JP6627575B2 - Resin sheet with support - Google Patents

Description

  The present invention relates to a resin sheet with a support. Furthermore, the present invention relates to a printed wiring board and a semiconductor device.

  As a method of manufacturing a printed wiring board (hereinafter, also referred to as a “wiring board”), a build-up method in which a conductor layer and an insulating layer on which a circuit is formed are alternately stacked is widely used. It is known that the resin composition layer is formed by curing a resin composition layer composed of two layers, a side in contact with the layer and a side to be plated (for example, see Patent Document 1).

JP 2014-17301A

  In recent years, as the amount of information communication has increased, the number of components mounted on the printed wiring board has been increasing, and with this, the heat history due to the reflow process given to the insulating layer in the printed wiring board has been increasing. I have.

  In addition, due to an increase in demand for small high-performance electronic devices in recent years, heat history due to reflow processing per unit volume of an insulating layer is also increasing.

  The present inventors have found that an insulating layer formed by curing a two-layered resin composition layer has increased thermal history, so that delamination (delamination) occurs at the interface between each cured resin composition layer. Have been found to occur.

  An object of the present invention is to provide a resin sheet with a support, a printed wiring board, and a semiconductor device that can suppress the occurrence of delamination occurring at the interface between each cured resin composition layer even if the heat history due to the reflow treatment increases. The task is to

  The present inventors have conducted intensive studies on the above problems, and as a result, have found that the difference between the moisture permeability coefficient of the thermoset of the first resin composition layer and the moisture permeability coefficient of the thermoset of the second resin composition layer is small. Further, the average linear thermal expansion coefficient (hereinafter referred to as “average linear thermal expansion coefficient”, “thermal expansion coefficient”, “thermal expansion coefficient”) of the thermosetting product of the resin sheet composed of the first and second resin composition layers , Or "CTE") of 30 ppm / ° C. or less, it is possible to suppress the occurrence of delamination occurring at the interface of each cured resin composition layer, even if the thermal history increases, and find the present invention. It was completed.

That is, the present invention includes the following contents.
[1] A resin sheet with a support, comprising: a support; and a resin sheet provided on the support,
A resin sheet, a first resin composition layer formed of the first resin composition, provided on the support side;
A second resin composition layer formed of the second resin composition, provided on the side opposite to the support side,
The compositions of the first resin composition and the second resin composition are different from each other,
Moisture permeability coefficient M1 of the first thermosetting product obtained by heat-curing the first resin composition at 200 ° C. for 90 minutes, and second moisture-curing coefficient M1 obtained by thermosetting the second resin composition at 200 ° C. for 90 minutes. The difference from the moisture permeability coefficient M2 of the thermosetting product of No. 2 is 0 to 4 (g / mm / m ² / 24h),
A resin sheet with a support, wherein the thermosetting product obtained by thermosetting the resin sheet at 200 ° C. for 90 minutes has an average linear thermal expansion coefficient of 30 ppm / ° C. or less.
[2] The resin sheet with a support according to [1], wherein the thickness of the resin sheet is 30 μm or less.
[3] The resin sheet with a support according to [1] or [2], wherein the thickness of the first resin composition layer is 5 μm or less.
[4] The resin sheet with a support according to any one of [1] to [3], wherein M1 and M2 satisfy a relationship of M1> M2.
[5] The resin sheet with a support according to any one of [1] to [4], wherein M1 is 2 (g / mm / m ² / 24h) or more.
[6] The second resin composition contains an inorganic filler, and the content of the inorganic filler is 60% by mass or more when the nonvolatile component in the second resin composition is 100% by mass. The resin sheet with a support according to any one of [1] to [5].
[7] The first resin composition contains a thermoplastic resin, and the content of the thermoplastic resin is 10% by mass or more when the nonvolatile component in the first resin composition is 100% by mass. The resin sheet with a support according to any one of [1] to [6].
[8] The resin sheet with a support according to any one of [1] to [7], wherein the difference between M1 and M2 is 3 (g / mm / m ² / 24h) or less.
[9] The first and second resin compositions contain an inorganic filler, the average particle diameter of the inorganic filler in the first resin composition is R1 (μm), and the inorganic filler in the second resin composition is The resin with a support according to any one of [1] to [8], wherein the ratio of R1 to R2 (R2 / R1) is 1 to 15 when the average particle size of the filler is R2 (μm). Sheet.
[10] The first resin composition and the second resin composition include an inorganic filler, the content of the inorganic filler in the first resin composition is A1 (% by mass), and the second resin composition The resin sheet with a support according to any one of [1] to [9], which satisfies the relationship of A1 <A2 when the content of the inorganic filler in the material is A2 (% by mass).
[11] The resin sheet with a support according to any one of [1] to [10], which is for forming an insulating layer of a printed wiring board.
[12] A printed wiring board including an insulating layer formed of the resin sheet with a support according to any one of [1] to [10].
[13] A semiconductor device comprising the printed wiring board according to [12].

  According to the present invention, it is possible to provide a resin sheet with a support, a printed wiring board, and a semiconductor device that can suppress the occurrence of delamination occurring at the interface of each cured resin composition layer even when the heat history increases. Now you can.

FIG. 1 is a schematic view showing one embodiment of the resin sheet with a support of the present invention.

  Hereinafter, the resin sheet with a support, the printed wiring board, and the semiconductor device of the present invention will be described in detail.

  Before describing the resin sheet with a support of the present invention in detail, when forming the first resin composition layer and the second resin composition layer included in the resin sheet in the resin sheet with a support of the present invention, The first resin composition and the second resin composition used for the following will be described.

(First resin composition)
The first resin composition forming the first resin composition layer is not particularly limited as long as the cured product has sufficient insulating properties. Examples of the first resin composition include a composition containing a curable resin and a curing agent thereof. As the curable resin, a conventionally known curable resin used when forming an insulating layer of a printed wiring board can be used, and among them, an epoxy resin is preferable. Thus, in one embodiment, the first resin composition includes (a) an epoxy resin, (b) a curing agent, and (c) an inorganic filler. The first resin composition may further contain a thermoplastic resin, a curing accelerator, a flame retardant, and an organic filler, if necessary.

  Hereinafter, each component that can be used as a material of the first resin composition will be described in detail.

-(A) Epoxy resin-
As the epoxy resin, 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, trisphenol type epoxy resin, Naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak Epoxy resin, biphenyl epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, complex Wherein the epoxy resin, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. The epoxy resins may be used alone or in combination of two or more. The component (a) is preferably an aromatic skeleton-containing epoxy resin from the viewpoint of reducing the average linear thermal expansion coefficient, and is a bisphenol A epoxy resin, a bisphenol F epoxy resin, a naphthalene epoxy resin, a biphenyl epoxy resin, and a diphenyl epoxy resin. It is preferably at least one selected from cyclopentadiene type epoxy resins. The aromatic skeleton is a chemical structure generally defined as aromatic, and also includes polycyclic aromatic and heteroaromatic rings.

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

  As the liquid 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, glycidylamine type epoxy resin, phenol novolak type epoxy resin, ester skeleton Alicyclic epoxy resin, cyclohexane dimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having a butadiene structure are preferable. Glycidylamine type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF Epoxy resins and naphthalene epoxy resins are more preferred. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, and “HP4032SS” (naphthalene epoxy resin) manufactured by DIC Corporation, “828US”, “jER828EL”, and “825” manufactured by Mitsubishi Chemical Corporation. "," Epicoat 828EL "(bisphenol A type epoxy resin)," jER807 "," 1750 "(bisphenol F type epoxy resin)," jER152 "(phenol novolak type epoxy resin)," 630 "," 630LSD "(glycidylamine) Epoxy resin), Nippon Steel & Sumitomo Chemical Co., Ltd. “ZX1059” (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), “EX-721” (Nishigake Chemtex Co., Ltd.) (glycidyl ester type) Epoxy resin), manufactured by Daicel Corporation "Celoxide 2021P" (an alicyclic epoxy resin having an ester skeleton), "PB-3600" (an epoxy resin having a butadiene structure), "ZX1658" and "ZX1658GS" (manufactured by Nippon Steel Chemical Co., Ltd.) 4-glycidylcyclohexane) and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used alone or in combination of two or more.

  Examples of the solid epoxy resin include a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferred, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferred. Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), and “N-690” manufactured by DIC Corporation. (Cresol novolak type epoxy resin), "N-695" (cresol novolak type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP-7200HH", "HP-7200H", "EXA" -7311 "," EXA-7311-G3 "," EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(naphthylene ether type epoxy resin)," EPPN "manufactured by Nippon Kayaku Co., Ltd. -502H "(trisphenol type epoxy resin)," NC7000L "(naphthol novolak type) NC3000H), "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "ESN485" (naphthol novolak) Epoxy resin), “YX4000H”, “YX4000”, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YX8800” (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation. "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF type epoxy resin), "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, Mitsubishi “JER1010” manufactured by Chemical Co., Ltd. (Solid bisphenol A type epoxy resin), "jER1031S" (tetraphenyl ethane epoxy resin) and the like. These may be used alone or in combination of two or more.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the ratio by weight (liquid epoxy resin: solid epoxy resin) is in the range of 0: 0.1 to 1:15 by mass ratio. preferable. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within the above range, i) moderate adhesiveness is obtained when used in the form of a resin sheet. Ii) When used in the form of a resin sheet In addition, effects such as improved flexibility, improved handleability, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the above effects i) to iii), the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 1 to 1:10. Preferably, the range of 1: 1.1 to 1: 8 is more preferable.

  The content of the epoxy resin in the first resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. 3% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention are exerted, but is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less.

  In the present invention, the content of each component in the resin composition is a value when the nonvolatile component in the resin composition is 100% by mass, unless otherwise specified.

  The epoxy equivalent of the epoxy resin is preferably 50 to 5,000, more preferably 50 to 3,000, further preferably 80 to 2,000, and still more preferably 110 to 1,000. Within this range, the crosslinked density of the cured product becomes sufficient and an insulating layer with small surface roughness can be obtained. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing one equivalent of an epoxy group.

  The weight average molecular weight of the epoxy resin is preferably from 100 to 5000, more preferably from 250 to 3000, and still more preferably from 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

-(B) Curing agent-
The curing agent is not particularly limited as long as it has a function of curing the epoxy resin.For example, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, and And carbodiimide-based curing agents. One type of curing agent may be used alone, or two or more types may be used in combination. The component (b) is preferably at least one selected from a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a carbodiimide-based curing agent, and a cyanate ester-based curing agent.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Above all, a phenol novolak curing agent containing a triazine skeleton is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to a conductor layer.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7851”, “MEH-7851H” and “MEH-7851H” manufactured by Meiwa Kasei Co., Ltd. "NHN", "CBN", "GPH" manufactured by Yakuhin Co., Ltd., "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN170" manufactured by Nippon Steel & Sumitomo Metal Corporation. “SN-375”, “SN-395”, “TD-2090”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “LA-3018” manufactured by DIC Corporation. , “EXB-9500” and the like.

  From the viewpoint of obtaining an insulating layer having excellent adhesion to the conductor layer, an active ester-based curing agent is also preferable. The active ester-based curing agent is not particularly limited, but generally has one molecule of an ester group having a high reaction activity, such as a phenol ester, a thiophenol ester, an N-hydroxyamine ester, or an ester of a heterocyclic hydroxy compound. Compounds having two or more of them are preferably used. The active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Examples include benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolak, and the like. Here, the “dicyclopentadiene-type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

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

  Commercially available active ester curing agents include, as active ester compounds having a dicyclopentadiene-type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-". "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound having a naphthalene structure; "EXB-8000L-65TM" (manufactured by DIC Corporation); and an active ester compound containing an acetylated phenol novolak. “DC808” (manufactured by Mitsubishi Chemical Corporation), “YLH1026” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated phenol novolak, and “DC808” as an active ester-based curing agent that is an acetylated phenol novolak ”( YLH1026 (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based curing agent which is a benzoylated phenol novolak. Chemical Co., Ltd.).

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

  Examples of the cyanate ester-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4 '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether; phenol Novolak and ku Polyfunctional cyanate resin derived from tetrazole novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of cyanate ester-based curing agents include “PT30” and “PT60” (both are phenol novolac-type polyfunctional cyanate ester resins), “BA230” and “BA230S75” (manufactured by Lonza Japan Co., Ltd.). A prepolymer in which a part or the whole is triazine-modified to form a trimer).

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

  The amount ratio between the epoxy resin and the curing agent is preferably in the range of 1: 0.01 to 1: 2 in a ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of curing agent], 1: 0.015 to 1: 1.5 is more preferred, and 1: 0.02 to 1: 1 is even more preferred. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, and differs depending on the type of the curing agent. Further, the total number of epoxy groups of the epoxy resin is a value obtained by summing the value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is The value obtained by dividing the mass of the solid content of each curing agent by the equivalent of the reactive group is the sum of all the curing agents. By setting the ratio between the epoxy resin and the curing agent in such a range, the heat resistance of the cured product of the resin composition is further improved.

  In one embodiment, the first resin composition contains the above-mentioned (a) epoxy resin and (b) curing agent. The resin composition comprises (a) a mixture of a liquid epoxy resin and a solid epoxy resin as the epoxy resin (the mass ratio of the liquid epoxy resin to the solid epoxy resin is preferably from 0: 0.1 to 1:15, more preferably 0: 0.3 to 1:12, more preferably 0: 0.6 to 1:10), and (b) a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and a carbodiimide-based curing agent as the curing agent. It is preferable to include at least one selected from the group consisting of an agent and a cyanate ester-based curing agent.

  The content of the curing agent in the first resin composition is not particularly limited, but is preferably 45% by mass or less, more preferably 43% by mass or less, and further preferably 40% by mass or less. The lower limit is not particularly limited, but is preferably 10% by mass or more, more preferably 15% by mass or more.

-(C) Inorganic filler-
Although the material of the inorganic filler is not particularly limited, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, silicon carbide and the like. Among these, silicon carbide and silica are preferred, and silica is particularly preferred. As the silica, spherical silica is preferable. One kind of the inorganic filler may be used alone, or two or more kinds may be used in combination.

  The average particle size of the inorganic filler is not particularly limited, but is preferably 2 μm or less, more preferably 1.5 μm or less, and still more preferably 1 μm, from the viewpoint of obtaining an insulating layer having a small surface roughness and improving the fine wiring formability. It is as follows. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.1 μm or more, and still more preferably 0.3 μm or more. Commercially available inorganic fillers having such an average particle size include, for example, "UFP-30" manufactured by Denka Corporation, "SPH516-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd., and Shinano Electric Smelting Co., Ltd. SER-A06).

  The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured on a volume basis using a laser diffraction scattering type particle size distribution measuring device, and the median diameter can be measured by setting the average particle size. As the measurement sample, one obtained by dispersing an inorganic filler in methyl ethyl ketone by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring device, “SALD-2200” manufactured by Shimadzu Corporation can be used.

  The inorganic filler is preferably surface-treated with at least one surface treatment agent of a silane coupling agent, an alkoxysilane compound, and an organosilazane compound, from the viewpoint of improving moisture resistance and dispersibility. These may be oligomers. Examples of the surface treatment agent include an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an organosilazane compound, and a titanate-based coupling agent. Commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and "KBM803" (3-mercaptopropyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type) Silane coupling agent). The surface treatment agent may be used alone or in combination of two or more.

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

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

  The content of the inorganic filler in the first resin composition is preferably 70% by mass or less, when the nonvolatile component in the first resin composition is 100% by mass, from the viewpoint of improving plating peel strength. It is more preferably at most 50% by mass, further preferably at most 45% by mass. The lower limit of the content of the component (c) in the first resin composition is not particularly limited and may be 0% by mass, but is usually 5% by mass or more, 10% by mass or more, 20% by mass or more. And

-(D) Thermoplastic resin-
The first resin composition may contain (d) a thermoplastic resin in addition to the components (a) to (c).

  As the thermoplastic resin, for example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyether Examples thereof include an ether ketone resin and a polyester resin, and a phenoxy resin is preferable. The thermoplastic resins may be used alone or in combination of two or more.

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

  Examples of the phenoxy resin include a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolak skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, and a terpene. Phenoxy resins having one or more skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group. The phenoxy resins may be used alone or in combination of two or more. Specific examples of the phenoxy resin include “1256” and “4250” (both phenoloxy resins containing a bisphenol A skeleton), “YX8100” (phenoxy resin containing a bisphenol S skeleton), and “YX6954” (produced by Mitsubishi Chemical Corporation). Bisphenol acetophenone skeleton-containing phenoxy resin), as well as "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "YX6954BH30", "YX7553", "YX7553BH30" manufactured by Mitsubishi Chemical Corporation. "YL7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7891BH30", "YL7482" and the like.

  Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, “Electric Butyral 4000-2”, “Electric Butyral 5000-A”, “Electric Butyral 6000-C”, “Electric Butyral 6000-EP”, and Sekisui Water manufactured by Denka Corporation. S-LEC BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, BM series, etc., manufactured by Chemical Industry Co., Ltd. are exemplified.

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

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

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

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

  Specific examples of the polyphenylene ether resin include oligophenylene ether / styrene resin “OPE-2St1200” manufactured by Mitsubishi Gas Chemical Company, Ltd.

  Among them, a phenoxy resin and a polyvinyl acetal resin are preferable as the thermoplastic resin. Accordingly, in one preferred embodiment, the thermoplastic resin comprises one or more selected from the group consisting of phenoxy resins and polyvinyl acetal resins.

  When the first resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 5% by mass or more, more preferably 8% by mass or more, and still more preferably 10% by mass or more. The upper limit is not particularly limited, but may be preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less.

-(E) Curing accelerator-
The first resin composition may contain (e) a curing accelerator in addition to the components (a) to (c).

  Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, and a metal-based curing accelerator. A curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are preferred, and an amine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are more preferred. The curing accelerator may be used alone or in combination of two or more.

  Examples of the phosphorus-based curing accelerator include triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate And tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

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

  Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2 Phenylimidazolium trimellitate, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-Ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyi Imidazole compounds such as -3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline; and adducts of imidazole compounds and epoxy resins; 2-ethyl-4-methylimidazole, 1-benzyl-2- Phenylimidazole is preferred.

  As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation.

  Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

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

  The content of the curing accelerator in the first resin composition is not particularly limited, but is preferably 0.01% by mass to 3% by mass when the nonvolatile components of the epoxy resin and the curing agent are 100% by mass.

-(F) Flame retardant-
The first resin composition may include (f) a flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. The flame retardants may be used alone or in combination of two or more.

  As the flame retardant, commercially available products may be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd. and "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd.

  When the first resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, More preferably, the content is 0.5% by mass to 10% by mass.

-(G) Organic filler-
The resin composition may include (g) an organic filler from the viewpoint of improving elongation. As the organic filler, any organic filler that can be used when forming an insulating layer of a printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles.

  As the rubber particles, commercially available products may be used, for example, “EXL2655” manufactured by Dow Chemical Japan Co., Ltd., and “AC3816N” manufactured by Ganz Chemical Co., Ltd.

  When the first resin composition contains an organic filler, the content of the organic filler is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass, and still more preferably. Is from 0.3% by mass to 5% by mass, or from 0.5% by mass to 3% by mass.

-(H) Optional additives-
The first resin composition may further contain other additives, if necessary. Examples of such other additives include organic copper compounds, organic zinc compounds and organic cobalt compounds. Examples include metal compounds and resin additives such as thickeners, defoamers, leveling agents, adhesion promoters, and colorants.

  In addition, from the viewpoint of manufacturing a flexible printed wiring board, the first resin composition preferably further contains a polyimide resin having a polybutadiene structure, a urethane structure, an imide structure, and a phenol structure at a molecular terminal in the molecule. . When the polyimide resin is contained, the content is preferably 10% by mass to 85% by mass, more preferably 12% by mass to 50% by mass, and still more preferably 15% by mass to 30% by mass.

  For details of the polyimide, the description in WO 2008/153208 can be referred to, and the contents thereof are incorporated herein.

(Second resin composition)
The second resin composition forming the second resin composition layer is not particularly limited as long as the composition is different from that of the first resin composition, and the second resin composition includes an inorganic filler. Those containing an inorganic filler, an epoxy resin, and a curing agent are more preferable.

  Examples of the inorganic filler in the second resin composition include the same inorganic fillers as described in the section (First resin composition).

  As the second resin composition, from the viewpoint of obtaining an insulating layer having a low average coefficient of linear thermal expansion, the content of the inorganic filler when the nonvolatile component in the second resin composition is 100% by mass is preferable. Is 60% by mass or more, more preferably 65% by mass or more, and still more preferably 67% by mass or more. The upper limit of the content of the inorganic filler in the second resin composition is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 80% by mass or less.

  When the content of the inorganic filler in the first resin composition is A1 (% by mass) and the content of the inorganic filler in the second resin composition is A2 (% by mass), the relationship of A1 <A2 is satisfied. It is preferable to satisfy the following. The difference between A1 and A2 (A2-A1) is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more. The upper limit of the difference (A2-A1) is not particularly limited, but may be usually 90% by mass or less, 80% by mass or less, or the like.

  The average particle size of the inorganic filler in the second resin composition is not particularly limited, but is preferably 2.5 μm or less, more preferably 2.0 μm or less, and still more preferably 1.5 μm from the viewpoint of improving the embedding property. It is as follows. The lower limit of the average particle size is not particularly limited, but is preferably 0.1 μm or more, more preferably 0.5 μm or more, and further preferably 1.0 μm or more. Commercially available inorganic fillers having such an average particle size include, for example, “SP60-05” and “SP507-05” manufactured by Nippon Steel & Sumikin Materials Co., Ltd., “YC100C” manufactured by Admatechs, and “ "YA050C", "YA050C-MJE", "YA010C", "UFP-30" manufactured by Denka Co., Ltd., "Silfill NSS-3N", "Silfill NSS-4N", "Silfill NSS-5N", manufactured by Tokuyama Corporation. "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" and the like manufactured by Admatechs Co., Ltd.

  When the average particle size of the inorganic filler in the first resin composition is R1 (μm) and the average particle size of the inorganic filler in the second resin composition is R2 (μm), the relationship of R1 ≦ R2 is satisfied. It is preferable to satisfy the following. The ratio of R1 and R2 (R2 / R1) is preferably 1 or more, more preferably 1.1 or more, further preferably 1.5 or more, or 2 or more. The upper limit of R2 / R1 is not particularly limited, but is preferably 15 or less, more preferably 10 or less, and further preferably 8 or less. For example, when a plurality of inorganic fillers are contained in the first resin composition, the average value of the average particle diameters of the plurality of inorganic fillers is R1 (the same applies to the second resin composition). ).

  In one embodiment, the second resin composition includes an epoxy resin and a curing agent together with the inorganic filler. The second resin composition may further contain additives such as a thermoplastic resin, a curing accelerator, a flame retardant, and an organic filler as needed.

  The epoxy resin, the curing agent and the additives contained in the second resin composition are the same as the (b) epoxy resin, (c) the curing agent and the additives described in the section (first resin composition). Is mentioned.

  The content of the epoxy resin in the second resin composition is preferably 0.1% by mass or more, more preferably 5% by mass or more, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. It is preferably at least 10% by mass. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention are exerted, but is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 22% by mass or less. Therefore, the content of the epoxy resin (a) in the second resin composition is preferably 0.1 to 30% by mass, more preferably 5 to 25% by mass, and still more preferably 8 to 22% by mass.

  When the content of the epoxy resin in the first resin composition is B1 (% by mass) and the content of the epoxy resin in the second resin composition is B2 (% by mass), the relationship of B1> B2 is satisfied. Is preferred. The difference between B1 and B2 (B1-B2) is preferably 5% by mass or more, more preferably 8% by mass or more, and further preferably 10% by mass or more. Although the upper limit of the difference (B1-B2) is not particularly limited, it can usually be 60% by mass or less, 50% by mass or less.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the ratio by weight (liquid epoxy resin: solid epoxy resin) is in the range of 0: 0.1 to 1:15 by mass ratio. preferable. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within the above range, i) moderate adhesiveness is obtained when used in the form of a resin sheet. Ii) When used in the form of a resin sheet In addition, effects such as improved flexibility, improved handleability, and iii) a cured product having sufficient breaking strength can be obtained. In light of the effects of i) to iii), the ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably in the range of 1: 1 to 1:10, and more preferably 1: 1 to 1:10. The range of 1.1 to 1: 8 is more preferable.

  The preferred ranges of the epoxy equivalent of the epoxy resin and the weight average molecular weight of the epoxy resin in the second resin composition are the same as those of the epoxy resin contained in the first resin composition.

  The content of the curing agent in the second resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably from the viewpoint of obtaining an insulating layer having a low dielectric loss tangent. 5 mass% or more. The upper limit of the content of the curing agent is not particularly limited as long as the effects of the present invention are exerted, but is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 12% by mass or less. Therefore, the content of the curing agent in the second resin composition is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 5 to 12% by mass.

  The amount ratio between the epoxy resin and the curing agent in the second resin composition is 1: 0.2 in the ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of curing agent]. The range is preferably from 1: 2 to 1: 2, more preferably from 1: 0.3 to 1: 1.5, and still more preferably from 1: 0.4 to 1: 1. By setting the ratio between the epoxy resin and the curing agent in such a range, the heat resistance of the cured product of the second resin composition is further improved.

  The content of the thermoplastic resin in the second resin composition is not particularly limited, but is preferably 0% by mass to 10% by mass, more preferably 0.2% by mass to 8% by mass, and still more preferably 0.5% by mass to 8% by mass. % By mass to 5% by mass.

  The content of the curing accelerator in the second resin composition is not particularly limited, but is preferably used in the range of 0.001% by mass to 3% by mass.

  The content of the flame retardant in the second resin composition is not particularly limited, but is preferably 0.2% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and still more preferably 0.8% by mass. The content is more preferably from 10% by mass to 10% by mass.

  The content of the organic filler in the second resin composition is preferably from 0.1% by mass to 20% by mass, more preferably from 0.2% by mass to 10% by mass.

  The second resin composition, like the first resin composition, may optionally contain any additives, for example, organic copper compounds, organic metal compounds such as organic zinc compounds and organic cobalt compounds, and organic fillers. It may contain a resin additive such as a thickener, an antifoaming agent, a leveling agent, an adhesion-imparting agent, and a coloring agent.

[Resin sheet with support]
The resin sheet with a support of the present invention is a resin sheet with a support including a support and a resin sheet provided on the support, wherein the resin sheet is a first resin sheet provided on the support side. A first resin composition layer formed of a resin composition, and a second resin composition layer formed of a second resin composition provided on the side opposite to the support side, The compositions of the first resin composition and the second resin composition are different from each other, and the moisture permeability coefficient M1 of the first thermosetting product obtained by thermosetting the first resin composition at 200 ° C. for 90 minutes is different from that of the first resin composition. The difference from the moisture permeability coefficient M2 of the second thermoset obtained by thermosetting the second resin composition at 200 ° C. for 90 minutes is 0 to 4 (g / mm / m ² / 24h); The average linear thermal expansion coefficient of the thermosetting product obtained by thermosetting the resin sheet at 200 ° C. for 90 minutes is 30 ppm / Less.

  FIG. 1 shows an example of the resin sheet with a support of the present invention. In FIG. 1, a resin sheet with a support 10 includes a support 11 and a resin sheet 12 provided on the support 11. In FIG. 1, the resin sheet 12 includes a first resin composition layer 13 provided on the support side and a second resin composition layer 14 provided on the side opposite to the support.

  Hereinafter, the support and the resin sheet of the resin sheet with a support of the present invention will be described in detail.

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

  When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) or polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”). ), Acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), and polyethers. Ketones, polyimides and the like can be mentioned. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When a metal foil is used as the support, examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. May be used.

  The support may be subjected to a mat treatment or a corona treatment on a surface to be joined to the first resin composition layer.

  Further, as the support, a support with a release layer having a release layer on the surface to be joined to the first resin composition layer may be used. Examples of the release agent used in the release layer of the support having a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used. For example, “SK-1” manufactured by Lintec Co., Ltd., which is a PET film having a release layer containing an alkyd resin-based release agent as a main component. , "AL-5", "AL-7" and the like.

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

<Resin sheet>
The resin sheet has a first resin composition layer provided on the support side and a composition different from the first resin composition forming the first resin composition layer provided on the opposite side to the support. And a second resin composition layer formed of the second resin composition.

  In the resin sheet with a support of the present invention, the thickness of the resin sheet is preferably 10 μm or more, more preferably 15 μm or more. The upper limit of the thickness of the resin sheet is preferably 30 μm or less, more preferably 25 μm or less, and still more preferably 20 μm or less, from the viewpoint of setting the thickness of the resin layer on the conductor.

  The thickness of the first resin composition layer made of the first resin composition is preferably 10 μm or less, more preferably 7 μm or less, and still more preferably 5 μm or less. The lower limit of the thickness of the first resin composition layer is not particularly limited, but from the viewpoint of obtaining an insulating layer exhibiting excellent peel strength with respect to the conductor layer after the roughening treatment, and from the viewpoint of ease of production of the resin sheet with a support. , Usually 0.05 μm or more, 0.1 μm or more. The presence of the first resin composition layer can improve the plating peelability.

  The thickness of the second resin composition layer made of the second resin composition is preferably 5 μm or more, more preferably 10 μm or more, and further preferably 15 μm or more. The upper limit of the thickness of the second resin composition layer is preferably 28 μm or less, more preferably 27 μm or less, and still more preferably 25 μm or less. The presence of the second resin composition layer can suppress warpage.

  In the present invention, the resin sheet comprises a first resin composition layer (a support side) and a second resin composition layer (the side opposite to the support) between the first and second resin composition layers. And a resin composition layer (not shown) having a composition different from that of the resin composition. Such an additional resin composition layer may be formed using the same material as the component described in the section (first resin composition).

  The resin sheet with a support of the present invention may further include a protective film on the surface of the resin sheet not joined to the support (that is, the surface on the opposite side to the support). The protective film contributes to preventing dust and the like from adhering to the surface of the resin sheet and preventing scratches. As the material of the protective film, the same material as described for the support may be used. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. When manufacturing a printed wiring board, the resin sheet with a support can be used by peeling off a protective film.

The moisture permeability coefficient M1 of the first thermosetting product obtained by thermosetting the first resin composition at 200 ° C. for 90 minutes is preferably 2 (g / mm / m ² / 24h) or more, more preferably 2 (g / mm / m ² / 24h). ^{.5 (g / mm / m 2} / 24h) or more, still more preferably ^{3 (g / mm / m 2} / 24h) or more. The upper limit is not particularly limited, but is preferably 7 (g / mm / m ² / 24h) or less, more preferably 6 (g / mm / m ² / 24h) or less, and still more preferably 5 (g / mm / m ^2). / 24h) or less. The moisture permeability coefficient can be measured according to the procedure described below (measurement of moisture permeability coefficient).

The moisture permeability coefficient M2 of the second thermosetting product obtained by thermosetting the second resin composition at 200 ° C. for 90 minutes is preferably 0.1 (g / mm / m ² / 24h) or more, more preferably Is 0.5 (g / mm / m ² / 24h) or more, more preferably 1 (g / mm / m ² / 24h) or more. No particular limitation is imposed on the upper limit, preferably ^{5 (g / mm / m 2} / 24h) or less, more preferably ^{3 (g / mm / m 2} / 24h) or less, more preferably ² (g / mm / ^m 2 / 24h) or less. The moisture permeability coefficient can be measured according to the procedure described below (measurement of moisture permeability coefficient).

In the present invention, the difference between M1 and ^{M2, 0~4 (g / mm /} m 2 / 24h) is, the upper limit is preferably ^{3 (g / mm / m 2} / 24h) or less, 2 (g / mm / m ² / 24h) or less. By setting the difference in such a range, gas generated at the time of thermosetting is easily released. For this reason, the pressure applied to the interface between the first and second thermosetting materials can be suppressed, and the occurrence of delamination can be suppressed.

The moisture permeability coefficient of the first thermosetting material is such that the gas generated during the thermosetting is easily released, and from the viewpoint of further suppressing the pressure applied to the interface between the first and second thermosetting materials, It is preferable to satisfy the relationship of M1> M2 which is larger than the moisture permeability coefficient of the material. Details, M1 is preferably greater ^{1 (g / mm / m 2} / 24h) or higher than M2, 1.2 and more preferably ^{(g / mm / m 2 /} 24h) or greater, 1.5 (g / Mm / m ² / 24h) or more. The upper limit is not particularly limited, but may be 4 (g / mm / m ² / 24h) or less.

  In the present invention, from the viewpoint of suppressing delamination occurring at the interface between the first and second thermosetting materials due to a dimensional change of the resin sheet, a thermosetting product obtained by thermosetting the resin sheet at 200 ° C. for 90 minutes. Has an average linear thermal expansion coefficient of 30 ppm / ° C. or less, preferably 25 ppm / ° C. or less, and more preferably 23 ppm / ° C. or less. The lower limit is not particularly limited, but may be 1 ppm / ° C. or more. The average coefficient of linear thermal expansion can be measured according to the procedure described below (measurement of average coefficient of linear thermal expansion (CTE) of resin sheet).

  Since the resin sheet with a support of the present invention can suppress delamination at the interface between the first and second resin composition layers, it shows a favorable result that swelling after reflow is suppressed. That is, even if the reflow process is repeated 10 times, the number of peeling points between the first thermosetting material and the second thermosetting material is less than 3, preferably 0. The swelling after reflow can be measured according to the procedure described later (evaluation of reflow resistance).

  Since the resin sheet with a support of the present invention can suppress the delamination of the interface between the first and second resin composition layers, it provides an insulating layer in which swelling after reflow is suppressed. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board), and the interlayer insulation of the printed wiring board can be improved. It can be more suitably used as a resin composition for forming a layer (resin composition for an interlayer insulating layer of a printed wiring board).

[Production method of resin sheet with support]
Hereinafter, an example of the method for producing a resin sheet with a support of the present invention will be described.

  First, a first resin composition layer made of a first resin composition and a second resin composition layer made of a second resin composition are formed on a support.

  As a method of forming the first resin composition layer and the second resin composition layer, for example, a method of laminating the first resin composition layer and the second resin composition layer so as to be bonded to each other is used. No. As a method of laminating the first resin composition layer and the second resin composition layer so as to be bonded to each other, for example, the first resin composition is applied to a support, the applied film is dried, and the first resin composition layer is dried. After the formation of the first resin composition layer, a method of applying the second resin composition on the first resin composition layer, drying the applied film and providing the second resin composition layer can be mentioned.

  In this method, the first resin composition layer is prepared by preparing a resin varnish in which the first resin composition is dissolved in an organic solvent, and applying the resin varnish on a support using a die coater or the like. It can be produced by drying the varnish.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol. , Aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. One organic solvent may be used alone, or two or more organic solvents may be used in combination.

  Drying of the resin varnish may be performed by a known drying method such as heating or blowing hot air. Depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the support is dried at 50 ° C. to 150 ° C. for 1 minute to 10 minutes. A first resin composition layer can be formed thereon.

  In the above method, the second resin composition layer is prepared by preparing a resin varnish obtained by dissolving the second resin composition in an organic solvent, and forming the resin varnish on a support using a die coater or the like. It can be prepared by applying the composition on the resin composition layer and drying the resin varnish.

  As the organic solvent used for preparing the resin varnish in which the second resin composition is dissolved, the same organic solvent as used in the preparation of the resin varnish in which the first resin composition is dissolved can be used. The resin varnish in which the composition has been dissolved can be dried by the same method as the method for drying the resin varnish in which the first resin composition has been dissolved.

  The resin sheet may be formed by a simultaneous coating method in which two types of resin varnishes are simultaneously coated other than the above-described coating method, and two types of resin varnishes are sequentially coated on one coating line. It may be formed by a tandem coating method. The resin sheet is formed by applying the first resin composition on the second resin composition layer, drying the applied film to form the first resin composition layer, and the first resin composition prepared separately. The resin composition layer and the second resin composition layer can be formed by laminating them so as to be bonded to each other.

  Further, in the present invention, for example, after a second resin composition layer and a first resin composition layer are sequentially formed on a protective film, a support is laminated on the first resin composition layer to support the first resin composition layer. A body-attached resin sheet may be produced.

[Printed wiring board]
The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin sheet in the resin sheet with a support of the present invention.

The printed wiring board of the present invention can be manufactured by a method including the following steps (I) and (II) using the resin sheet with a support described above.
(I) Step of laminating a resin composition layer of a resin sheet with a support on an inner layer substrate so as to be bonded to the inner layer substrate (II) Step of thermosetting the resin composition layer to form an insulating layer

  The “inner layer substrate” used in the step (I) mainly means a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or one or both surfaces of the substrate. Refers to a circuit board on which a patterned conductor layer (circuit) is formed. When manufacturing a printed wiring board, an inner circuit board of an intermediate product on which an insulating layer and / or a conductor layer is to be further formed is also included in the “inner layer board” in the present invention. When the printed wiring board is a circuit board with a built-in component, an inner layer board with a built-in component may be used.

  The lamination of the inner layer substrate and the resin sheet with the support can be performed, for example, by heat-pressing the resin sheet with the support to the inner layer substrate from the support side. Examples of a member (hereinafter, also referred to as a “thermocompression member”) for thermocompression-bonding the resin sheet with the support to the inner layer substrate include a heated metal plate (such as a SUS mirror plate) or a metal roll (SUS roll). Can be In addition, instead of directly pressing the thermocompression bonding member on the resin sheet with the support, it is preferable to press the resin sheet with an elastic material such as heat-resistant rubber so that the resin sheet with the support sufficiently follows the surface unevenness of the inner layer substrate. preferable.

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

  Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurized laminator manufactured by Meiki Seisakusho Co., Ltd., and a vacuum applicator manufactured by Nikko Materials Co., Ltd.

  After the lamination, the laminated resin sheet with a support may be subjected to a smoothing process under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same as the thermocompression bonding conditions for the laminate. The smoothing treatment can be performed with a commercially available laminator. Note that the lamination and the smoothing treatment may be continuously performed using the above-described commercially available vacuum laminator.

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

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

  The thermosetting conditions of the resin composition layer are not particularly limited, and conditions usually employed when forming an insulating layer of a printed wiring board may be used.

  For example, the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition and the like, but the curing temperature is in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 220 ° C, more preferably 170 ° C to 170 ° C). The curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

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

  In manufacturing the printed wiring board, (III) a step of forming a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further performed. These steps (III) to (V) may be performed according to various methods known to those skilled in the art used for manufacturing a printed wiring board. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or It may be carried out between IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer in the steps (II) to (V) may be repeatedly performed to form a multilayer wiring board. In this case, the thickness (t1 in FIG. 1) of the insulating layer between the respective conductor layers is preferably within the above range.

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

  Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment are not particularly limited, and well-known procedures and conditions usually used for forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened by performing a swelling process using a swelling solution, a roughening process using an oxidizing agent, and a neutralizing process using a neutralizing solution in this order. The swelling solution is not particularly limited, but includes an alkali solution, a surfactant solution, and the like, and is preferably an alkali solution. As the alkali solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan KK. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in a swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the cured product in a swelling liquid at 40 ° C to 80 ° C for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent, For example, alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in aqueous solution of sodium hydroxide is mentioned. The roughening treatment using an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 ° C. to 80 ° C. for 10 minutes to 30 minutes. Further, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan KK. As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercial product, for example, “Reduction Solution Securiganto P” manufactured by Atotech Japan KK can be mentioned. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 ° C. to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, it is preferable to immerse the object roughened with an oxidizing agent in a neutralization solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes.

  In one embodiment, the arithmetic average roughness Ra of the insulating layer surface after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, still more preferably 300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less, or 100 nm or less. It is. The arithmetic average roughness (Ra) of the insulating layer surface can be measured using a non-contact type surface roughness meter. As a specific example of the non-contact type surface roughness meter, “WYKO NT3300” manufactured by B Coin Instruments Inc. is exemplified.

  Step (V) is a step of forming a conductor layer. When the conductor layer is not formed on the inner substrate, the step (V) is a step of forming a first conductor layer. When the conductor layer is formed on the inner substrate, the conductor layer is formed on the first conductor layer. Step (V) is a step of forming a second conductor layer.

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

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

  The thickness of the conductive layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

  In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. Hereinafter, an example in which a conductor layer is formed by a semi-additive method will be described.

  First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern for exposing a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like, so that a conductor layer having a desired wiring pattern can be formed.

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

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

  The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The “conductive portion” is a “portion for transmitting an electric signal on the printed wiring board”, and the location may be a surface or an embedded portion. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The method of mounting a semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively. Specifically, a wire bonding mounting method, a flip chip mounting method, and no bump There are a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like. Here, the “mounting method using a bump-free build-up layer (BBUL)” refers to a “mounting method for directly embedding a semiconductor chip in a recess of a printed wiring board and connecting the semiconductor chip to wiring on the printed wiring board”. It is.

  Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. In the following description, “parts” and “%” mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.

<Preparation of resin varnish 1>
16 parts of liquid bisphenol A type epoxy resin (epoxy equivalent: 180, "Epicoat 828EL" manufactured by Mitsubishi Chemical Corporation), 18 parts of biphenyl type epoxy resin (epoxy equivalent: 269, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), naphthalene One part of a type 4 functional epoxy resin (epoxy equivalent: 163, “HP-4710” manufactured by DIC Corporation), phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation), cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass. 30 parts of a 1: 1 solution) and 30 parts of a polyvinyl butyral resin (1: 1 solution of ethanol and toluene having a solid content of 15% "KS-1" manufactured by Sekisui Chemical Co., Ltd.) are stirred into 30 parts of MEK and 10 parts of cyclohexanone. While heating. There, 12 parts of a 60% by weight solid solution of a triazine-containing phenol novolak resin (hydroxy equivalent: 125, "LA-7054" manufactured by DIC Corporation, nitrogen content: about 12% by weight) in a MEK solution, 12 parts of a naphthol-based curing agent (hydroxyl group) 12 parts of a MEK solution having an equivalent weight of 215 and a solid content of 60% by weight of Nippon Steel & Sumitomo Metal Corporation "SN485"), spherical silica (average particle diameter 0.1 μm, Denka Corporation "UFP-30", with aminosilane treatment) 45 parts, 5 parts of a solution prepared by adjusting an adduct-type curing accelerator (P200-H50, manufactured by Mitsubishi Chemical Corporation, nonvolatile component 50%) to a nonvolatile content of 25% with cyclohexanone, N, N-dimethyl-4-aminopyridine (( DMAP), manufactured by Tokyo Kasei Kogyo Co., Ltd.), 1 part of a solution adjusted to 5% of non-volatile content with MEK is mixed and uniformly dispersed with a high-speed mixer to prepare a resin varnish 1. did.

<Preparation of resin varnish 2>
5 parts of liquid bisphenol A type epoxy resin (epoxy equivalent: 180, "Epicoat 828EL" manufactured by Mitsubishi Chemical Corporation), 20 parts of biphenyl type epoxy resin (epoxy equivalent: 269, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), biphenyl 10 parts of epoxy resin (epoxy equivalent: 185, "YX4000" manufactured by Mitsubishi Chemical Corporation), 3 parts of naphthalene-type tetrafunctional epoxy resin (epoxy equivalent: 163, "HP-4710" manufactured by DIC Corporation), phenoxy resin (Mitsubishi) 5 parts of “YL7553BH30” (manufactured by Chemical Co., Ltd., a 1: 1 solution of cyclohexanone: methylethylketone (MEK) having a solid content of 30% by mass) were dissolved in 10 parts of MEK and 15 parts of cyclohexanone while stirring. There, 6 parts of a 60% by weight MEK solution of a triazine-containing phenol novolak resin (hydroxy equivalent: 125, “LA-7054” manufactured by DIC Corporation, nitrogen content: about 12% by weight), and a triazine-containing cresol novolak resin ( Hydroxyl equivalent 151, 6 parts of 1-methoxy-2-propanol solution of 50 wt% solid content of "LA-3018" (manufactured by DIC Corporation, nitrogen content about 18 wt%), naphthol-based curing agent (hydroxyl equivalent 215, 12 parts of a 60 wt% solid content MEK solution of Nippon Steel & Sumitomo Metal Corporation "SN485"), a reactive flame retardant (hydroxyl equivalent 162, "HCA-HQ" manufactured by Sanko Corporation, phosphorus content 9.5%) 3 parts, 190 parts of spherical silica (average particle size: 1.4 μm, “SP60-05” manufactured by Nippon Steel & Sumikin Materials, with aminosilane treatment), N, N-dimethyl-4-a Nopirijin ((DMAP), Tokyo Chemical Industry Co., Ltd.) were mixed solution 1 parts of a nonvolatile content adjusted to 5% MEK, and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish 2.

<Preparation of resin varnish 3>
5 parts of liquid bisphenol A type epoxy resin (epoxy equivalent: 180, "Epicoat 828EL" manufactured by Mitsubishi Chemical Corporation), 20 parts of biphenyl type epoxy resin (epoxy equivalent: 269, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), biphenyl 10 parts of type epoxy resin (epoxy equivalent: 185, “YX4000” manufactured by Mitsubishi Chemical Corporation), 5 parts of naphthalene type epoxy resin (epoxy equivalent: 283, “ESN475v” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), phenoxy resin (Mitsubishi Chemical ( 15 parts of “YL7553BH30”, a 1: 1 solution of cyclohexanone: methylethylketone (MEK) having a solid content of 30% by mass, was dissolved by heating in 10 parts of MEK and 15 parts of cyclohexanone with stirring. There, 6 parts of a 1-methoxy-2-propanol solution having a solid content of 50% by weight of a triazine-containing cresol novolak resin (hydroxyl equivalent 151, “LA-3018” manufactured by DIC Corporation, nitrogen content about 18% by weight), 25 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC Corporation, a toluene solution of 65% by mass of a nonvolatile content having an active group equivalent of about 223), a reactive flame retardant (hydroxyl equivalent 162, manufactured by Sanko Co., Ltd.) "HCA-HQ", 3 parts of phosphorus content 9.5%, spherical silica (average particle size: 1.0 m, "SP507-05" manufactured by Nippon Steel & Sumikin Materials, with aminosilane treatment) 160 parts, magnesium hydroxide (average) Particle size 0.8 μm, 10 parts of “MGZ-5R” manufactured by Sakai Chemical Co., Ltd., N, N-dimethyl-4-aminopyridine ((DMAP), manufactured by Tokyo Chemical Industry Co., Ltd.) One part of a solution adjusted to 5% of nonvolatile content with K, and 5 parts of a solution of 1-benzyl-2-phenylimidazole (“1B2PZ” manufactured by Shikoku Chemicals Co., Ltd.) adjusted to 5% of nonvolatile content with MEK are mixed. The resin varnish 3 was prepared by uniformly dispersing with a rotary mixer.

<Preparation of resin varnish 4>
5 parts of a liquid bisphenol A type epoxy resin (epoxy equivalent: 180, "Epicoat 828EL" manufactured by Mitsubishi Chemical Corporation) and 10 parts of a dicyclopentadiene type epoxy resin (epoxy equivalent: 277, "HP-7200H" manufactured by DIC Corporation) Was heated and dissolved in 20 parts of MEK while stirring. There, 10 parts of a 1-methoxy-2-propanol solution having a solid content of 50% by weight of a triazine-containing cresol novolak resin (hydroxyl equivalent 151, “LA-3018” manufactured by DIC Corporation, nitrogen content about 18% by weight), 5 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC Corporation, a toluene solution of 65% by mass of a nonvolatile matter having an active group equivalent of about 223) and a modified polybutadiene resin (hereinafter referred to as “resin”) synthesized as described below A) 40 parts, 90 parts of spherical silica (average particle size 0.2 μm, “SP516-05” manufactured by Nippon Steel & Sumikin Materials, with aminosilane treatment), N, N-dimethyl-4-aminopyridine ((DMAP)) , Tokyo Chemical Industry Co., Ltd.), 2 parts of a solution prepared by adjusting the nonvolatile content to 5% with MEK, 1-benzyl-2-phenylimidazole (manufactured by Shikoku Chemicals Co., Ltd.) 1B2PZ ”) was mixed with 15 parts of a solution prepared by adjusting the nonvolatile content to 5% with MEK, and uniformly mixed with a high-speed mixer to prepare a resin varnish 4.

<Synthesis of modified polybutadiene (resin A)>
50 g of G-3000 (bifunctional hydroxyl group-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl equivalent weight = 1798 g / eq., Solid content 100 w%: manufactured by Nippon Soda Co., Ltd.) and Ipsol 23.5 g of 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When the mixture became homogeneous, the temperature was raised to 50 ° C., and 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq.) Was added with further stirring, and the reaction was performed for about 3 hours. Then, the reaction product was cooled to room temperature, and 8.96 g of benzophenonetetracarboxylic dianhydride (acid anhydride equivalent = 161.1 g / eq.), 0.07 g of triethylenediamine, and ethyldiglycol were added thereto. 40.4 g of acetate (manufactured by Daicel Chemical Industries, Ltd.) was added, and the mixture was heated to 130 ° C. with stirring and reacted for about 4 hours. The disappearance of the NCO peak at 2250 cm ^-1 was confirmed by FT-IR. When the NCO peak disappearance was confirmed, it was regarded as the end point of the reaction. The reaction product was cooled to room temperature, and then filtered through a 100-mesh filter cloth to obtain a butadiene elastomer.
Properties of butadiene elastomer:
Viscosity = 7.5 Pa · s (25 ° C., E-type viscometer)
Acid value = 16.9 mgKOH / g
Solid content = 50% by mass
Number average molecular weight = 13723
Content of polybutadiene structural portion = 50 × 100 / (50 + 4.8 + 8.96) = 78.4% by mass

<Preparation of resin varnish 5>
5 parts of naphthalene type epoxy resin (epoxy equivalent 144, "HP4032" manufactured by DIC Corporation), 10 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, "Epicoat 828EL" manufactured by Mitsubishi Chemical Corporation), and biphenyl type epoxy 25 parts of resin (epoxy equivalent: 269, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), 5 parts of biphenyl type epoxy resin (epoxy equivalent: 185, "YX4000" manufactured by Mitsubishi Chemical Corporation), naphthalene type tetrafunctional epoxy resin (epoxy) Equivalent 163, 3 parts of "HP4710" manufactured by DIC Corporation, 15 parts of phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: methylethylketone (MEK) having a solid content of 30% by mass), Polyvinyl butyral resin (Sekisui Chemical Co., Ltd. "KS-1" solid content 15 Of ethanol and toluene 1: 1 solution) 10 parts, MEK15 parts, were dissolved by heating with stirring to 15 parts of cyclohexanone. There, 12 parts of a MEK solution of a triazine-containing phenol novolak resin (hydroxy equivalent: 125, “LA7054” manufactured by DIC Corporation, nitrogen content: about 12% by weight) having a solid content of 60% by weight, a naphthol-based curing agent (hydroxyl equivalent: 215) 12 parts of a 60% by weight solid content MEK solution of "SN485" manufactured by Nippon Steel & Sumitomo Metal Co., Ltd., and 120 parts of spherical silica (average particle size: 0.2 [mu] m, "SP516-05" manufactured by Nippon Steel & Sumikin Materials, with aminosilane treatment) , 3 parts of reactive flame retardant (hydroxy equivalent 162, "HCA-HQ" manufactured by Sanko Co., Ltd., phosphorus content 9.5%), N, N-dimethyl-4-aminopyridine ((DMAP), Tokyo Chemical Industry) (Manufactured by Co., Ltd.) was mixed with 2 parts of a solution adjusted to have a nonvolatile content of 5% using MEK, and the mixture was uniformly dispersed with a high-speed mixer to prepare a resin varnish 5.

<Preparation of resin varnish 6>
16 parts of liquid bisphenol A type epoxy resin (epoxy equivalent: 180, “Epicoat 828EL” manufactured by Mitsubishi Chemical Corporation), 18 parts of biphenyl type epoxy resin (epoxy equivalent: 269, “NC3000” manufactured by Nippon Kayaku Co., Ltd.), naphthalene One part of a type 4 functional epoxy resin (epoxy equivalent: 163, “HP-4710” manufactured by DIC Corporation), phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation), cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass. 15 parts of a 1: 1 solution) and 30 parts of a polyvinyl butyral resin (1: 1 solution of ethanol and toluene having a solid content of 15% "KS-1" manufactured by Sekisui Chemical Co., Ltd.) are stirred into 15 parts of MEK and 10 parts of cyclohexanone. While heating. There, 12 parts of a 60% by weight solid solution of a triazine-containing phenol novolak resin (hydroxy equivalent: 125, "LA-7054" manufactured by DIC Corporation, nitrogen content: about 12% by weight) in a MEK solution, 12 parts of a naphthol-based curing agent (hydroxyl group) 12 parts of MEK solution having an equivalent weight of 215, a solid content of 60% by weight of Nippon Steel & Sumitomo Metal Corporation "SN485", a flame retardant (hydroxyl equivalent 162, "HCA-HQ" manufactured by Sanko Corporation, phosphorus content 9.5%) ) 3 parts, spherical silica (average particle size 0.3 μm, “SO-C1” manufactured by Admatechs Co., Ltd., with aminosilane treatment) 45 parts, N, N-dimethyl-4-aminopyridine ((DMAP), Tokyo Chemical Industry Co., Ltd.) (Manufactured by K.K.) was mixed with 1 part of a solution adjusted to have a nonvolatile content of 5% using MEK, and the mixture was uniformly dispersed with a high-speed mixer to prepare a resin varnish 6.

  The following table shows the materials used in the preparation of each resin varnish and the compounding amounts (parts by mass of nonvolatile components).

<Example 1: Production of resin sheet 1 with support>
The resin varnish 1 was uniformly released with a die coater onto a PET film ("PET501010", manufactured by Lintec Co., Ltd., thickness: 50 μm) from which the resin varnish 1 was released so that the thickness of the resin composition layer after drying was 5 μm. After coating and drying at 80 to 100 ° C. (average 90 ° C.) for 5 minutes, it was provisionally cured at 180 ° C. for 10 minutes to form a first resin composition layer on a PET film (support). The resin varnish 2 is uniformly coated on the surface of the first resin composition layer by a die coater so that the thickness of the resin varnish 2 becomes 20 μm, and dried at 80 to 100 ° C. (average 90 ° C.) for 5 minutes. Was prepared.

<Example 2: Production of resin sheet 2 with support>
A resin sheet 2 with a support was produced in the same manner as in Example 1 except that the resin varnish 1 was applied so that the thickness of the resin composition layer after drying was 3 μm.

<Example 3: Production of resin sheet 3 with support>
A resin sheet 3 with a support was produced in the same manner as in Example 1 except that the resin varnish 1 was applied so that the thickness of the resin composition layer after drying was 7 μm.

<Example 4: Production of resin sheet 4 with support>
A resin sheet 4 with a support was produced in the same manner as in Example 1 except that the resin varnish 2 was changed to the resin varnish 3.

<Example 5: Production of resin sheet 5 with support>
A resin sheet with a support was produced in the same manner as in Example 1, except that the resin varnish 1 was changed to the resin varnish 4 and the resin varnish 2 was changed to the resin varnish 5.

<Comparative Example 1: Production of resin sheet 6 with support>
A resin sheet 6 with a support was produced in the same manner as in Example 1 except that the varnish 4 was used instead of the resin varnish 1.

<Comparative Example 2: Production of resin sheet 7 with support>
A resin sheet with a support was produced in the same manner as in Example 1, except that the resin varnish 1 was changed to the resin varnish 4 and the resin varnish 2 was changed to the resin varnish 6.

<Evaluation>
(Measurement of average linear thermal expansion coefficient (CTE) of resin sheet)
The resin sheet with a support produced in each of Examples and Comparative Examples was fixed at four sides by a jig, cured in an oven at 200 ° C. for 90 minutes, taken out, and cut into a test piece having a width of about 5 mm and a length of about 15 mm. did. The support was peeled off, and thermomechanical analysis was performed by a tensile load method (JIS K7197) using a thermomechanical analyzer (Thermo Plus TMA8310, manufactured by Rigaku Corporation). After attaching the test piece to the above-mentioned apparatus, measurement was continuously performed twice under a load of 1 g, a heating rate of 5 ° C./min, and measuring conditions of 30 ° C. to 150 ° C. The average coefficient of linear thermal expansion (ppm / ° C.) from 30 ° C. to 150 ° C. in the second measurement was calculated, and the results are shown in the table.

(Measurement of moisture permeability coefficient)
Each resin varnish was uniformly released on a PET film ("PET501010", manufactured by Lintec Co., Ltd., thickness: 50 μm), which had been subjected to a release treatment, using a die coater so that the thickness of the resin composition layer after drying was 5 μm. After coating and drying at 80 ° C to 100 ° C (average 90 ° C) for 5 minutes, it was provisionally cured at 180 ° C for 10 minutes to form a resin composition layer on the support.

The resin composition layer was thermally cured at 200 ° C. for 90 minutes on the formed support to obtain a cured product for evaluation. The cured product for evaluation was cut into a circle having a diameter of 70 mm, and the moisture permeability was measured according to the moisture permeability test method (cup method) of JIS Z0208. Specifically, the moisture permeability (g / m ² · 24h) was determined by measuring the weight of the moisture permeating the sample at 60 ° C. and 85% RH for 24 hours. · ^mm / m 2 · 24h) was calculated. The average value of the three test pieces is shown in the table below.

(Evaluation of reflow resistance)
Using a reflow apparatus ("HAS-6116" manufactured by Antom Japan Co., Ltd.) with a peak temperature of 260 ° C, a simulated reflow process was performed on the laminated board with a conductor layer with a temperature profile based on IPC / JEDEC J-STD-020C. Repeated 10 times. Thereafter, the state of adhesion between the first thermosetting product and the second thermosetting product, that is, the presence or absence of peeling, was visually checked, and evaluated according to the following criteria. Manufacture of the laminated board with a conductor layer was performed as follows.
[Evaluation criteria]
：: There was no peeling.
Δ: Peeling was 1 or more and less than 3 out of 10 times during 10 times.
×: Peeling was 3 or more out of 10 times.

((Production of laminated board with conductor layer))
-Fabrication of inner layer circuit board-
IPC MULTI-PURPOSE TEST BOARD NO. Was applied to a glass cloth base epoxy resin double-sided copper-clad laminate [copper foil thickness 18 μm, substrate thickness 0.8 mm, R5715ES manufactured by Matsushita Electric Works, Ltd.]. A pattern of IPC C-25 (line / space = 600/660 um comb tooth pattern (residual copper ratio: 48%)) was formed, and a roughening treatment was performed with a microetching agent (CZ8100 manufactured by Mec Co., Ltd.). A circuit board was manufactured.

-Compression of resin sheet with support-
The resin sheet with a support produced in each of the examples and comparative examples was laminated on both surfaces of the inner circuit board using a laminator with a two-chamber press (MVLP500 / 600-IIB manufactured by Meiki Co., Ltd.). Lamination in the first chamber was performed by reducing the pressure to 13 hPa or less by reducing the pressure for 30 seconds, and then performing pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. In the 2nd chamber, pressure reduction was not performed, but pressure bonding was performed at 100 ° C. and a pressure of 0.55 MPa.

-Peeling of support-
After the resin sheet was pressed against the inner circuit board, the support was peeled from the formed first and second resin composition layers. Thereafter, the laminate was thermoset at 180 ° C. for 30 minutes to obtain a laminate.

-Roughening also serves as desmearing-
The obtained laminate was first immersed in a swelling liquid, Swellingdip Securiganto P containing diethylene glycol monobutyl ether from Atotech Japan KK at 60 ° C. for 10 minutes. Then a roughening solution, concentrate compact _P of Atotech Japan Co., Ltd. at 80 ° C. 20 minutes _(KMnO 4:: 60g / L and aqueous NaOH 40 g / L) (Example 1-4), 10 (Example 5, Comparative Examples 1 and 2). After the water washing treatment of the laminate, the laminate was finally immersed in a reduction solution Securiganto P of Atotech Japan KK at 40 ° C. for 5 minutes as a neutralizing solution. Then, it dried at 130 degreeC for 15 minutes. By the above treatment, the surface of the first resin composition layer was subjected to a roughening treatment (and a desmear treatment).

-Formation of conductor layer-
An electroless copper plating step (an electroless copper plating step using a chemical manufactured by Atotech Japan KK) was performed to form a conductor layer on the surface of the roughened laminate. This step was performed so that the thickness of the electroless copper plating layer was 1 μm. Details of the electroless copper plating step and the electrolytic copper plating step are as follows.

−−Electroless copper plating process−−
1. Alkali cleaning (cleaning of the surface of the laminate and charge adjustment)
Washing was performed at 60 ° C. for 5 minutes using Cleaning Cleaner Security 902 (trade name).
2. Soft etching (cleaning of electroless copper plating layer)
Washing was performed at 30 ° C. for 1 minute using an aqueous solution of sulfuric acid-acidic sodium peroxodisulfate.
3. Predip (Adjustment of charge on the surface of the laminate for Pd application)
It processed for 1 minute at room temperature using Pre. Dip Neoganth B (brand name).
4. Activator (Pd application to the surface of the laminate)
It processed at 35 degreeC for 5 minutes using Activator Neoganth 834 (brand name).
5. Reduction (reduction of Pd applied to laminate)
The mixture was treated at 30 ° C. for 5 minutes using a mixture of Reducer Neoganth WA (trade name) and Reducer Accelerator 810 mod. (Trade name).
6. Electroless copper plating (copper is deposited on the surface of the laminate (the surface of the applied Pd))
Basic Solution Printganth MSK-DK (trade name), Copper Solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name) and a mixture of Reducer Cu (trade name) treated at 35 ° C. for 20 minutes at 35 ° C.

-Electrolytic copper plating process-
Next, an electrolytic copper plating step was performed to form a thick conductor layer (copper layer) so that the total thickness was 30 μm. Further, annealing was performed at 190 ° C. for 60 minutes to produce a laminate with a conductor layer.

Reference Signs List 10 resin sheet with support 11 support 12 resin sheet 13 first resin composition layer 14 second resin composition layer

Claims (16)

A support, a resin sheet with a support, comprising a resin sheet provided on the support,
A resin sheet, a first resin composition layer formed of the first resin composition, provided on the support side;
A second resin composition layer formed of the second resin composition, provided on the side opposite to the support side,
The compositions of the first resin composition and the second resin composition are different from each other,
Moisture permeability coefficient M1 of the first thermosetting product obtained by heat-curing the first resin composition at 200 ° C. for 90 minutes, and second moisture-curing coefficient M1 obtained by thermosetting the second resin composition at 200 ° C. for 90 minutes. The difference from the moisture permeability coefficient M2 of the thermosetting product of No. 2 is 0 to 4 (g / mm / m ² / 24h),
A resin sheet with a support, wherein the thermosetting product obtained by thermosetting the resin sheet at 200 ° C. for 90 minutes has an average linear thermal expansion coefficient of 30 ppm / ° C. or less.   The resin sheet with a support according to claim 1, wherein the thickness of the resin sheet is 30 µm or less.   The resin sheet with a support according to claim 1 or 2, wherein the thickness of the first resin composition layer is 5 µm or less.   The resin sheet with a support according to any one of claims 1 to 3, wherein M1 and M2 satisfy a relationship of M1> M2. M1 is 2 is ^{(g / mm / m 2 /} 24h) or more, the support coated resin sheet according to any one of claims 1 to 4. The first and second resin compositions include an epoxy resin,
Assuming that the content of the epoxy resin in the first resin composition is B1 (% by mass) and the content of the epoxy resin in the second resin composition is B2 (% by mass), the difference between B1 and B2 (B1 The resin sheet with a support according to any one of claims 1 to 5, wherein -B2) is from 5% by mass to 60% by mass. The second resin composition contains an inorganic filler, and the content of the inorganic filler is 60% by mass or more when the nonvolatile component in the second resin composition is 100% by mass. 7. The resin sheet with a support according to any one of items 6 to 6 . The first resin composition contains a thermoplastic resin, and the content of the thermoplastic resin is 10% by mass or more when a nonvolatile component in the first resin composition is 100% by mass. 8. The resin sheet with a support according to any one of items 7 to 7 . The resin sheet with a support according to any one of claims 1 to 8 , wherein a difference between M1 and M2 is 3 (g / mm / m ² / 24h) or less. The first and second resin compositions include an inorganic filler, the average particle diameter of the inorganic filler in the first resin composition is R1 (μm), and the average particle diameter of the inorganic filler in the second resin composition is The resin sheet with a support according to any one of claims 1 to 9 , wherein a ratio (R2 / R1) of R1 and R2 is 1 to 15 when an average particle size is R2 (μm). The first and second resin compositions include an inorganic filler, the average particle size of the inorganic filler in the first resin composition is R1 (μm), and the average particle size of the inorganic filler in the second resin composition is The resin sheet with a support according to any one of claims 1 to 10, wherein a ratio (R2 / R1) of R1 and R2 is 1.1 to 15 when an average particle diameter is R2 (μm). . The first resin composition and the second resin composition contain an inorganic filler, the content of the inorganic filler in the first resin composition is A1 (% by mass), and the content of the second resin composition is The resin sheet with a support according to any one of claims 1 to 11 , which satisfies a relationship of A1 <A2 when the content of the inorganic filler is A2 (% by mass). The first and second resin compositions include an inorganic filler,
When the content of the inorganic filler in the first resin composition is A1 (% by mass) and the content of the inorganic filler in the second resin composition is A2 (% by mass), the difference between A1 and A2 is The resin sheet with a support according to any one of claims 1 to 12, wherein (A2-A1) is 10% by mass or more and 90% by mass or less. A insulating layer formed of a printed wiring board, the support coated resin sheet according to any one of claims 1 to 1 3. Comprising an insulating layer formed by a support with a resin sheet according to any one of claims 1 to 1 3, a printed wiring board. It comprises a printed wiring board according to claim 1 5, the semiconductor device.

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