film (Oji F-Tex Corporation "Alphan MA-411") was then bonded to the smooth side of this resin surface, creating a resin sheet 1 with a support structure of support (38 μm PET film) / first resin composition layer / second resin composition layer / protective film (MA-411). It should be noted that the thickness was measured using a contact film thickness gauge (Mitutoyo MCD-25MJ).

[0327] <Example 2: Fabrication of resin sheet 2 with support>

[0328] Instead of the resin composition 1 prepared in Preparation Example 1, the resin composition 2 prepared in Preparation Example 2 was used, and the resin sheet 2 with the support was prepared in the same manner as in Example 1.

[0329] <Example 3: Fabrication of resin sheet 3 with support>

[0330] Instead of the resin composition 1 prepared in Preparation Example 1, the resin composition 3 prepared in Preparation Example 3 was used, and the resin sheet 3 with the support was prepared in the same manner as in Example 1.

[0331] <Example 4: Fabrication of resin sheet 4 with support>

[0332] Instead of the resin composition 1 prepared in Preparation Example 1, the resin composition 4 prepared in Preparation Example 4 was used, and the resin sheet 4 with the support was prepared in the same manner as in Example 1.

[0333] <Example 5: Fabrication of resin sheet 5 with support>

[0334] Instead of the resin composition 1 prepared in Preparation Example 1, the resin composition 5 prepared in Preparation Example 5 was used, and the resin sheet 5 with the support was prepared in the same manner as in Example 1.

[0335] <Example 6: Fabrication of resin sheet 6 with support>

[0336] Instead of the resin composition 1 prepared in Preparation Example 1, the resin composition 6 prepared in Preparation Example 6 was used, and the resin sheet 6 with the support was prepared in the same manner as in Example 1.

[0337] <Example 7: Fabrication of resin sheet 7 with support>

[0338] Instead of the resin composition 1 prepared in Preparation Example 1, the resin composition 7 prepared in Preparation Example 7 was used, and the resin sheet 7 with the support was prepared in the same manner as in Example 1.

[0339] <Example 8: Fabrication of resin sheet 8 with support>

[0340] Instead of the resin composition 1 prepared in Preparation Example 1, the resin composition 8 prepared in Preparation Example 8 was used, and the resin sheet 8 with the support was prepared in the same manner as in Example 1.

[0341] <Example 9: Fabrication of resin sheet 9 with support>

[0342] Instead of the resin composition 10 prepared in Preparation Example 9, the resin composition 11 prepared in Preparation Example 10 was used, and the resin sheet 9 with the support was otherwise made in the same manner as in Example 1.

[0343] <Example 10: Fabrication of resin sheet 10 with support>

[0344] Instead of the resin composition 1 prepared in Preparation Example 1, the resin composition 13 prepared in Preparation Example 12 was used, and the resin sheet 10 with the support was otherwise made in the same manner as in Example 1.

[0345] <Comparative Example 1: Fabrication of Resin Sheet 1' with Support>

[0346] As a support, a 38 μm thick PET film (Lintec Corporation "AL5") was prepared. On this support, the varnish-like resin composition 1 prepared in Preparation Example 1 was uniformly coated using a die coater to achieve a 30 μm thickness of the dried resin composition layer. The coating was dried at 80–120°C (average 100°C) for 3 minutes. A 15 μm thick polypropylene film (Oji F-Tex Corporation "Alphan MA-411") was then laminated onto the smooth side of the resin surface to form a resin sheet 1' with a support (38 μm PET film) / resin composition layer / protective film (MA-411).

[0347] <Comparative Example 2: Fabrication of Resin Sheet 2' with Support>

[0348] Instead of the resin composition 1 prepared in Preparation Example 1, the resin composition 10 prepared in Preparation Example 9 was used, and the resin sheet 2' with the support was prepared in the same manner as in Comparative Example 1.

[0349] <Comparative Example 3: Fabrication of Resin Sheet 3' with Support>

[0350] Instead of resin composition 1 prepared in Preparation Example 1, resin composition 12 prepared in Preparation Example 11 was used, and resin sheet 3' with support was prepared in the same manner as in Example 1.

[0351] <Comparative Example 4: Fabrication of Resin Sheet 4' with Support>

[0352] Instead of the resin composition 10 prepared in Preparation Example 9, the resin composition 14 prepared in Preparation Example 13 was used, and the resin sheet 4' with the support was otherwise made in the same manner as in Example 1.

[0353] <Comparative Example 5: Fabrication of Resin Sheet 5' with Support>

[0354] The thickness of the first resin composition layer formed by resin composition 1 was changed from 25 μm to 10 μm (total thickness 30 μm), and the resin sheet 5' with the support was otherwise made in the same manner as in Example 1.

[0355] <Experimental Example 1: Evaluation of Halo Suppression>

[0356] (1) Copper-clad laminate

[0357] As a copper-clad laminate, a glass cloth substrate epoxy resin double-sided copper-clad laminate with copper foil layers on both sides is prepared (copper foil thickness 3μm, substrate thickness 0.15mm, Mitsubishi Gas Chemical Co., Ltd. "HL832NSF LCA", size 255×340mm).

[0358] (2) Lamination of resin sheets

[0359] The protective film was peeled from the resin sheets with supports prepared in the examples and comparative examples, and laminated onto both sides of the copper clad laminate using an intermittent vacuum pressure laminator (Nikko-Materials, 2-stage build-up laminator, CVP700), with the resin composition layer adjoining the copper clad laminate. The lamination was performed by depressurizing the pressure to below 13 hPa for 30 seconds, followed by pressing at 130°C and 0.74 MPa for 45 seconds. Then, hot pressing was performed at 120°C and 0.5 MPa for 75 seconds.

[0360] (3) Thermosetting of the resin composition layer

[0361] A copper-clad laminate containing resin sheets is placed in an oven at 100°C for 30 minutes, then transferred to an oven at 180°C for 30 minutes for thermosetting to form an insulating layer. The PET is then removed from the mold. This is used as the cured substrate A.

[0362] (4) CO2 laser through-hole processing

[0363] Using a CO2 laser processing machine (Mitsubishi Electric Corporation "605GTWIII(-P)"), laser light was irradiated through a metal-coated film onto an insulating layer to form multiple vias with a top diameter of approximately 40 μm on the insulating layer. The laser irradiation conditions were: mask diameter 1 mm, pulse width 16 μs, energy 0.2 mJ / emission, emission number 2, burst mode (10 kHz).

[0364] (5) Roughening treatment

[0365] The through-hole processing substrate with laser-formed vias on the insulating layer is subjected to a desmearing process as a roughening treatment. It should be noted that the following wet desmearing process is performed as the desmearing treatment.

[0366] Wet stain removal treatment:

[0367] The substrate was immersed in a swelling solution (Swelling Dip Securiganth P manufactured by Ammet Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 10 minutes, followed by immersion in an oxidizing agent solution (Concentrate Compact CP manufactured by Ammet Japan, an aqueous solution of approximately 6% potassium permanganate and approximately 4% sodium hydroxide) at 80°C for 20 minutes, and finally immersed in a neutralization solution (Reduction Solution Securiganth P manufactured by Ammet Japan, an aqueous solution of sulfuric acid) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes. This was used as roughened substrate A.

[0368] (6) Measurement of the dimensions of the through hole after roughening treatment

[0369] Roughened substrate A was used as the sample. For this roughened substrate A, cross-sectional observation was performed using a FIB-SEM composite apparatus (SMI3050SE, SIINano Technology). Specifically, using FIB (Focused Ion Beam), the insulating layer was cut to reveal a cross-section parallel to the thickness direction of the insulating layer and passing through the center of the bottom of the via. This cross-section was observed using SEM (Scanning Electron Microscopy), and the top and bottom diameters of the via were determined from the observed images.

[0370] The aforementioned measurements were performed using five randomly selected through-holes. The average of the measured top diameters of the five through-holes was then used as the top diameter Lt of the through-hole in the sample. Furthermore, the average of the measured bottom diameters of the five through-holes was used as the bottom diameter Lb of the through-hole in the sample.

[0371] (7) Measurement of the halo distance after roughening treatment

[0372] For roughened substrate A, cross-sectional observation was performed using a FIB-SEM composite apparatus (SII Nano Technology Co., Ltd., "SMI3050SE"). Specifically, using FIB (Focused Ion Beam), the insulating layer was cut to reveal a cross-section parallel to the thickness direction of the insulating layer and passing through the center of the bottom of the via. This cross-section was then observed using SEM (Scanning Electron Microscopy). The observation revealed a gap formed by the continuous peeling of the insulating layer from the copper foil layer of the inner substrate, starting from the edge of the bottom of the via. From the observed image, the distance r3 from the center of the bottom of the via to the edge of the bottom of the via (corresponding to the inner radius of the halo) and the distance r4 from the center of the bottom of the via to the more distant end of the aforementioned gap (corresponding to the outer radius of the halo) were measured. The difference between these distances r3 and r4, r4-r3, was calculated as the halo distance from the edge of the bottom of the via at the measurement location.

[0373] The aforementioned measurements were performed using five randomly selected through-holes. Subsequently, the average value of the measured halo distances of the five through-holes was taken as the halo distance Wb of the sample from the bottom edge of the through-hole.

[0374] The halo ratio Hb is calculated using the values ​​of the bottom diameter Lb of the through-hole and the halo distance Wb. The halo ratio Hb after roughening is represented as the ratio of the halo distance Wb from the edge of the bottom of the roughened through-hole to the radius (Lb / 2) of the bottom of the roughened through-hole, "Wb / (Lb / 2)". If the halo ratio Hb is below 35%, the halo suppression evaluation is judged as "○"; if the halo ratio Hb is greater than 35%, the halo suppression evaluation is judged as "×".

[0375] <Reference Example 1: Fabrication of resin sheet a with a support>

[0376] Using the resin composition 1 prepared in Preparation Example 1, a resin sheet a with a support, having a resin composition layer of 1 layer, was prepared in the same manner as in Comparative Example 1.

[0377] <Reference Example 2: Fabrication of resin sheet b with support>

[0378] Instead of resin composition 1 prepared in Preparation Example 1, resin composition 2 prepared in Preparation Example 2 was used, and resin sheet b with support was prepared in the same manner as in Reference Example 1.

[0379] <Reference Example 3: Fabrication of resin sheet c with support>

[0380] Instead of resin composition 1 prepared in Preparation Example 1, resin composition 3 prepared in Preparation Example 3 was used, and resin sheet c with support was prepared in the same manner as in Reference Example 1.

[0381] <Reference Example 4: Fabrication of resin sheet d with support>

[0382] Instead of resin composition 1 prepared in Preparation Example 1, resin composition 4 prepared in Preparation Example 4 is used, and resin sheet d with support is prepared in the same manner as in Reference Example 1.

[0383] <Reference Example 5: Fabrication of resin sheet e with support>

[0384] Instead of the resin composition 1 prepared in Preparation Example 1, the resin composition 5 prepared in Preparation Example 5 is used, and the resin sheet e with the support is otherwise made in the same manner as in Reference Example 1.

[0385] <Reference Example 6: Fabrication of a resin sheet f with a support>

[0386] Instead of the resin composition 1 prepared in Preparation Example 1, the resin composition 6 prepared in Preparation Example 6 was used, and the resin sheet f with the support was otherwise made in the same manner as in Reference Example 1.

[0387] <Reference Example 7: Fabrication of resin sheet g with support>

[0388] Instead of the resin composition 1 prepared in Preparation Example 1, the resin composition 7 prepared in Preparation Example 7 was used, and the resin sheet g with the support was otherwise prepared in the same manner as in Reference Example 1.

[0389] <Refer to Example 8: Fabrication of a resin sheet h with a support>

[0390] Instead of the resin composition 1 prepared in Preparation Example 1, the resin composition 8 prepared in Preparation Example 8 was used, and the resin sheet h with the support was otherwise made in the same manner as in Reference Example 1.

[0391] <Refer to Example 9: Fabrication of resin sheet i with support>

[0392] Instead of the resin composition 1 prepared in Preparation Example 1, the resin composition 10 prepared in Preparation Example 9 was used, and the resin sheet i with the support was otherwise made in the same manner as in Reference Example 1.

[0393] <Reference Example 10: Fabrication of resin sheet j with support>

[0394] Instead of the resin composition 1 prepared in Preparation Example 1, the resin composition 11 prepared in Preparation Example 10 was used, and the resin sheet j with the support was otherwise made in the same manner as in Reference Example 1.

[0395] <Reference Example 11: Fabrication of resin sheet k with support>

[0396] Instead of resin composition 1 prepared in Preparation Example 1, resin composition 12 prepared in Preparation Example 11 was used, and resin sheet k with support was otherwise made in the same manner as in Reference Example 1.

[0397] <Reference Example 12: Fabrication of a resin sheet l with a support>

[0398] Instead of the resin composition 1 prepared in Preparation Example 1, the resin composition 13 prepared in Preparation Example 12 was used, and the resin sheet 1 with the support was otherwise made in the same manner as in Reference Example 1.

[0399] <Reference Example 13: Fabrication of resin sheet m with support>

[0400] Instead of resin composition 1 prepared in Preparation Example 1, resin composition 14 prepared in Preparation Example 13 was used, and resin sheet m with support was otherwise prepared in the same manner as in Reference Example 1.

[0401] <Reference Test Example 1: Determination of Elastic Modulus>

[0402] The untreated side of the release PET film (Lintec Corporation "501010", 38μm thick, 240mm square) is placed on the glass cloth substrate epoxy resin double copper clad laminate (Panasonic Electric Works Corporation "R5715ES", 0.7mm thick, 255mm square) in a way that connects to the surface of the film. The four sides of the release PET film are then fixed with polyimide adhesive tape (10mm wide).

[0403] The resin sheets (167×107mm square) with supports prepared in each reference example were laminated in the center using an intermittent vacuum pressure laminator (Nikko-Materials, 2-stage laminator, CVP700), with the second resin composition layer in contact with the release surface of the release PET film. The lamination process was performed by depressurizing the air pressure to below 13 hPa for 30 seconds, followed by pressing at 100°C and 0.74 MPa for 30 seconds.

[0404] Next, the support is peeled off, and the resin sheet layer is thermo-cured at 190°C for 90 minutes.

[0405] After heat curing, the polyimide adhesive tape is peeled off, and the cured layer is removed from the epoxy resin double-sided copper-clad laminate of the glass cloth substrate. Then, the release PET film is peeled off from the cured layer to obtain a sheet-like cured product (evaluation cured product).

[0406] The cured material for evaluation was cut into dumbbell-shaped pieces (No. 1) to obtain test specimens. Tensile tests were performed on these specimens using a Tensilon universal testing machine (manufactured by A&D Corporation) according to Japanese Industrial Standard (JIS K7127), and the elastic modulus at 23°C was measured. This operation was performed three times, and the average values ​​were calculated, as shown in Table 1.

[0407] <Reference Experiment 2: Determination of Relative Permittivity and Dielectric Loss Tangent>

[0408] The resin sheets with supports prepared in each reference example were laminated onto a laminate (a copper foil etching product, MCL-E-700G, manufactured by Hitachi Chemical Co., Ltd.) using an intermittent vacuum pressure laminator (MVLP-500, Meiki Seisakusho). The lamination process involved depressurizing the pressure for 30 seconds to below 13 hPa, followed by pressing at 120°C and 0.74 MPa for 30 seconds. Then, the PET film was peeled off, and the resin composition layer was cured at 190°C for 90 minutes to obtain a cured sample.

[0409] The cured sample was cut into test pieces with a width of 2 mm and a length of 80 mm. For these test pieces, the relative permittivity and dielectric loss tangent were measured using an Agilent Technologies HP8362B resonant cavity perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23 °C. Measurements were performed on three test pieces, and the average values ​​were calculated, as shown in Table 1.

[0410] <Experimental Example 2: Evaluation of the overall dielectric loss tangent of the cured layer (insulating layer)>

[0411] Based on the dielectric loss tangent of the cured layer calculated in Reference Test Example 2, obtained by curing each resin composition layer used in the Examples and Comparative Examples, and the thickness of each resin composition layer in the Examples and Comparative Examples, the dielectric loss tangent d of the entire cured layer (insulating layer) composed of the first cured layer and the second cured layer is calculated according to the following formula. all ,

[0412] d all =d1×t1 / (t1+t2)+d2×t2 / (t1+t2)···(5)

[0413] In formula (5), t1 is the thickness of the first resin composition layer (μm), t2 is the thickness of the second resin composition layer (μm), d1 is the dielectric loss tangent of the first cured layer formed by the first resin composition layer, and d2 is the dielectric loss tangent of the second cured layer formed by the second resin composition layer.

[0414] The overall dielectric loss tangent d of the cured layer (insulating layer) all If it is below 0.0055, the evaluation of low dielectric loss tangent will be judged as "○"; if the overall dielectric loss tangent of the cured layer (insulating layer) is d all If the value is greater than 0.0055, the evaluation of low dielectric loss tangent will be judged as "×".

[0415] The amounts of raw materials used in the resin compositions of the examples and comparative examples, the thickness of the resin composition layers, the measurement results, calculation results and evaluation results of the test examples and reference test examples are shown in Table 1 below.

[0416] [Table 1]

[0417]

[0418] As shown in Table 1, in Comparative Example 2, where a single cured layer can suppress the halo phenomenon, there is a problem of a high dielectric loss tangent. On the other hand, in Comparative Example 1, where a single cured layer has a low dielectric loss tangent, the formation of halos becomes significant. Furthermore, in Comparative Example 3, where a two-layer cured layer does not satisfy condition (3), and in Comparative Example 5, where a two-layer cured layer does not satisfy condition (1), the formation of halos is suppressed, but there is a problem of a high dielectric loss tangent for the two-layer cured layer as a whole. In Comparative Example 4, where a two-layer cured layer does not satisfy condition (2), the dielectric loss tangent for the two-layer cured layer as a whole is suppressed to a low level, but the formation of halos becomes significant. In contrast, it can be seen that when using the resin composition of the present invention that satisfies all conditions (1) to (3), these problems can be overcome.

[0419] Symbol Explanation

[0420] 1. Resin sheet with support

[0421] 2 Resin sheet layer

[0422] 3 Support body

[0423] 10 First resin composition layer

[0424] 10' First Curing Layer

[0425] 20 Second resin composition layer

[0426] 20' Second curing layer

[0427] 100 insulation layer

[0428] The side of the 100U insulating layer opposite to the conductor layer.

[0429] 110 Through Hole

[0430] 120 Through Hole Bottom

[0431] 120C Center of the bottom of the through hole

[0432] 130 Through Hole Top

[0433] 140 Color-changing section

[0434] The edge of the bottom of the 150 through hole

[0435] 160 Gap

[0436] 170 The end of the outer peripheral side of the gap

[0437] Edge of the top of the 180 through hole

[0438] 190 The outer periphery of the discoloration part

[0439] 200 Inner Layer Substrate

[0440] 210 Conductor Layer

[0441] Lb is the diameter of the bottom of the through hole.

[0442] Lt is the diameter at the top of the through hole.

[0443] Wb is the distance of the halo from the bottom edge of the through-hole.

[0444] Wt is the distance of the halo from the edge of the top of the through hole.

Claims

1. A resin sheet with a support, comprising a support and a resin sheet layer disposed on the support. in, The resin sheet layers, starting from the support side, sequentially have: The first resin composition layer formed from the first resin composition, and A second resin composition layer formed by a second resin composition having a different composition from the first resin composition. When the thickness of the first resin composition layer is set to t1 μm, the thickness of the second resin composition layer is set to t2 μm, the elastic modulus of the first cured layer formed by curing the first resin composition layer at 190°C for 90 minutes is set to y1 GPa, the elastic modulus of the second cured layer formed by curing the second resin composition layer at 190°C for 90 minutes is set to y2 GPa, the dielectric loss tangent of the first cured layer is set to d1, the dielectric loss tangent of the second cured layer is set to d2, the relative permittivity of the first cured layer is set to p1, and the relative permittivity of the second cured layer is set to p2, all conditions of equations (1), (2), (3), and (4) below are satisfied. 1≤t1 / t2≤10 ・・・(1) y2 / y1≤0.70 ・・・(2) 1<d2 / d1 ・・・(3) p2 / p1 < 1 ・・・(4) The elastic modulus of the first cured layer mentioned above is the elastic modulus measured at a temperature of 23°C, and the elastic modulus of the second cured layer mentioned above is the elastic modulus measured at a temperature of 23°C. The dielectric loss tangent of the first cured layer was measured at a frequency of 5.8 GHz and a temperature of 23°C. The dielectric loss tangent of the second cured layer was also measured at a frequency of 5.8 GHz and a temperature of 23°C. The relative permittivity of the first cured layer was measured at a frequency of 5.8 GHz and a temperature of 23 °C, and the relative permittivity of the second cured layer was measured at a frequency of 5.8 GHz and a temperature of 23 °C.

2. A resin sheet with a support, comprising a support and a resin sheet layer disposed on the support. in, The resin sheet layers, starting from the support side, sequentially have: The first resin composition layer formed from the first resin composition, and A second resin composition layer formed by a second resin composition having a different composition from the first resin composition. When the thickness of the first resin composition layer is set to t1 μm, the thickness of the second resin composition layer is set to t2 μm, the elastic modulus of the first cured layer formed by curing the first resin composition layer at 190°C for 90 minutes is set to y1 GPa, the elastic modulus of the second cured layer formed by curing the second resin composition layer at 190°C for 90 minutes is set to y2 GPa, the dielectric loss tangent of the first cured layer is set to d1, and the dielectric loss tangent of the second cured layer is set to d2,... y1 is above 8.0 GPa. And it satisfies all the conditions of equations (1), (2) and (3) below. 1≤t1 / t2≤10 ・・・(1) y2 / y1≤0.70 ・・・(2) 1<d2 / d1 ・・・(3) The elastic modulus of the first cured layer mentioned above is the elastic modulus measured at a temperature of 23°C, and the elastic modulus of the second cured layer mentioned above is the elastic modulus measured at a temperature of 23°C. The dielectric loss tangent of the first cured layer was measured at a frequency of 5.8 GHz and a temperature of 23 °C, and the dielectric loss tangent of the second cured layer was measured at a frequency of 5.8 GHz and a temperature of 23 °C.

3. A resin sheet with a support, comprising a support and a resin sheet layer disposed on the support. in, The resin sheet layers, starting from the support side, sequentially have: The first resin composition layer formed from the first resin composition, and A second resin composition layer formed by a second resin composition having a different composition from the first resin composition. When the thickness of the first resin composition layer is set to t1 μm, the thickness of the second resin composition layer is set to t2 μm, the elastic modulus of the first cured layer formed by curing the first resin composition layer at 190°C for 90 minutes is set to y1 GPa, the elastic modulus of the second cured layer formed by curing the second resin composition layer at 190°C for 90 minutes is set to y2 GPa, the dielectric loss tangent of the first cured layer is set to d1, and the dielectric loss tangent of the second cured layer is set to d2,... y2 is below 3.5 GPa. And it satisfies all the conditions of equations (1), (2) and (3) below. 1≤t1 / t2≤10 ・・・(1) y2 / y1≤0.70 ・・・(2) 1<d2 / d1 ・・・(3) The elastic modulus of the first cured layer mentioned above is the elastic modulus measured at a temperature of 23°C, and the elastic modulus of the second cured layer mentioned above is the elastic modulus measured at a temperature of 23°C. The dielectric loss tangent of the first cured layer was measured at a frequency of 5.8 GHz and a temperature of 23 °C, and the dielectric loss tangent of the second cured layer was measured at a frequency of 5.8 GHz and a temperature of 23 °C.

4. A resin sheet with a support, comprising a support and a resin sheet layer disposed on the support. in, The resin sheet layers, starting from the support side, sequentially have: The first resin composition layer formed from the first resin composition, and A second resin composition layer formed by a second resin composition having a different composition from the first resin composition. The first resin composition contains a (C) free radical polymerizable compound. When the thickness of the first resin composition layer is set to t1μm, the thickness of the second resin composition layer is set to t2μm, the elastic modulus of the first cured layer formed by curing the first resin composition layer at 190℃ for 90 minutes is set to y1GPa, the elastic modulus of the second cured layer formed by curing the second resin composition layer at 190℃ for 90 minutes is set to y2GPa, the dielectric loss tangent of the first cured layer is set to d1, and the dielectric loss tangent of the second cured layer is set to d2, all conditions of the following equations (1), (2), and (3) are satisfied. 1≤t1 / t2≤10 ・・・(1) y2 / y1≤0.70 ・・・(2) 1<d2 / d1 ・・・(3) The elastic modulus of the first cured layer mentioned above is the elastic modulus measured at a temperature of 23°C, and the elastic modulus of the second cured layer mentioned above is the elastic modulus measured at a temperature of 23°C. The dielectric loss tangent of the first cured layer was measured at a frequency of 5.8 GHz and a temperature of 23 °C, and the dielectric loss tangent of the second cured layer was measured at a frequency of 5.8 GHz and a temperature of 23 °C.

5. The resin sheet with a support body according to any one of claims 1 to 4, wherein, The second resin composition contains (A) a thermosetting resin.

6. The resin sheet with a support body according to claim 5, wherein, The thermosetting resin is epoxy resin.

7. The resin sheet with a support body according to any one of claims 1 to 4, wherein, The first resin composition and the second resin composition each contain (B) an inorganic filler material.

8. The resin sheet with a support body according to claim 7, wherein, The ratio of the content of inorganic filler (B) in the second resin composition to the content of inorganic filler (B) in the first resin composition, i.e., the ratio of the second resin composition to the first resin composition, is 0.40 or less. The unit of the content is mass.

9. The resin sheet with a support body according to claim 7, wherein, The ratio of the content of inorganic filler (B) in the second resin composition to the content of inorganic filler (B) in the first resin composition, i.e., the ratio of the second resin composition to the first resin composition, is 0.30 or less. The unit of the content is mass.

10. The resin sheet with a support according to claim 7, wherein, The ratio of the content of inorganic filler (B) in the second resin composition to the content of inorganic filler (B) in the first resin composition, i.e., the ratio of the second resin composition to the first resin composition, is 0.20 or more. The unit of the content is mass.

11. The resin sheet with a support according to claim 7, wherein, The ratio of the content of inorganic filler (B) in the second resin composition to the content of inorganic filler (B) in the first resin composition, i.e., the ratio of the second resin composition to the first resin composition, is 0.25 or more. The unit of the content is mass.

12. The resin sheet with a support according to any one of claims 1 to 4, wherein, The first resin composition contains a (C) free radical polymerizable compound.

13. The resin sheet with a support according to any one of claims 1 to 4, wherein, In the condition of equation (2), y2 / y1 is greater than or equal to 0.

25.

14. The resin sheet with a support according to any one of claims 1 to 4, wherein, In the condition of equation (2), y2 / y1 is greater than 0.

28.

15. The resin sheet with a support according to any one of claims 1 to 4, wherein, In the condition of equation (2), y2 / y1 is less than 0.

45.

16. The resin sheet with a support according to any one of claims 1 to 4, wherein, In the condition of equation (2), y2 / y1 is less than 0.

40.

17. The resin sheet with a support according to any one of claims 1 to 4, wherein, In the condition of equation (3), d2 / d1 is less than 5.

18. The resin sheet with a support according to any one of claims 1 to 4, wherein, In the condition of equation (3), d2 / d1 is less than 4.

19. The resin sheet with a support according to any one of claims 1 to 4, wherein, In the condition of equation (3), d2 / d1 is 2 or more.

20. The resin sheet with a support according to claim 19, wherein, In the condition of equation (3), d2 / d1 is greater than 2.

5.

21. The resin sheet with a support according to claim 19, wherein, In the condition of equation (3), d2 / d1 is 3 or more.

22. The resin sheet with a support according to any one of claims 1 to 4, wherein, The elastic modulus y1 of the first cured layer is below 12.0 GPa.

23. The resin sheet with a support according to any one of claims 1 to 4, wherein, The elastic modulus y1 of the first cured layer is below 11.5 GPa.

24. The resin sheet with a support according to any one of claims 1 to 4, wherein, The elastic modulus y1 of the first cured layer is above 8.0 GPa.

25. The resin sheet with a support according to any one of claims 1 to 4, wherein, The elastic modulus y1 of the first cured layer is above 8.5 GPa.

26. The resin sheet with a support according to any one of claims 1 to 4, wherein, The elastic modulus y2 of the second cured layer is below 3.5 GPa.

27. The resin sheet with a support according to any one of claims 1 to 4, wherein, The elastic modulus y2 of the second cured layer is below 3.3 GPa.

28. The resin sheet with a support according to any one of claims 1 to 4, wherein, The elastic modulus y2 of the second cured layer is above 2.5 GPa.

29. The resin sheet with a support according to any one of claims 1 to 4, wherein, The elastic modulus y2 of the second cured layer is above 3.0 GPa.

30. The resin sheet with a support according to any one of claims 1 to 4, wherein, The dielectric loss tangent d1 of the first cured layer is below 0.

004.

31. The resin sheet with a support according to any one of claims 1 to 4, wherein, The dielectric loss tangent d1 of the first cured layer is below 0.

003.

32. The resin sheet with a support according to any one of claims 1 to 4, wherein, The dielectric loss tangent d2 of the second cured layer is below 0.

010.

33. The resin sheet with a support according to any one of claims 1 to 4, wherein, The dielectric loss tangent d2 of the second cured layer is below 0.

008.

34. The resin sheet with a support according to any one of claims 1 to 4, wherein, When the relative permittivity of the first cured layer is set to p1 and the relative permittivity of the second cured layer is set to p2, the following condition (4) is further satisfied. p2 / p1 < 1 ・・・(4) The relative permittivity of the first cured layer was measured at a frequency of 5.8 GHz and a temperature of 23 °C, and the relative permittivity of the second cured layer was measured at a frequency of 5.8 GHz and a temperature of 23 °C.

35. The resin sheet with a support according to claim 34, wherein, In the conditions of equation (4), p2 / p1 is less than 0.

95.

36. The resin sheet with a support according to any one of claims 1 to 4, wherein, The dielectric loss tangent d of the entire cured layer consisting of the first and second cured layers, calculated by the following equation (5), is given by equation (5). all Below 0.005 d all =d1×t1 / (t1+t2)+d2×t2 / (t1+t2) ・・・(5)。 37. The resin sheet with a support according to claim 36, wherein, In the condition of equation (5), d all It is below 0.

004.

38. A solidified material having: The first cured layer formed by the cured product of the first resin composition, and A second cured layer is formed on the first cured layer by a cured product of a second resin composition having a different composition from the first resin composition. The first resin composition contains a (C) free radical polymerizable compound. Let the thickness of the first cured layer be t. 1' μm, set the thickness of the second curing layer to t 2' When the elastic modulus of the first cured layer is set to y1 GPa, the elastic modulus of the second cured layer is set to y2 GPa, the dielectric loss tangent of the first cured layer is set to d1, the dielectric loss tangent of the second cured layer is set to d2, the relative permittivity of the first cured layer is set to p1, and the relative permittivity of the second cured layer is set to p2, all the conditions of the following equations (1'), (2), (3), and (4) are satisfied. 1≤t 1' / t 2' ≤10 ・・・(1') y2 / y1≤0.70 ・・・(2) 1<d2 / d1 ・・・(3) p2 / p1 < 1 ・・・(4) The elastic modulus of the first cured layer mentioned above is the elastic modulus measured at a temperature of 23°C, and the elastic modulus of the second cured layer mentioned above is the elastic modulus measured at a temperature of 23°C. The dielectric loss tangent of the first cured layer was measured at a frequency of 5.8 GHz and a temperature of 23°C. The dielectric loss tangent of the second cured layer was also measured at a frequency of 5.8 GHz and a temperature of 23°C. The relative permittivity of the first cured layer was measured at a frequency of 5.8 GHz and a temperature of 23 °C, and the relative permittivity of the second cured layer was measured at a frequency of 5.8 GHz and a temperature of 23 °C.

39. A solidified material having: The first cured layer formed by the cured product of the first resin composition, and A second cured layer is formed on the first cured layer by a cured product of a second resin composition having a different composition from the first resin composition. Let the thickness of the first cured layer be t. 1' μm, set the thickness of the second curing layer to t 2' When the elastic modulus of the first cured layer is set to y1 GPa, the elastic modulus of the second cured layer is set to y2 GPa, the dielectric loss tangent of the first cured layer is set to d1, and the dielectric loss tangent of the second cured layer is set to d2, μm, ... y1 is above 8.0 GPa. And it satisfies all the conditions of the following equations (1'), (2) and (3). 1≤t 1' / t 2' ≤10 ・・・(1') y2 / y1≤0.70 ・・・(2) 1<d2 / d1 ・・・(3) The elastic modulus of the first cured layer mentioned above is the elastic modulus measured at a temperature of 23°C, and the elastic modulus of the second cured layer mentioned above is the elastic modulus measured at a temperature of 23°C. The dielectric loss tangent of the first cured layer was measured at a frequency of 5.8 GHz and a temperature of 23 °C, and the dielectric loss tangent of the second cured layer was measured at a frequency of 5.8 GHz and a temperature of 23 °C.

40. A solidified material having: The first cured layer formed by the cured product of the first resin composition, and A second cured layer is formed on the first cured layer by a cured product of a second resin composition having a different composition from the first resin composition. Let the thickness of the first cured layer be t. 1' μm, set the thickness of the second curing layer to t 2' When the elastic modulus of the first cured layer is set to y1 GPa, the elastic modulus of the second cured layer is set to y2 GPa, the dielectric loss tangent of the first cured layer is set to d1, and the dielectric loss tangent of the second cured layer is set to d2, μm, ... y2 is below 3.5 GPa. And it satisfies all the conditions of the following equations (1'), (2) and (3). 1≤t 1' / t 2' ≤10 ・・・(1') y2 / y1≤0.70 ・・・(2) 1<d2 / d1 ・・・(3) The elastic modulus of the first cured layer mentioned above is the elastic modulus measured at a temperature of 23°C, and the elastic modulus of the second cured layer mentioned above is the elastic modulus measured at a temperature of 23°C. The dielectric loss tangent of the first cured layer was measured at a frequency of 5.8 GHz and a temperature of 23 °C, and the dielectric loss tangent of the second cured layer was measured at a frequency of 5.8 GHz and a temperature of 23 °C.

41. A solidified material having: The first cured layer formed by the cured product of the first resin composition, and A second cured layer is formed on the first cured layer by a cured product of a second resin composition having a different composition from the first resin composition. The first resin composition contains a (C) free radical polymerizable compound. Let the thickness of the first cured layer be t. 1' μm, set the thickness of the second curing layer to t 2' When the elastic modulus of the first cured layer is set to y1 GPa, the elastic modulus of the second cured layer is set to y2 GPa, the dielectric loss tangent of the first cured layer is set to d1, and the dielectric loss tangent of the second cured layer is set to d2, all the conditions of the following equations (1'), (2), and (3) are satisfied. 1≤t 1' / t 2' ≤10 ・・・(1') y2 / y1≤0.70 ・・・(2) 1<d2 / d1 ・・・(3) The elastic modulus of the first cured layer mentioned above is the elastic modulus measured at a temperature of 23°C, and the elastic modulus of the second cured layer mentioned above is the elastic modulus measured at a temperature of 23°C. The dielectric loss tangent of the first cured layer was measured at a frequency of 5.8 GHz and a temperature of 23 °C, and the dielectric loss tangent of the second cured layer was measured at a frequency of 5.8 GHz and a temperature of 23 °C.

42. A printed wiring board having an insulating layer formed from the cured material according to any one of claims 38 to 41.

43. A semiconductor device comprising the printed wiring board of claim 42.

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