KR20170064478A - Resin sheet - Google Patents

Abstract

[PROBLEMS] To provide a resin sheet capable of reducing deflection of a substrate and having excellent parts embedding property.
[MEANS FOR SOLVING PROBLEMS] A resin sheet comprising a support and a curable resin composition layer provided on a support, wherein the curable resin composition layer contains an inorganic filler, the content of the inorganic filler in the curable resin composition layer is 74 mass% In which the average particle diameter of the filler is 1.6 占 퐉 or less and the product of the specific surface area [m2 / g] of the inorganic filler and the true density [g / cm3] is 6 to 8 and the minimum melt viscosity of the curable resin composition layer is 12000 poise or less. .

Description

Resin Sheet {RESIN SHEET}

The present invention relates to a resin sheet, a wiring board, and a semiconductor device.

Recently, demand for small and high-performance electronic devices such as smart phones and tablet PCs is increasing. Accordingly, a printed wiring board used in these small electronic apparatuses is required to have higher functionality and miniaturization.

Components such as a bare chip, a chipped capacitor, and a chip inductor are mounted on the printed wiring board. Conventionally, such a component has been mounted only on the surface circuit of the printed wiring board, but its mounting amount is limited, and it has been difficult to cope with the recent demand for more sophisticated and miniaturized printed wiring boards.

To solve the above problems, there has been proposed a component built-in circuit board in which components are mounted on an inner-layer circuit board to reduce the size (thinness) while increasing the amount of components to be mounted (see, for example, Patent Document 1).

Japanese Patent Publication No. 4114629

However, in order to improve the component embedding property in the recess in which the parts of the component built-in circuit board are disposed, it is necessary to reduce the content of the inorganic filler in the resin composition used for embedding the component, Although it is conceivable to use such a small resin, the thermal expansion rate is increased and the substrate warpage tends to become large. On the other hand, in order to reduce the substrate warpage of the component built-in circuit board, it is conceivable to increase the content of the inorganic filler in the resin composition. However, there is a problem that the melt viscosity becomes high and the component filling property in the cavity tends to lower .

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a resin sheet which is capable of reducing warping of a substrate and having an excellent part embedding property.

The present inventors have conducted intensive studies on the above problems and have found that the curable resin composition for forming a curable resin composition layer has an average particle diameter of 1.6 占 퐉 or less and a specific surface area [m2 / g] and a true density [g / Of an inorganic filler having a product of 6 to 8 in an amount of not less than 74 mass% and a minimum melt viscosity of not more than 12000 poise in the curable resin composition layer, thereby completing the present invention . The present invention is based on this novel knowledge.

That is, the present invention includes the following contents.

[1] A resin sheet comprising a support and a curable resin composition layer provided on a support, wherein the curable resin composition layer contains an inorganic filler, the content of the inorganic filler in the curable resin composition layer is 74% Wherein a product of the specific surface area [m 2 / g] of the inorganic filler and the true density [g / cm 3] is 6 to 8 and the minimum melt viscosity of the curable resin composition layer is 12000 poise or less.

[2] A resin sheet according to [1], wherein the inorganic filler is silica.

[3] The curable resin composition layer according to [1] or [2], wherein the curable resin composition layer contains (a) an epoxy resin, the epoxy resin contains a liquid epoxy resin, and the content of the liquid epoxy resin in the curable resin composition layer is 1% 2].

[4] (a) an epoxy resin, and the mass of solid epoxy resin of the mass (M _L) of a liquid epoxy resin in the contained, and the curable resin composition layer is a solid epoxy resin ratio of _{(M S) (M S /} M _L ) of the resin sheet is 0.6 to 10.

[5] The resin sheet according to [3] or [4], wherein the epoxy resin (a) is an epoxy resin having an aromatic structure (a ').

[6] The curable resin composition layer according to any one of [1] to [3], wherein the curable resin composition layer further comprises a resin (d): a resin having a functional group with a glass transition temperature of 25 ° C or lower and a resin having a functional group To (5).

[7] The thermosetting resin composition according to [1], wherein the component (d) has at least one functional group selected from the group consisting of hydroxyl group, acid anhydride group, phenolic hydroxyl group, epoxy group, isocyanate group and urethane group, Having at least one structural unit selected from a butadiene structural unit, an isoprene structural unit, an isobutylene structural unit, a chloroprene structural unit, a urethane structural unit, a polycarbonate structural unit, a (meth) acrylate structural unit, and a polysiloxane structural unit ].

[8] A resin sheet according to any one of [1] to [7], which is for a component internal circuit board.

[9] A wiring board comprising an insulating layer formed by curing a curable resin composition layer of the resin sheet described in any one of [1] to [8], and a conductor layer.

[10] A semiconductor device comprising a wiring board according to [9].

According to the present invention, it is possible to provide a resin sheet which is capable of reducing warping of the substrate and having excellent parts embedding property.

1A is a schematic diagram (1) showing a procedure for preparing a circuit board to which a component is attached, which is used in a method of manufacturing a component built-in circuit board using the resin sheet of the present invention.
Fig. 1B is a schematic diagram (2) showing a procedure for preparing a circuit board to which a component is attached, which is used in a method for manufacturing a component built-in circuit board using the resin sheet of the present invention.
Fig. 1C is a schematic diagram (3) showing a procedure for preparing a circuit board to which components are attached, which is used in the method for manufacturing the component built-in circuit board using the resin sheet of the present invention.
FIG. 1D is a schematic diagram (4) showing a procedure for preparing a circuit board to which components are attached, which is used in a method of manufacturing a component built-in circuit board using the resin sheet of the present invention.
2 is a schematic diagram showing one form of the resin sheet of the present invention.
3A is a schematic view (1) for explaining a method of manufacturing a component built-in circuit board using the resin sheet of the present invention.
3B is a schematic view (2) for explaining a method of manufacturing a component built-in circuit board using the resin sheet of the present invention.
3C is a schematic diagram (3) for explaining a manufacturing method of the component built-in circuit board using the resin sheet of the present invention.
Fig. 3D is a schematic diagram (4) for explaining a manufacturing method of the component built-in circuit board using the resin sheet of the present invention.
Fig. 3E is a schematic view (5) for explaining a manufacturing method of the component built-in circuit board using the resin sheet of the present invention.
Fig. 3F is a schematic diagram (6) for explaining a manufacturing method of the component built-in circuit board using the resin sheet of the present invention.
Fig. 3G is a schematic view (7) for explaining a manufacturing method of the component built-in circuit board using the resin sheet of the present invention.

Before describing the resin sheet of the present invention in detail, the curable resin composition used in forming the curable resin composition layer (also referred to as " resin composition layer ") in the resin sheet of the present invention Will be described.

<Curable resin composition>

The curable resin composition for forming the curable resin composition layer preferably has an average particle diameter of 1.6 占 퐉 or less and an inorganic filler having a specific surface area [m2 / g] and a true density [g / cm3] And the cured product (insulating layer) may have sufficient hardness and insulating properties. Examples of the curable resin composition include a composition containing a curable resin and a curing agent together with an inorganic filler. As the curable resin, conventionally known curable resins used for forming the insulating layer of the printed wiring board can be used. Of these, an epoxy resin is preferable. Accordingly, in one embodiment, the curable resin composition contains (a) an epoxy resin, (b) a curing agent and (c) an inorganic filler. (C) an inorganic filler; and (d) an epoxy resin having a functional group having a glass transition temperature of 25 占 폚 or less. A resin, and a resin having a functional group which is liquid at 25 占 폚. In the present invention, the curable resin composition may further contain additives such as a thermoplastic resin, a curing accelerator, a flame retardant, and rubber particles, if necessary.

(B) a curing agent; (c) an inorganic filler; (d) a resin having a functional group with a glass transition temperature of 25 占 폚 or less; and a functional group which is liquid at 25 占 폚 , And (e) the additive will be described.

(a) an epoxy resin

Examples of the epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, Cresol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bicalcylenol type epoxy resin, glycidylamine resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, A cresol novolak type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic epoxy resin, a spirocyclic epoxy resin, a glycidyl ester type epoxy resin, Epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, Trimethylol-type epoxy resins, and tetraphenylethanepolyoxy resins. The epoxy resin may be used singly or in combination of two or more kinds.

Examples of the epoxy resin include a group consisting of a mixture of a bisphenol type epoxy resin, a fluorinated epoxy resin (for example, a bisphenol AF type epoxy resin), a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, Is preferably used as the epoxy resin.

In a preferred embodiment, as the epoxy resin (a), an epoxy resin (a ') having an aromatic structure is preferable. The epoxy resin (a ') having an aromatic structure is not particularly limited as long as it has an aromatic structure, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin and the like Naphthalene type epoxy resin, naphthol novolak type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthalene type epoxy resin, naphthalene type epoxy resin, An epoxy resin, an anthracene epoxy resin, a cresol novolak epoxy resin, a biphenyl epoxy resin, a naphthylene ether epoxy resin, a tetraphenyl ethane epoxy resin, a biquileneol epoxy resin and the like.

From the viewpoint of lowering the minimum melt viscosity of the curable resin composition layer, it is preferable that the epoxy resin contains an epoxy resin which is liquid at room temperature (hereinafter referred to as &quot; liquid epoxy resin &quot;). In the present specification, "room temperature" means 25 ° C.

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, it is preferable that at least 50% by mass or more of the epoxy resin is an epoxy resin having two or more epoxy groups in one molecule. Among these, a liquid epoxy resin having two or more epoxy groups in one molecule and an epoxy resin (hereinafter referred to as &quot; solid epoxy resin &quot;) having at least three epoxy groups in one molecule and being solid at room temperature are preferably contained . By using a liquid epoxy resin and a solid epoxy resin together as the epoxy resin, a curable resin composition having excellent flexibility can be obtained. Further, the breaking strength of the cured product (insulating layer) of the curable resin composition is also improved.

Examples of the liquid epoxy resin (a1) include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, phenol novolak type epoxy resins, An alicyclic epoxy resin and an epoxy resin having a butadiene structure are preferable, and a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin and a naphthalene type epoxy resin are more preferable. Especially, the aromatic skeleton-containing epoxy resin is also preferable for lowering the average linear thermal expansion coefficient. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin), "828US" and "jER828EL" (bisphenol A type epoxy resin manufactured by Mitsubishi Kagaku Co., Quot; jER807 &quot; (bisphenol F type epoxy resin), &quot; jER152 &quot; (phenol novolak type epoxy resin), &quot; ZX1059 &quot; (bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Shinnitetsu Sumi Kagaku Co., EX-721 &quot; (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Co., Ltd., &quot; SEROCIDE 2021P &quot; (manufactured by Daicel Co., Resin) and &quot; PB-3600 &quot; (epoxy resin having a butadiene structure). These may be used singly or in combination of two or more kinds.

Examples of the solid epoxy resin (a2) include naphthalene type tetrafunctional epoxy resins, cresol novolak type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether Type epoxy resin, an anthracene epoxy resin, a bisphenol A epoxy resin and a tetraphenyl ethane epoxy resin are preferable, and a naphthalene type tetrafunctional epoxy resin, a naphthol type epoxy resin and a biphenyl type epoxy resin are more preferable. Particularly, the polyfunctional epoxy resin is preferable for decreasing the average linear heat expansion rate because the number of crosslinking points increases. Specific examples of the solid epoxy resin include HP4032H (naphthalene type epoxy resin), HP-4700, HP-4710 (naphthalene type tetrafunctional epoxy resin), N-690 (Cresol novolak type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200L", (dicyclopentadiene type epoxy resin), " EXA7311-G4 "," EXA7311-G4S "," HP6000 "(naphthylene ether type epoxy resin)," EPPN-502H "(trisphenol type epoxy resin manufactured by Nippon Kayaku Co., Quot; NC3000L &quot;, &quot; NC3100 &quot; (biphenyl type epoxy resin), &quot; NC7000L &quot; (naphthol novolac epoxy resin), NC3000H, ESN475V "(naphthol type epoxy resin)," ESN485 "(naphthol novolak type epoxy resin)," YX4000H "," YL6121 "(biphenyl type epoxy resin)," YX4000HK " PG-100 "," CG-500 "manufactured by Osaka Gas Chemical Co., Ltd.," YL7800 "(fluorene type) manufactured by Mitsubishi Kagaku Co., (Solid bisphenol A type epoxy resin), "jER1031S" (tetraphenyl ethane type epoxy resin) and "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Kagaku Co., Ltd. have.

If the epoxy resin, and containing a solid epoxy resin and liquid epoxy resin, a ratio (M _S / M _L) of the mass of solid epoxy resin to the weight of the liquid epoxy resin (M _L) (M _S) is 0.6 to 10 &lt; / RTI &gt; By setting the M _S / M _L within this range, sufficient tackiness is obtained when i) is used in the form of a resin sheet, ii) sufficient flexibility is obtained when used in the form of a resin sheet, And (iii) a cured product (insulating layer) having a sufficient breaking strength can be obtained.

The content of the epoxy resin (a) in the curable resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably 5% by mass or more, from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability Mass% or more. The upper limit of the content of the epoxy resin is not particularly limited insofar as the effect of the present invention is exhibited, but is preferably 40 mass% or less, more preferably 35 mass% or less, further preferably 30 mass% or less.

Therefore, the content of the epoxy resin (a) in the curable resin composition is preferably 0.1 to 50 mass%, more preferably 10 to 45 mass%, and still more preferably 20 to 42 mass%. In the present invention, the content of each component in the curable resin composition is a value obtained by assuming that the non-volatile component in the curable resin composition is 100% by mass, unless otherwise specified.

The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, still more preferably 110 to 1000. By setting this range, the cross-linking density of the cured product becomes sufficient, resulting in an insulating layer having a small surface roughness. The epoxy equivalent can be measured in accordance with JIS K7236, and is the mass of the resin containing one equivalent of an epoxy group.

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

(b) Curing agent

The curing agent is not particularly limited as long as it has a function of curing an epoxy resin, and examples thereof include 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 a carbodiimide- . The curing agent may be used singly or in combination of two or more kinds.

As the phenol-based curing agent and 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 viewpoints of heat resistance and water resistance. Further, from the viewpoint of adhesion with a conductor layer (circuit wiring), a nitrogen-containing phenol-based curing agent is preferable, and a phenol resin containing a triazine structure and an alkylphenol resin containing a triazine structure are more preferable. Among them, it is preferable to use a phenol-based curing agent containing a triazine structure from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion (peel strength) with a conductor layer.

Specific examples of the phenol-based curing agent and naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375" and "SN395" manufactured by Totogasayi Co., LA7052 &quot;, &quot; LA7054 &quot;, and &quot; LA3018 &quot; manufactured by DIC Corporation.

The active ester-based curing agent is not particularly limited, but generally includes ester groups having a high reaction activity such as esters of phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compounds, Are preferably used. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. From the viewpoint of heat resistance improvement, an active ester type curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester type 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, catechol, alpha -naphthol, beta -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadienyldiphenol, phenol novolac, and the like.

Specifically, there can be mentioned an active ester compound containing a dicyclopentadienyldiphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, an active ester compound containing a phenol novolac benzoylate Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadienyldiphenol structure are more preferable.

EXB9451 "," EXB9460 "," EXB9460S "," HPC-8000-65T "(manufactured by DIC Corporation) as the active ester compound containing a dicyclopentadienyldiphenol structure as commercial products of the active ester curing agent, EXB9416-70BK "(manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure," DC808 "(manufactured by Mitsubishi Chemical Corp.) as an active ester compound containing an acetylated product of phenol novolac, YLH1026 &quot; (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoyl moiety of boric acid, and the like.

Specific examples of the benzoxazine type curing agent include "HFB2006M" manufactured by Shawako Co., Ltd., "P-d" and "F-a" manufactured by Shikoku Kasei Corporation.

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4'-methylene bis -Dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis Cyanate phenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis Cyanate phenyl) thioether, and bis (4-cyanate phenyl) ether, polyfunctional cyanate resins derived from phenol novolak and cresol novolak, and cyanate resins derived from these cyanate resins, , And the like. Specific examples of the cyanate ester curing agent include &quot; PT30 &quot; and &quot; PT60 &quot; (both phenol novolak type polyfunctional cyanate ester resins), &quot; BA230 &quot; (part or all of bisphenol A dicyanate Trimellitized trimellitic prepolymer), and the like.

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

In the present invention, the curing agent (b) preferably contains at least one member selected from the group consisting of a phenol-based curing agent, a cyanate ester-based curing agent and an active ester-based curing agent. The phenolic resin containing a triazine structure, More preferably at least one selected from an alkyl phenol resin, a cyanate ester curing agent and an active ester curing agent.

The content of the curing agent (b) in the curable resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.5% by mass or more from the viewpoint of obtaining an insulating layer having high peel strength and low dielectric loss tangent Is not less than 1% by mass. The upper limit of the content of the curing agent (b) is not particularly limited insofar as the effect of the present invention is exhibited, but is preferably 30 mass% or less, more preferably 25 mass% or less, and further preferably 20 mass% or less .

Therefore, the content of the curing agent (b) in the curable resin composition is preferably 0.1 to 30 mass%, more preferably 0.5 to 25 mass%, and still more preferably 1 to 20 mass%.

The amount ratio (ratio) of the epoxy resin (a) to the curing agent (b) is preferably from 1: 0.2 to 1: 1 in terms of the ratio of [(a) the total number of epoxy groups of the epoxy resin] 1: 2, more preferably 1: 0.3 to 1: 1.5, further preferably 1: 0.4 to 1: 1. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like and varies depending on the kind of the curing agent. The total number of epoxy groups in the epoxy resin means the value obtained by dividing the solid content of each epoxy resin by the epoxy equivalent in terms of the epoxy resin and the total number of reactors in the curing agent means the total amount of the solid components in the curing agent Divided by the total amount of the curing agent. The heat resistance of the cured product (insulating layer) of the curable resin composition is further improved by adjusting the amount ratio of the epoxy resin and the curing agent within this range.

(c) inorganic filler

The inorganic filler is not limited as long as it has an average particle diameter of 1.6 탆 or less and a product (specific surface area x true density) of specific surface area [m 2 / g] and true density [g / cm 3] of 6 to 8, Silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, Magnesium, barium nitrate, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium titanate, barium zirconate, calcium zirconate , Zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly suitable. As the silica, spherical silica is preferable. The inorganic fillers may be used singly or in combination of two or more kinds. As commercially available products of silica used as an inorganic filler, for example, Adomapine manufactured by Adomex Co., Ltd., SFP series manufactured by Denki Kagaku Kogyo Co., Ltd., Shinnitetsu Sumikin Materials Co., Quot; SP (H) series &quot;, &quot; Sciqas series &quot; manufactured by Sakai Kagaku Kogyo Co., Ltd. and &quot; Sephaster series &quot; manufactured by Nippon Shokubai Co., &Quot; AZ, AX series &quot;, manufactured by Mitsubishi Chemical Corporation.

In the present invention, the average particle diameter of the inorganic filler is 1.6 占 퐉 or less. The average particle diameter of the inorganic filler is preferably 1.5 占 퐉 or less, more preferably 1.4 占 퐉 or less. On the other hand, from the viewpoints of obtaining a resin varnish having appropriate viscosity and good handleability when forming a resin varnish by using a curable resin composition and preventing the rise of the melt viscosity of the curable resin composition layer, the average particle diameter of the inorganic filler is , Preferably 0.5 m or more, more preferably 0.6 m or more, and even more preferably 0.7 m or more.

The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured with a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter is determined as the average particle diameter. The measurement sample can be preferably those in which an inorganic filler is dispersed in water by ultrasonic waves. As the laser diffraction particle size distribution measuring apparatus, "SALD-2200" manufactured by Shimadzu Corporation may be used.

The specific surface area of the inorganic filler can be measured by the BET method. For the measurement of the specific surface area, a BET automatic specific surface area measuring apparatus (Macsorb HM-1210 manufactured by Moon Tec Co., Ltd.) or the like can be used. The true density of the inorganic filler can be measured using a micro-ultra-peak furnace (MUPY-21T manufactured by KANTA CHROME INSTRUMENTS, Japan).

According to the present invention, by setting the product of the specific surface area [m 2 / g] and the true density [g / cm 3] of the inorganic filler to 6 or more, the inflow of the curable resin composition into the cavity is made good, The expansion ratio can be lowered. The lower limit of the product of the specific surface area and the true density of the inorganic filler is preferably 6.1 or more, more preferably 6.3 or more. The product of the specific surface area and the true density of the inorganic filler is preferably 7.7 or less, more preferably 7.5 or less.

From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler is preferably selected from the group consisting of an amino silane coupling agent, an epoxy silane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane compound, an organosilazane compound, It is preferable that the surface treatment agent is treated with at least one surface treatment agent such as a coupling agent. As commercially available products of the surface treatment agent, for example, KBM403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM803 (3-mercapto KBE903 "(3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.," KBM573 "(manufactured by Shin-Etsu Chemical Co., SZ-31 (hexamethyldisilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM103 (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin- ) &Quot; KBM-4803 &quot; (long-chain epoxy type silane coupling agent).

The degree of the surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably at least 0.02 mg / m 2, more preferably at least 0.1 mg / m 2, and most preferably at least 0.2 mg / m 2 from the viewpoint of improving the dispersibility of the inorganic filler. On the other hand, it is preferably 1 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, still more preferably 0.5 mg / m 2 or less from the viewpoint of preventing the melt viscosity of the resin varnish or the melt viscosity in the sheet form from rising .

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to an inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25 캜 for 5 minutes. After the supernatant is removed and the solid content is dried, 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 Seisakusho Co., Ltd. and the like can be used.

The content of the inorganic filler (c) in the curable resin composition is 74 mass% or more, preferably 76 mass% or more, and more preferably 78 mass% or more. The upper limit of the content of the inorganic filler (c) is preferably 90% by mass or less, more preferably 85% by mass or less, from the viewpoint of obtaining an insulating layer capable of forming fine wiring thereon.

(d) a resin having a functional group having a glass transition temperature of 25 DEG C or lower, and a resin having a functional group liquid at 25 DEG C (component (d)).

In a preferred embodiment, the curable resin composition contains component (d) together with an epoxy resin (a ') having an aromatic structure (component (a' ')). (insulation layer) of the curable resin composition layer can be reduced by containing a flexible resin such as the component (d), and the occurrence of warpage of the wiring board, which can be produced by using the resin sheet of the present invention, .

The glass transition temperature of the component (d) having a functional group having a glass transition temperature (Tg) of 25 占 폚 or lower is preferably 20 占 폚 or lower, more preferably 15 占 폚 or lower. The lower limit of the glass transition temperature of the component (d) is not particularly limited, but it is usually -15 캜 or higher.

In a resin having a functional group which is liquid at 25 占 폚, if the liquid is liquid at 25 占 폚, the Tg of the resin may naturally be considered to be 25 占 폚 or lower.

The functional group of the component (d) preferably has a functional group capable of reacting with the component (a) or (a '). In a preferred embodiment, the functional group of the component (d) is at least one functional group selected from the group consisting of a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group. Of these, as the functional group, a hydroxyl group, an acid anhydride group, an epoxy group and a phenolic hydroxyl group are preferable, and a hydroxyl group, an acid anhydride group and an epoxy group are more preferable. However, when an epoxy group is contained as the functional group, the component (d) does not have an aromatic structure.

From the viewpoint of obtaining a curable resin composition layer having a low elastic modulus, the component (d) is preferably an alkylene structural unit having 2 to 15 carbon atoms (preferably 3 to 10 carbon atoms, more preferably 5 to 6 carbon atoms ), An alkyleneoxy structural unit having 2 to 15 carbon atoms (preferably 3 to 10 carbon atoms, more preferably 5 to 6 carbon atoms), a butadiene structural unit, an isoprene structural unit, an isobutylene structural unit (Meth) acrylate structural unit, and a polysiloxane structural unit, and more preferably at least one structural unit selected from a butadiene structural unit, a urethane structural unit, a (meth) acrylate structural unit, And more preferably at least one structural unit selected from an acrylate structural unit. Further, "(meth) acrylate" refers to methacrylate and acrylate.

One suitable embodiment of the component (d) is a saturated and / or unsaturated butadiene resin containing a functional group which is liquid at 25 占 폚. Examples of the saturated and / or unsaturated butadiene resin which is liquid at 25 占 폚 include saturated and / or butadiene resins containing an acid anhydride group in liquid state at 25 占 폚, saturated and / or butadiene resins containing phenolic hydroxyl groups in a liquid state at 25 占 폚, Containing saturated and / or butadiene resin, a liquid saturated isocyanate group-containing saturated and / or butadiene resin at 25 占 폚, and a saturated and / or butadiene-containing urethane group liquid at 25 占 폚. Is preferable. Here, the term &quot; saturated and / or unsaturated butadiene resin &quot; refers to a resin containing a saturated butadiene skeleton and / or an unsaturated butadiene skeleton. In these resins, saturated butadiene skeleton and / or unsaturated butadiene skeleton are included in the main chain May be included.

The number average molecular weight (Mn) of the functional group-containing saturated and / or unsaturated butadiene resin which is liquid at 25 占 폚 is preferably 500 to 50000, more preferably 1000 to 10000. Here, the number average molecular weight (Mn) of the resin is the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

The functional group equivalent of the functional group-containing saturated and / or unsaturated butadiene resin which is liquid at 25 占 폚 is preferably 100 to 10000, more preferably 200 to 5000. [ The functional group equivalent is a mass of a resin containing one equivalent of a functional group. For example, the epoxy equivalent of the resin can be measured according to JIS K7236.

As the saturated and / or unsaturated butadiene resin which is liquid at 25 占 폚, a saturated and / or butadiene skeleton-containing epoxy resin which is liquid at 25 占 폚 is preferable and a polybutadiene skeleton-containing epoxy resin which is liquid at 25 占 폚, Is more preferable, and a polybutadiene skeleton-containing epoxy resin which is liquid at 25 占 폚 and a hydrogenated polybutadiene skeleton-containing epoxy resin which is liquid at 25 占 폚 are more preferable. Here, the &quot; hydrogenated polybutadiene skeleton-containing epoxy resin &quot; refers to an epoxy resin in which at least a part of the polybutadiene skeleton is hydrogenated, and the polybutadiene skeleton does not necessarily have to be a completely hydrogenated epoxy resin. Specific examples of the polybutadiene skeleton-containing resin which is liquid at 25 占 폚 and the hydrogenated polybutadiene skeleton-containing resin which is liquid at 25 占 폚 include "PB3600", "PB4700" (polybutadiene skeletal epoxy resin) manufactured by Daicel Co., FCA-061L &quot; (hydrogenated polybutadiene skeletal epoxy resin) manufactured by Tex Corporation.

As the saturated and / or unsaturated butadiene resin containing an acid anhydride group which is liquid at 25 占 폚, a saturated and / or unsaturated butadiene skeleton-containing acid anhydride resin which is liquid at 25 占 폚 is preferable. As the phenolic hydroxyl group-containing saturated and / or unsaturated butadiene resin which is in a liquid state at 25 占 폚, a phenol resin containing a saturated and / or unsaturated butadiene skeleton which is liquid at 25 占 폚 is preferable. As the unsaturated and / or unsaturated butadiene resin having an isocyanate group which is in a liquid state at 25 占 폚, a saturated and / or unsaturated butadiene skeleton-containing isocyanate resin which is liquid at 25 占 폚 is preferable. As the saturated and / or unsaturated butadiene resin having a urethane group which is in a liquid state at 25 占 폚, a urethane resin containing a saturated and / or unsaturated butadiene skeleton which is liquid at 25 占 폚 is preferable.

Another suitable embodiment of the component (d) is a functional group-containing acrylic resin having a Tg of 25 캜 or lower. Acrylic acid-containing acrylic resin having a Tg of 25 占 폚 or lower, an acrylic resin containing a phenolic hydroxyl group having a Tg of 25 占 폚 or lower, an isocyanate group-containing acrylic resin having a Tg of 25 占 폚 or lower, Or less and an epoxy group-containing acrylic resin having a Tg of 25 占 폚 or less.

The number-average molecular weight (Mn) of the functional group-containing acrylic resin having a Tg of 25 占 폚 or lower is preferably 10,000 to 1,000,000, more preferably 30,000 to 900,000. Here, the number average molecular weight (Mn) of the resin is the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

The functional group equivalent of the functional group-containing acrylic resin having a Tg of 25 占 폚 or less is preferably 1000 to 50000, more preferably 2500 to 30000.

The epoxy group-containing acrylic resin having a Tg of 25 占 폚 or less is preferably an epoxy group-containing acrylic ester copolymer resin having a Tg of 25 占 폚 or less. Specific examples thereof include "SG-80H" (epoxy group- SG-P3 &quot; (an epoxy group-containing acrylic ester copolymer resin (number-average molecular weight (Mn): 350000 g / mol, epoxy: 0.07 eq / Average molecular weight (Mn): 850000 g / mol, epoxy: 0.21 eq / kg, Tg 12 DEG C).

As the acid anhydride group-containing acrylic resin having a Tg of 25 DEG C or lower, an acrylic acid ester copolymer resin containing an acid anhydride group having a Tg of 25 DEG C or lower is preferable.

As the phenolic hydroxyl group-containing acrylic resin having a Tg of 25 占 폚 or lower, a phenolic hydroxyl group-containing acrylic ester copolymer resin having a Tg of 25 占 폚 or lower is preferable. Specific examples thereof include "SG-790" (Number average molecular weight (Mn): 500000 g / mol, hydroxyl value: 40 mgKOH / kg, Tg -32 占 폚).

One suitable embodiment of the component (d) is a polyimide resin having a butadiene structural unit, a urethane structural unit and an imide structural unit in the molecule, and the polyimide resin preferably has a phenol structure at the molecular end .

The number average molecular weight (Mn) of the polyimide resin is preferably 1000 to 100000, more preferably 10000 to 15000. Here, the number average molecular weight (Mn) of the resin is the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

The acid value of the polyimide resin is preferably 1 KOH / g to 30 KOH / g, and more preferably 10 KOH / g to 20 KOH / g.

The content of the butadiene structure of the polyimide resin is preferably 60 to 95% by mass, and more preferably 75 to 85% by mass.

Details of the polyimide resin can be taken into account in the disclosure of International Publication No. 2008/153208, the contents of which are incorporated herein.

From the viewpoint of improving the breaking strength, the component (d) is preferably highly compatible with components other than the component (d). That is, it is preferable that the component (d) is dispersed in the curable resin composition layer.

The content of the component (d) in the curable resin composition is not particularly limited, but is preferably 14 mass% or less, more preferably 13 mass% or less, further preferably 12 mass% or less. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, further preferably 4% by mass or more.

The curable resin composition may contain additives (e) such as thermoplastic resins, curing accelerators, flame retardants and rubber particles in addition to the above (a), (b), (c) and (d).

(e) Additive

- Thermoplastic resin -

Examples of the thermoplastic resin include thermoplastic resins such as phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyether sulfone resin, Ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins. Of these, phenoxy resins are preferable. The thermoplastic resin may be used singly or in combination of two or more kinds.

The weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably in the range of 5,000 to 100,000, 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 of the thermoplastic resin in terms of polystyrene is measured by a gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight of the thermoplastic resin in terms of polystyrene was measured using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K (manufactured by Showa Denko K.K. -804L / K-804L as a mobile phase, chloroform at a column temperature of 40 占 폚, and using a standard polystyrene calibration curve.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, A phenoxy resin having at least one skeleton selected from the group consisting of a skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethyl cyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used singly or in combination of two or more kinds. Specific examples of the phenoxy resin include "1256" and "4250" (both phenol resins containing a bisphenol A skeleton), "YX8100" (phenoxy resin containing a bisphenol S skeleton), and "YX6954" (Phenoxy resin containing a bisphenol acetophenone skeleton), "FX280" and "FX293" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., "YL6954BH30" and "YX7553" manufactured by Mitsubishi Kagaku Co., YL7769BH30 "," YL6794 "," YL7213 "," YL7290 ", and" YL7482 ".

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 "DENKA BUTYLAL 4000-2", "DENKA BUTYLAL 5000-A", "DENKA BUTYLAL 6000-C" and "DENKA BUTYLAL 6000-C" manufactured by Denki Kagaku Kogyo Co., Butyral 6000-EP &quot;, S-Rex BH series, BX series, KS series, BL series, BM series manufactured by Sekisui Igakugo Kogyo Co., Ltd., and the like.

Specific examples of the polyimide resin include "Rika Coat SN20" and "Rika Coat PN20" manufactured by Shin-Nihon Rika K.K.

Specific examples of the polyamide-imide resin include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo Co., Ltd.

Specific examples of the polyether sulfone resin include "PES 5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

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 an oligophenylene ether styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Kagaku Co., Ltd., and the like.

Of these, phenoxy resins and polyvinyl acetal resins are preferable as the thermoplastic resin from the viewpoint of obtaining an insulating layer having a lower surface roughness and better adhesion to the conductor layer in combination with other components. Accordingly, in a preferred embodiment, the thermoplastic resin component contains at least one member selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin.

The content of the thermoplastic resin in the curable resin composition is preferably 0% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, still more preferably 0% by mass to 10% by mass from the viewpoint of appropriately adjusting the melt viscosity of the curable resin composition layer Is from 0.6% by mass to 8% by mass.

- Curing accelerator -

Examples of the curing accelerator include phosphorus hardening accelerator, amine hardening accelerator, imidazole hardening accelerator, guanidine hardening accelerator, phosphorus hardening accelerator, amine hardening accelerator and imidazole hardening accelerator , An amine-based curing accelerator, and an imidazole-based curing accelerator are more preferable. The curing accelerator may be used singly or in combination of two or more kinds.

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

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl- Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 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- [ Imidazolyl- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- Triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl- , 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-di Methylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and the like, which are commercially available, such as 1-hydroxy-1H-pyrrolo [ Azole compounds, and adducts of an imidazole compound and an epoxy resin, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As the imidazole-based curing accelerator, a commercially available product may be used, and for example, "P200-H50" manufactured by Mitsubishi Kagaku Co., Ltd. and the like can be mentioned.

Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, , Trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [ 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and the like, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferred.

The content of the curing accelerator in the curable resin composition is not particularly limited, but is preferably in the range of 0.05% by mass to 3% by mass.

- Flame retardant -

The curable resin composition may contain a flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicon-based flame retardant, a metal hydroxide, and the like. The flame retardant may be used alone, or two or more flame retardants may be used in combination.

As the flame retardant, a commercially available product may be used, for example, "HCA-HQ" manufactured by Sanko Co., Ltd., "PX-200" manufactured by Ohachi Kagaku Kogyo Co.,

The content of the flame retardant in the curable resin composition is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, still more preferably 1.5% by mass to 10% Do.

- Organic filler -

The curable resin composition may further contain a glass filler. As the organic filler, any organic filler that can be used in forming the insulating layer of the printed wiring board may be used. Examples thereof include rubber particles, polyamide fine particles, and silicone particles. Rubber particles are preferred.

As the rubber particles, a commercially available product may be used, and for example, "EXL2655" manufactured by Dow Chemical Co., Ltd., "AC3816N" manufactured by Aika Kogyo Co., Ltd. and the like can be mentioned.

The content of the organic filler in the curable resin composition is preferably 0.5% by mass to 20% by mass, and more preferably 0.7% by mass to 10% by mass.

The curable resin composition may further contain a flame retardant and other additives other than the organic filler as required. Examples of such other additives include organometallic compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds Compounds, and resin additives such as organic fillers, thickeners, antifoaming agents, leveling agents, adhesion-imparting agents, and coloring agents.

- Liquid amino resin -

From the viewpoint that the minimum melt viscosity of the curable resin composition layer is 12000 poise or less, the curable resin composition may further contain an amino resin (liquid amino resin) which is liquid at room temperature. The liquid amino resin can be used in place of, or in combination with, liquid epoxy resin. Examples of the liquid amino resin include alkylated melamine resins such as methylmelamine. The alkylated melamine resin may be produced by, for example, reacting melamine with formaldehyde to replace part or all of the hydrogen atoms of the amino group with a methylol group and then further reacting with an alcohol compound to convert a part or all of the methylol group into an alkoxymethyl group .

[Resin sheet]

Hereinafter, the resin sheet of the present invention will be described.

The resin sheet of the present invention comprises a support and a curable resin composition layer formed from the curable resin composition, wherein the curable resin composition layer has a minimum melt viscosity of 12000 poise or less. It is also preferable that the average linear thermal expansion coefficient of the insulating layer (cured product) obtained by curing the above-mentioned curable resin composition layer between 25 ° C and 150 ° C is not more than 17 ppm / ° C.

An example of the resin sheet of the present invention is shown in Fig. 2, the resin sheet 10 includes a support 11 and a curable resin composition layer 12 provided on the support 11. As shown in Fig.

<Support>

As the support, for example, a film made of a plastic material, a metal foil and a release paper can be mentioned, and a film or a metal foil made of a plastic material is preferable.

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter abbreviated as "PEN" (Hereinafter, abbreviated as "PC") and polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

In the case of using a metal foil as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, or a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, It is also good.

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

As the support, a support having a release layer having a release layer on the surface to be bonded to the curable resin composition layer may be used. Examples of the release agent used for the release layer of the release layer-adhered support include at least one release agent selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin. A commercially available product may be used as the release layer adherend. For example, "LUMINA-T6AM" manufactured by Toray Co., Ltd., a PET film having a release layer composed mainly of an alkyd resin-based release agent, SK-1 "," AL-5 ", and" AL-7 ".

The thickness of the support is not particularly limited, but is preferably in the range of 5 탆 to 75 탆, more preferably in the range of 10 탆 to 60 탆. When a release layer-adhered support is used, it is preferable that the thickness of the entirety of the release layer-adhered support is in the above range.

<Curable resin composition layer>

In the present invention, the lowest melt viscosity of the curable resin composition layer is preferably 12000 poise or less, preferably 10000 poise or less, more preferably 10000 poise or less, from the viewpoint of realizing good filling property of the inside of the cavity when the component built- 8000poise or less. The lower limit of the lowest melt viscosity of the curable resin composition layer is not particularly limited and may be usually 500 poise or more, 1000 poise or more, or the like.

Here, the &quot; minimum melt viscosity &quot; of the curable resin composition layer means the lowest viscosity exhibited by the curable resin composition layer when the resin of the curable resin composition layer is melted. Specifically, when the resin is melted by heating the curable resin composition layer at a constant heating rate, the melt viscosity of the resin is lowered along with the temperature rise in the initial stage, and then, when the temperature exceeds a certain temperature, the melt viscosity increases with the temperature rise . The "minimum melt viscosity" refers to the melt viscosity of such a minimum point. The minimum melt viscosity of the curable resin composition layer can be measured by a dynamic viscoelasticity method. Specifically, the lowest melt viscosity of the curable resin composition layer can be obtained by performing dynamic viscoelasticity measurement under conditions of a measurement start temperature of 60 占 폚, a temperature raising rate of 5 占 폚 / min, a frequency of 1 Hz, and elasticity 1 deg. As a dynamic viscoelasticity measuring device, for example, "Rheosol-G3000" manufactured by Yu-Bi Co., Ltd. may be mentioned.

In the present invention, the average linear thermal expansion coefficient of the insulating layer formed by curing the curable resin composition layer between 25 DEG C and 150 DEG C is 17 ppm / DEG C or less from the viewpoint of realizing an integrated circuit board in which the problem of warping is suppressed, Preferably not more than 16 ppm / 占 폚, more preferably not more than 15 ppm / 占 폚. The lower limit of the average linear thermal expansion coefficient is not particularly limited, but may be usually 1 ppm / ° C or more, 2 ppm / ° C or more, 3 ppm / ° C or more, and the like. The average linear heat expansion coefficient can be measured by a known method such as thermomechanical analysis. As a thermomechanical analyzer, for example, "Thermo Plus TMA8310" manufactured by Rigaku Corporation can be mentioned. In the present invention, the average linear thermal expansion coefficient of the insulating layer is an average linear thermal expansion coefficient of 25 to 150 DEG C in the planar direction when thermomechanical analysis is performed by the tensile weighting method.

In the present invention, the thickness of the curable resin composition layer made of the curable resin composition is preferably 300 占 퐉 or less, and more preferably 200 占 퐉 or less. The lower limit of the thickness of the curable resin composition layer is not particularly limited, but from the viewpoints of obtaining an insulating layer showing excellent peel strength to the conductor layer after the roughening treatment, and in view of ease of production of the resin sheet, Or more.

The resin sheet 10 of the present invention may further include a protective film on the surface of the curable resin composition layer 12 not bonded to the support 11 (that is, the surface opposite to the support). The protective film contributes to prevention of adhesion and scratches of dust or the like on the surface of the curable resin composition layer 12. [ As the material of the protective film, the same material as described for the support 11 may be used. The thickness of the protective film is not particularly limited, but is, for example, 1 m to 40 m. The resin sheet 10 can be used by peeling the protective film when producing a printed wiring board.

INDUSTRIAL APPLICABILITY The resin sheet of the present invention realizes good filling of parts inside the cavity at the time of manufacturing the component built-in circuit board and can realize the component built-in circuit board in which the problem of warping is suppressed. Therefore, the resin sheet of the present invention can be suitably used particularly for embedding the parts inside the cavity (for cavity filling) at the time of manufacturing the component built-in circuit board, and can be suitably used also in the use of mold underfill (encapsulation) . The resin sheet of the present invention can also be used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board). Since the resin sheet of the present invention can cause an insulating layer capable of forming fine wirings thereon, in the production of a printed wiring board by the build-up method, in order to form an insulating layer (for a build- ) Can be suitably used and more suitably used for forming a conductor layer by plating (for a build-up insulating layer of a printed wiring board on which a conductor layer is formed by plating).

<Production method of resin sheet>

Hereinafter, an example of a method for producing a resin sheet of the present invention will be described. A curable resin composition layer made of a curable resin composition is formed on a support.

As a method of forming the curable resin composition layer, for example, there can be mentioned a method of applying a curable resin composition to a support and drying the coating film to provide a curable resin composition layer.

In this method, the curable resin composition layer can be produced by preparing a resin varnish obtained by dissolving a curable resin composition in an organic solvent, applying the resin varnish on a support using a die coater or the like, and drying the resin varnish.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve, Carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. The organic solvent may be used singly or in combination of two or more kinds.

The resin varnish may be dried by a known drying method such as heating or hot air blowing. When a resin varnish containing, for example, 30 to 60% by mass of an organic solvent is used, it is dried at 50 to 150 ° C for 3 minutes to 10 minutes to form a resin varnish on the support A curable resin composition layer can be formed.

Further, in the present invention, for example, a resin sheet may be produced by laminating a support on a curable resin composition layer after forming a curable resin composition layer on a protective film.

<Wiring Board>

The wiring board of the present invention comprises an insulating layer formed by curing the curable resin composition layer of the resin sheet of the present invention and a conductor layer. Hereinafter, the component built-in circuit board which is one embodiment of the wiring board of the present invention will be described.

A component built-in circuit board includes: (A) a circuit board having first and second main surfaces and having a cavity penetrating between the first and second main surfaces, and a bonding material bonding to the second main surface of the circuit board , A resin sheet of the present invention is applied to a circuit board to which a component is attached, which includes a component adhered by the adhesive material in the cavity of the circuit board, (B) a heat treatment step of heat-treating the circuit board on which the resin sheet is laminated, (C) a step of peeling the attachment material from the second main surface of the circuit board A second lamination step of vacuum laminating the second resin sheet so that the curable resin composition layer is bonded to the second main surface of the circuit board; and (D) a second lamination step of dipping the curable resin composition layer of the resin sheet and the second resin sheet Curable resin And a step of thermally curing the composition layer in this order. Prior to the description of each process, the &quot; circuit board to which a component is attached &quot; using the resin sheet 10 of the present invention will be described.

(Circuit board with attached parts)

A circuit board (hereinafter also referred to as a &quot; component mounting circuit board &quot; or &quot; cavity substrate &quot;) to which components are attached has first and second main surfaces, and a cavity penetrating between the first and second main surfaces is formed A circuit board, a mounting material which is bonded to the second main surface of the circuit board, and a component which is attached by the mounting material inside the cavity of the circuit board.

The component-affixed circuit board can be prepared according to any conventionally known procedure at the time of manufacturing the component-embedded circuit board. Hereinafter, with reference to Figs. 1A to 1D, an example of a procedure for preparing a component mounting circuit board will be described, but the present invention is not limited thereto.

First, a circuit board is prepared (Fig. 1A). Means a plate-like substrate having opposing first and second main surfaces and having circuit wirings pattern-processed on one or both of the first and second major surfaces. 1A schematically shows a cross section of a circuit board 1. The circuit board 1 includes a substrate 2 and circuit wirings 3 such as via wirings and surface wirings. In the following description, the first main surface of the circuit board refers to the upper main surface of the circuit board shown for convenience, and the second main surface of the circuit board refers to the lower main surface of the circuit board.

Examples of the substrate 2 used for the circuit board 1 include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. A glass epoxy substrate is preferred. Further, when manufacturing the printed wiring board, the inner circuit board of the intermediate product in which the insulating layer and / or the conductor layer is to be formed is also included in the &quot; circuit board &quot;.

The thickness of the substrate 2 of the circuit board 1 is preferably thin in view of the thickness of the component built-in circuit board, preferably less than 400 m, more preferably 350 m or less, More preferably not more than 250 mu m, particularly preferably not more than 200 mu m, not more than 180 mu m, not more than 170 mu m, not more than 160 mu m, or not more than 150 mu m. The lower limit of the thickness of the substrate 2 is not particularly limited, but is preferably 50 占 퐉 or more, more preferably 80 占 퐉 or more, and even more preferably 100 占 퐉 or more, from the viewpoint of improvement in handling during transportation.

The dimensions of the circuit wiring 3 provided in the circuit board 1 may be determined according to desired characteristics. For example, the thickness of the surface wiring is preferably 40 占 퐉 or less, more preferably 35 占 퐉 or less, further preferably 30 占 퐉 or less, still more preferably 25 占 퐉 or less , Particularly preferably not more than 20 mu m, not more than 19 mu m, or not more than 18 mu m. The lower limit of the thickness of the surface wiring is not particularly limited, but is usually 1 占 퐉 or more, 3 占 퐉 or more, 5 占 퐉 or more, or the like.

Next, a cavity (recess) for accommodating the component is provided on the circuit board (Fig. 1B). A cavity 2a may be formed at a predetermined position of the substrate 2 so as to pass between the first and second main surfaces of the circuit board as schematically shown in Fig. The cavity 2a can be formed by a known method using, for example, a drill, a laser, a plasma or an etching medium in consideration of the characteristics of the substrate 2.

Although only one cavity 2a is shown in Fig. 1B, a plurality of cavities 2a may be provided at a predetermined interval from each other. The pitch between the cavities 2a is preferably short from the viewpoint of miniaturization of the component built-in circuit board. The pitch between the cavities 2a varies depending on the opening dimension of the cavity 2a itself, but is preferably 10 mm or less, more preferably 9 mm or less, further preferably 8 mm or less, 7 mm or less, particularly preferably 6 mm or less. According to the method of the present invention, even when the cavity is provided at such a short pitch, the occurrence of substrate warpage can be suppressed. The lower limit of the pitch between the cavities 2a varies depending on the opening dimension of the cavity 2a itself, but is usually 1 mm or more, 2 mm or more, and the like. The pitches between the cavities 2a need not be the same across the circuit board, and may be different.

The shape of the opening of the cavity 2a is not particularly limited and may be any shape such as a rectangle, a circle, a substantially rectangular shape, or a substantially circular shape. The opening dimension of the cavity 2a differs depending on the design of the circuit wiring. For example, when the opening shape of the cavity 2a is rectangular, it is preferably 5 mm x 5 mm or less, Mm or less, or more preferably 2 mm x 2 mm or less. The lower limit of the opening dimension varies depending on the dimensions of the parts to be accommodated, but is usually 0.5 mm x 0.5 mm or more. The opening shape and opening dimension of the cavity 2a are not necessarily the same across the circuit board, and may be different.

Next, an attaching material is laminated on the second main surface of the circuit board on which the cavity is provided (Fig. 1C). Is not particularly limited as long as it has a pressure-sensitive adhesive surface exhibiting sufficient tackiness for attaching the component, and any conventionally known adhesive material may be used in manufacturing the component built-in circuit board. 1C, the film-like adhesive material 4 is laminated so that the adhesive surface of the adhesive material 4 adheres to the second main surface of the circuit board. As a result, the adhesive surface of the adhesive material 4 is exposed through the cavity 2a.

Examples of the adhesive material on the film include UC series (UV tape for wafer dicing) manufactured by FURUKAWA DENKI KOGYO CO., LTD.

Next, the parts are attached to the adhesive surface of the exposed adhesive material exposed through the cavity (Fig. 1D). In the form schematically shown in Fig. 1 (d), the component 5 is attached to the adhesive surface of the adhesive material 4 exposed through the cavity 2a.

As the component 5, an appropriate electric component may be selected in accordance with a desired characteristic, and examples thereof include passive components such as capacitors, inductors and resistors, and active components such as semiconductor bear chips. The same component 5 may be used for all the cavities, or a different component 5 may be used for each cavity.

The circuit board 3 may be provided after the cavity 2a is formed on the substrate 2 and the circuit board 3 may be mounted on the circuit board 2 by attaching the adhesive material 4 to the circuit The cavity 2a may be formed after being laminated on the second main surface of the substrate.

A method of manufacturing the component built-in circuit board using the resin sheet of the present invention will be described. In the following description, the resin sheet of the present invention which is laminated on the first main surface and the second main surface of the component built-in circuit board is referred to as "first resin sheet 10" and "second resin sheet 20" . As the first resin sheet 10 and the second resin sheet 20, the same or different ones may be used. In the following description, the case where the support 11 of the first resin sheet 10 is referred to as the first support 11 to distinguish the first resin sheet 10 from the second resin sheet 20 have.

&Lt; (A) First lamination step (lamination of first resin sheet) >

First, a resin sheet (first resin sheet 10) of the present invention is laminated on a circuit board to which components are attached (first lamination step). Specifically, on a circuit board 1 ' The first resin sheet 10 is vacuum laminated so that the curable resin composition layer 12 is bonded to the first main surface of the circuit board (see Fig. 3A). Here, the first resin sheet 10 is laminated on the curable resin composition layer In the case of a constitution comprising a protective film covering the protective film 12, the protective film is peeled off, and then lamination to the circuit board is carried out.

The vacuum lamination of the resin sheet 10 to the component attaching circuit board 1 'can be performed by, for example, applying a first resin sheet 10 on the component mounting circuit board 1 '). As a member for heating and pressing the first resin sheet 10 to the component mounting circuit board 1 '(not shown) (hereinafter also referred to as "hot pressing member"), for example, a heated metal plate Etc.) or a metal roll (SUS roll). The first resin sheet 10 is bonded to the projections and depressions caused by the circuit wiring 3 and the cavity 2a of the attachment circuit board 1 'without directly pressing the heat press member onto the first resin sheet 10, It is preferable to press through an elastic material such as heat-resistant rubber.

The heat pressing temperature is preferably 80 to 160 占 폚, more preferably 100 to 140 占 폚, the heat pressing pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa , And the heat pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The vacuum lamination is preferably performed under a reduced pressure of 26.7 hPa or less.

The vacuum lamination can be performed by a commercial vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressurized laminator manufactured by Meikishesakusho Co., Ltd., a vacuum applicator manufactured by Nichigo Morton Co., Ltd., and a two stage build-up laminator manufactured by Nichigo Morton Co., .

After the first laminating step, a smoothing step for performing smoothing of the laminated first resin sheet 10 by pressurizing under normal pressure (at atmospheric pressure), for example, a hot press member on the first support 11 side . The press condition of the smoothing process may be the same as that of the vacuum lamination.

The smoothing process can be performed by a commercial laminator. The first laminating step and the smoothing step may be carried out continuously using the commercial vacuum laminator.

After the first laminating process, the curable resin composition layer 12 is filled in the cavity 2a, and the component 5 in the cavity 2a is embedded in the curable resin composition layer 12 3b).

&Lt; (B) Heat treatment step >

Next, the circuit board on which the first resin sheet 10 is laminated is subjected to heat treatment (heat treatment step). The heating temperature in this step is preferably 155 占 폚 or lower, more preferably 150 占 폚 or lower, still more preferably 145 占 폚 or lower, still more preferably 140 占 폚 or lower. The lower limit of the heating temperature is preferably 110 占 폚 or higher, more preferably 115 占 폚 or higher, even more preferably 120 占 폚 or higher, even more preferably 125 占 폚 or higher.

The heating time in the heat treatment process varies depending on the heating temperature, but is preferably 10 minutes or more, more preferably 15 minutes or more, and even more preferably 20 minutes or more. The upper limit of the heating time is not particularly limited, but it is usually 60 minutes or less.

The heating treatment of the curable resin composition layer 12 in the heat treatment step is preferably performed under atmospheric pressure (normal pressure).

The heat treatment of the curable resin composition layer 12 in the heat treatment step may be performed in a state where the first support body 11 is attached to the curable resin composition layer 12 and the first support body 11 is peeled off Or after the curable resin composition layer 12 is exposed. In a preferred embodiment, the heat treatment of the curable resin composition layer 12 is carried out with the first support 11 adhered to the first curable resin composition layer 12. This is advantageous in terms of prevention of adhesion of foreign matter and prevention of damage to the curable resin composition layer.

When the heat treatment of the curable resin composition layer 12 in the heat treatment step is carried out with the first support 11 attached thereto, the first support 11 hardens the curable resin composition layer 12 (Circuit wiring) to the insulating layer (cured product) obtained by the first laminating step, for example, may be peeled off between the first heat treatment step and the second laminating step described later, and the second laminating step And the thermosetting step (to be described later), or may be peeled off after the thermosetting step. In a preferred embodiment, the first support 11 is peeled off after the heat curing step. In the case of using a metal foil such as copper foil as the first supporting member 11, since the conductor layer (circuit wiring) can be provided by using such a metal foil as described later, the first supporting member 11 You do not have to peel off.

In a preferred embodiment, the circuit board may be cooled to room temperature (room temperature) during the heat treatment process of the first laminating process.

In a preferred embodiment, the curable resin composition layer 12 becomes a curable resin composition layer (heat treated body) 12 'by performing a heat treatment process (see Fig. 3C). 3C shows a form in which a curable resin composition layer (heat treated body) 12 'is obtained by heat treatment in a state where the first support body 11 is attached.

&Lt; (C) Second lamination step (lamination of second resin sheet) >

After the heat treatment process, the adhesive material 4 is peeled off from the second main surface of the circuit board to expose the second main surface of the circuit board 2. The second resin sheet 20 is then vacuum laminated so that the curable resin composition layer 22 is bonded to the second main surface (lower surface side) of the circuit board 2 (see Fig. 3d). Here, the second resin sheet includes a support body 21 (also referred to as a second support body) and a curable resin composition layer 22 (also referred to as a second curable resin composition layer) bonded to the support body. As the second resin sheet, it is preferable to use the resin sheet of the present invention. The constitution of the second support or the second curable resin composition layer is the same as that of the above-mentioned resin sheet of the present invention and the curable resin composition layer. The second resin sheet may be a resin sheet having a different structure from the first resin sheet (for example, a resin sheet having a plurality of layers of curable resin composition layers of different compositions, or a resin sheet having a different minimum melt viscosity condition , And a layer of a curable resin composition which does not satisfy the average linear thermal expansion coefficient) may be used.

The peeling of the attachment material 4 may be performed according to a conventionally known method depending on the type of the attachment material 4. [ For example, when a UV tape for wafer dicing such as UC series manufactured by Furukawa Electric Kogyo K.K. is used as the adhesive material 4, the adhesive material 4 is subjected to UV irradiation, and the adhesive material 4 ) Can be peeled off. The conditions such as the amount of UV irradiation and the like can be said to be well-known conditions that are generally employed in manufacturing the component built-in circuit board.

It is possible to suppress the occurrence of substrate warpage even in the case of using a circuit board having a high cavity density or a thin circuit board by carrying out the heat treatment step and hence the substrate transfer from the heat treatment step to the second laminating step It is possible to smoothly perform the second laminating process without causing trouble. Further, since the curable resin composition layer is subjected to the heat treatment under specific conditions, it is possible to suppress the positional shift (displacement) of the component accompanying the vacuum lamination in the second laminating step, Can be satisfactorily realized.

The vacuum lamination of the second resin sheet 20 in the second lamination step may be performed by the same method and conditions as the vacuum lamination of the first resin sheet 10 in the first lamination step.

In a preferred embodiment, a process of cooling the circuit board to room temperature (room temperature) may be performed between the heat treatment step and the second laminating step.

In the second laminating step, the second curable resin composition layer 22 and the second support body 21 are laminated on the second main surface of the circuit board 2 (see Fig. 3E).

The second support body 21 may be peeled off prior to the step of providing the conductor layer (circuit wiring) on the insulating layer obtained by curing the second curable resin composition layer 22, and for example, It may be peeled off between the hardening step or the hardening step. In a preferred embodiment, the second support 21 is peeled off after the curing process. In the case where a metal foil such as copper foil is used as the second support member 21, since the conductor layer (circuit wiring) can be provided by using such a metal foil as described later, the second support member 21 You do not have to peel off.

&Lt; (D) Curing Process >

In the curing process, the curable resin composition layer 12 of the first resin sheet 10 and the second curable resin composition layer 22 of the second resin sheet 20 are thermally cured. Thereby, on the first main surface of the circuit board 2, the curable resin composition layer (heat treatment body) 12 'forms the insulating layer 12' '(cured product) On the two main surfaces, the second curable resin composition layer 22 forms the insulating layer 22 "(cured product) (see Fig. 3F).

The conditions for thermal curing are not particularly limited, and the conditions that are generally employed when forming the insulating layer of the component internal circuit board may be used.

The heat curing conditions of the curable resin composition layers 12 and 22 of the first and second resin sheets 10 and 20 vary depending on the composition of the curable resin composition used for each curable resin composition layer, (Preferably in the range of 150 to 210 占 폚, more preferably in the range of 170 to 190 占 폚), and the curing time is in the range of 5 to 90 minutes (preferably in the range of 10 to 75 Minute, more preferably 15 minutes to 60 minutes).

The curable resin composition layer 12 and the second curable resin composition layers 12 and 22 may be preheated to a temperature lower than the curing temperature before thermosetting. The curable resin composition layers 12 and 22 may be cured at a temperature of 50 占 폚 to 120 占 폚 (preferably 60 占 폚 to 110 占 폚, and more preferably 70 占 폚 to 100 占 폚) May be preheated for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes). In the case of performing the preheating, this preheating is also included in the curing process.

The thermosetting of the respective curable resin composition layers in the curing step is preferably carried out under atmospheric pressure (atmospheric pressure).

In a preferred embodiment, a process of cooling the circuit board to room temperature (room temperature) may be performed between the second laminating step and the curing step.

In the present invention, the average linear thermal expansion coefficient of the insulating layers 12 "and 22" formed by curing the curable resin composition layer 12 and the second curable resin composition layer 22 between 25 ° C and 150 ° C, It is preferably not more than 17 ppm / 占 폚, more preferably not more than 15 ppm / 占 폚, from the viewpoint of reducing warpage.

Although the embodiment using the attaching material has been described in detail above, the component built-in circuit board may be manufactured by using the resin sheet instead of the attaching material. The resin sheet to be used in place of the attachment material may be the same as the second resin sheet described above, and the resin sheet of the present invention or other resin sheet may be used. In the case where a resin sheet is used in place of the attachment material, the peeling step of the adhesive material is unnecessary.

<Other Processes>

When the component built-in circuit board is manufactured, a step of punching the insulating layer (perforating step), a step of roughening the surface of the insulating layer (roughening step), a step of forming a conductor layer on the surface of the roughened insulating layer Forming process). These processes may be carried out according to various methods known to those skilled in the art, which are used in the manufacture of the component internal circuit board. When the supports 11 and 12 of the respective resin sheets 10 and 20 are peeled off after the curing step, the peeling of the supports 11 and 21 may be performed between the curing step and the punching step, between the punching step and the blending step, It may be carried out between the roughening step and the conductor layer forming step.

The piercing step is a step of piercing the insulating layers 12 " and 22 "(cured product), thereby forming holes such as via holes in the insulating layers 12 " and 22 ". For example, holes can be formed in the insulating layers 12 "and 22" by using a drill, a laser (carbon dioxide gas laser, YAG laser or the like), plasma or the like. In the component built-in circuit board, the insulating layers 12 "and 22" are generally conducted by a via hole.

The roughening step is a step of roughening the insulating layers 12 "and 22 ". The procedure and conditions of the harmonic treatment are not particularly limited, and known procedures and conditions that are usually used when forming the insulating layers 12 " and 22 "of the component built-in circuit board can be adopted. For example, the roughening treatment of the insulating layers 12 "and 22" is performed by swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralizing treatment with a neutralizing liquid in this order, Quot; can be harmonized. The swelling liquid is not particularly limited, but an alkaline solution, a surfactant solution and the like can be mentioned, and an alkaline solution is preferable, and a sodium hydroxide solution and a potassium hydroxide solution are more preferable as the alkaline solution. Examples of commercially available swelling liquids include Swelling Dip · Sucuregan P, Swelling · Dip · Sucureganus SBU manufactured by Atotech Japan Co., Ltd., and the like. The swelling treatment by the swelling liquid is not particularly limited, and can be carried out, for example, by immersing the swelling liquid at 30 to 90 DEG C for 1 minute to 20 minutes in the insulating layers 12 ", 22 ". It is preferable to immerse the insulating layers 12 "and 22" in the swollen liquid at 40 to 80 DEG C for 5 seconds to 15 minutes from the viewpoint of suppressing the swelling of the resin of the insulating layers 12 "and 22" . The oxidizing agent is not particularly limited, and for example, an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide may be mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the first and second insulating layers in an oxidizing agent solution heated to 60 ° C to 80 ° C for 10 minutes to 30 minutes. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of the commercially available oxidizing agent include alkaline permanganic acid solutions such as Concentrate Compact P manufactured by Atotech Japan Co., Ltd., and Dozing Solution, Sucuregan P, and the like. As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, for example, Reduction Soluble Sucrine · Sucurentan P manufactured by Atotech Japan Co., Ltd. may be mentioned. The treatment with the neutralizing liquid can be carried out by immersing the treated surface subjected to the roughening treatment with the oxidizing agent solution in a neutralizing solution at 30 to 80 캜 for 5 minutes to 30 minutes. From the viewpoint of workability and the like, it is preferable to immerse the object subjected to the roughening treatment with the oxidizing agent solution in a neutralizing solution at 40 to 70 캜 for 5 minutes to 20 minutes.

The conductor layer forming step is a step of forming a conductor layer (circuit wiring) on the surface of the harmonized insulating layer.

The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, do. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys of two or more metals selected from the above-mentioned group (for example, nickel-chromium alloy, copper-nickel alloy, Alloy). Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, a copper-nickel alloy And an alloy layer of a copper-titanium alloy is preferable and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper or an alloy layer of a nickel- chromium alloy is more preferable, Is more preferable.

The conductor layer may have a single-layer structure or a multi-layer structure in which two or more single-metal layers or alloy layers made of different kinds 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 conductor layer is generally 3 mu m to 35 mu m, preferably 5 mu m to 30 mu m although it varies depending on the design of the desired component built-in circuit board.

The method of forming the conductor layer is not particularly limited as long as it can form a conductor layer (circuit wiring) having a desired pattern. In a preferred embodiment, the conductor layer can be formed by plating. For example, a conductor layer (circuit wiring) having a desired pattern can be formed by plating the surfaces of the first and second insulating layers by a conventionally well-known technique such as a semi-custom method or a pull-in method. Hereinafter, an example in which the conductor layer is formed by the semi-

First, a plating seed layer is formed on the surfaces of the two insulating layers 12 " and 22 "by electroless plating. Subsequently, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired pattern.

(Via wiring) is formed in the via hole by these steps, and the circuit wiring 3 provided on the surface of the insulating layers 12 "and 22" is electrically connected to the circuit wiring of the circuit board, 100) is obtained (see Fig. 3G).

When a metal foil such as copper foil is used as the first supporting body 11 and the second supporting body 21, a conductor layer may be formed by a subtractive method using the metal foil. Alternatively, the conductor layer may be formed by electrolytic plating using copper foil as the plating seed layer.

The manufacturing method of the component built-in circuit board may further include a step of disengaging the component built-in circuit board.

In the disassembling step, for example, a conventionally known dicing apparatus having a rotary blade is cut, and the obtained structure can be divided into individual component internal circuit board units.

[Semiconductor device]

The semiconductor device of the present invention includes the wiring board of the present invention (for example, the above-mentioned component internal circuit board).

Examples of such a semiconductor device include various semiconductor devices provided in electric products (such as a computer, a mobile phone, a digital camera and a television) and a vehicle (such as a motorcycle, a car, a train, .

[Example]

Hereinafter, the present invention will be described concretely with reference to examples, but the present invention is not limited to these examples. In the following description, &quot; part &quot; and &quot;% &quot; mean &quot; part by mass &quot; and &quot;% by mass &quot;, respectively, unless otherwise specified.

<Production of Resin Sheet>

Using the resin varnish (curable resin composition) prepared in the following procedure, resin sheets of Examples and Comparative Examples were prepared.

(Carrying inorganic filler)

As the silica 1 to 6, "ADMAPINE" manufactured by ADOMATEX, "SFP series" manufactured by Denki Kagaku Kogyo Co., Ltd., "SP (H) series" manufactured by Shinnitetsu Sumikin Materials Co., , "Sciqas series" manufactured by Sakai Kagaku Kogyo Co., Ltd., and "Sephaster Series" manufactured by Nihon Shokubai Co., Ltd. were subjected to surface treatment either singly or in combination, and then the particle size distribution and specific surface area Were measured and used in Examples and Comparative Examples.

As the alumina, surface treatment was carried out using "AZ series" and "AX series" (manufactured by Shinnitetsu Sumikin Materials Co., Ltd.), and then the particle size distribution and specific surface area were measured by the following method, 4.

(1) Measurement of average particle diameter

100 mg of powder of silica 1 to 6 or 100 mg of alumina powder, 0.1 g of dispersant ("SN9228" manufactured by SANNOK CO., LTD.) And 10 g of methyl ethyl ketone were weighed into a vial bottle and dispersed by ultrasonic wave for 20 minutes. The particle size distribution was measured in a batch cell system using a laser diffraction particle size distribution analyzer (SALD-2200, manufactured by Shimadzu Corporation), and the average particle diameter was calculated.

(2) Measurement of specific surface area

The specific surface area of silica 1 to 6 and alumina was measured using a BET automatic specific surface area measuring apparatus (Macsorb HM-1210 manufactured by Moon Tec Co., Ltd.) and is shown in Table 2.

(3) Measurement of true density

The true densities of silica 1 to 6 and alumina were measured by a micro-ultra-peak meter (MUPY-21T manufactured by KANTA CHROME · INSTRUMENTS, Japan) and are shown in Table 2.

(Preparation of resin varnish 1)

4 parts of bisphenol type liquid epoxy resin ("ZX1059" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent of about 169, 1: 1 mixture of bisphenol A type and bisphenol F type), 4 parts of naphthylene ether type epoxy resin , 10 parts of epoxy resin ("EXA-7311-G4", epoxy equivalent of about 213), 6 parts of biquilene type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, , 10 parts of a flame retardant (&quot; NC3000L &quot;, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: about 272) and 4 parts of a flame retardant ("PX-200" manufactured by Ohashi Chemical Industry Co., The solution was heated and dissolved while stirring. After cooling to room temperature, 10 parts of a triazine skeleton-containing cresol novolak curing agent ("LA3018-50P" manufactured by DIC Corporation, hydroxyl group equivalent of about 151, 50% solids content of 2-methoxypropanol solution) , 4 parts of phenol novolak type curing agent containing triazine skeleton ("LA-7054" manufactured by DIC Corporation, hydroxyl group equivalent of about 125, MEK solution of solid content 60%), 4 parts of a naphthol curing agent (manufactured by Shinnitetsu Sumikin Kagaku Co., 1 part of an amine-based curing accelerator (4-dimethylaminopyridine (DMAP), 5% by mass of a solid content MEK solution), 10 parts of an aminosilane-based coupling agent (SN-495V, a hydroxyl group equivalent of about 231 and a solid content of 60% 220 parts of spherical silica 1 (average particle diameter 1.47 占 퐉, specific surface area 3.07 m2 / g, carbon amount per unit surface area 0.30 mg / m2) surface-treated with a high-speed vulcanizing agent (KBM573, manufactured by Shin-Etsu Chemical Co., After uniformly dispersing in a rotary mixer, the mixture was filtered with a cartridge filter (&quot; SHP050 &quot; manufactured by ROKITECHNO) 1 was prepared.

(Preparation of resin varnish 2)

6 parts of a glycidylamine type liquid epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight: about 95), 6 parts of a biscylenol type epoxy resin (YX4000HK manufactured by Mitsubishi Kagaku Co., 6 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238), 6 parts of naphthalene type epoxy resin ("ESN475V" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., ) And 15 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) in a solid content of 30 mass%) were added 20 parts of solvent naphtha, Hexane and 5 parts of hexane in a mixed solvent under heating with stirring. After cooling to room temperature, 12 parts of a triazine skeleton-containing cresol novolac curing agent ("LA3018-50P" manufactured by DIC Corporation, hydroxyl group equivalent of about 151, 50% solids content of 2-methoxypropanol solution) 12 parts of an active ester type curing agent ("EXB-8000L-65M" manufactured by DIC Corporation, active agent equivalent of about 220, and a nonvolatile component of 65 mass% in MEK solution), 12 parts of amine curing accelerator (4-dimethylaminopyridine 1 part of a flame retardant (HCA-HQ manufactured by Sankyo Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenan (2 parts), rubber particles (EXL2655, manufactured by Dow Chemical Co., Ltd.), 2 parts of phenyltrimethoxysilane (KBM103 manufactured by Shin-Etsu Chemical Co., Ltd.) , 190 parts of spherical silica 2 (average particle diameter 1.33 mu m, specific surface area 3.38 m &lt; 2 &gt; / g, carbon amount per unit surface area 0.28 mg / m 2) After that, the mixture was filtered through a cartridge filter (manufactured by ROKITECHNO "SHP050"), to prepare a resin varnish 2.

(Preparation of resin varnish 3)

, 8 parts of a bisphenol type liquid epoxy resin ("ZX1059" manufactured by Shinnitetsu Sumikin Chemical Co., Ltd., epoxy equivalent weight: about 169, a 1: 1 mixture of bisphenol A type and bisphenol F type), naphthalene type liquid epoxy resin 3 parts of a naphthalene type epoxy resin (HP-4710, manufactured by DIC Corporation, epoxy equivalent weight: about 170), 4 parts of a biphenyl type epoxy resin (Nippon Kayaku Co., (1: 1 solution of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corp., cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass) Were dissolved by heating in a mixed solvent of 20 parts of solvent naphtha and 5 parts of cyclohexanone with stirring. After cooling to room temperature, 8 parts of a triazine skeleton-containing phenol novolac curing agent ("LA-7054" manufactured by DIC Corporation, a hydroxyl group equivalent of about 125, and a solid content of 60% 12 parts of an imidazole-based curing accelerator (&quot; 1B2PZ &quot; manufactured by Shinko Chemical Industry Co., Ltd., SN-485, hydroxyl group equivalent of about 212 and a solid content of 60% 1 part of a flame retardant (HCA-HQ manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9- (Average particle diameter: 2 mu m), 4 parts of an aminosilane coupling agent (&quot; KBM573 &quot; manufactured by Shin-Etsu Chemical Co., (Diameter: 1.06 mu m, specific surface area: 3.01 m &lt; 2 &gt; / g, carbon content per unit surface area: 0.31 mg / m 2) were mixed and uniformly dispersed with a high speed rotary mixer. SHP050 &quot;) to prepare a resin varnish 3.

(Preparation of resin varnish 4)

50 parts of the component (d) prepared as described below, and 3 parts of a bisphenol-type epoxy resin ("ZX1059" manufactured by Shinnittetsu Kagaku Co., Ltd., a 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169) , 2 parts of a bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238), and 2 parts of a flame retardant ("HCA-HQ", 10- Phenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 2 mu m) was dissolved by heating in a mixed solvent of 15 parts of solvent naphtha and 5 parts of cyclohexanone with stirring. 2 parts of an active ester type curing agent ("EXB-8000L-65M" manufactured by DIC Corporation, an activating group equivalent of about 220, and a nonvolatile component of 65 mass% of MEK solution), 2 parts of an imidazole type curing accelerator 1 part of 1B2PZ 1-benzyl-2-phenylimidazole, 5% solids in MEK solution) and a phenylamino silane coupling agent (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) 190 parts of a spherical alumina (average particle diameter 1.52 μm, specific surface area 1.70 m 2 / g, carbon content 0.11 mg / m 2 per unit surface area) was uniformly dispersed in a high-speed rotary mixer to prepare a cartridge filter ("SHP050" manufactured by ROKITECHNO Co., ) To obtain a resin varnish 4.

[Production of component (d)] [

50 g of a G-3000 (bifunctional hydroxyl terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl group equivalent = 1798 g / eq., Solid content: 100% by mass: manufactured by Nippon Soda Co., Ltd.) , 23.5 g of i-PEP 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Sekiyu Kagaku Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. After the temperature became uniform, the temperature was raised to 50 占 폚, and 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq.) Was added while stirring again to carry out the reaction for about 3 hours. Subsequently, the reaction product was cooled to room temperature, and then 8.96 g of benzophenone tetracarboxylic acid dianhydride (acid anhydride equivalent = 161.1 g / eq.), 0.07 g of triethylenediamine, 0.09 g of ethyldiglycol acetate Cell preparation) was added, the temperature was raised to 130 캜 with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm &lt; -1 &gt; was confirmed by FT-IR. The reaction product was cooled to room temperature and filtered through a 100-mesh follicle to obtain a polymer resin A having an imide skeleton, a urethane skeleton and a butadiene skeleton.

Viscosity: 7.5 Pa · s (25 ° C, E type viscometer)

Acid value: 16.9 mg KOH / g

Solid content: 50 mass%

Number average molecular weight: 13723

Glass transition temperature: -10 ° C

Content ratio of polybutadiene structural part: 50 / (50 + 4.8 + 8.96) x 100 = 78.4 mass%

(Preparation of resin varnish 5)

Except that 220 parts of silica 4 (average particle diameter 1.73 mu m, specific surface area 2.71 m &lt; 2 &gt; / g, carbon amount 0.26 mg / m 2 per unit surface area) of resin 1 of the resin varnish 1 was replaced with 220 parts of a cartridge filter (SHP100 &Quot;), a resin varnish 5 was prepared in the same manner as resin varnish 1.

(Preparation of resin varnish 6)

Except that 190 parts of silica 2 (190 parts) of Resin Varnish 2 was replaced with 190 parts of Silica 5 (average particle diameter of 1.11 mu m, specific surface area of 2.66 m2 / g, carbon amount per unit surface area of 0.22 mg / Resin Varnish 6 was prepared.

(Preparation of resin varnish 7)

Except that 120 parts of silica 6 (average particle diameter 0.77 占 퐉, specific surface area 5.76 m2 / g, carbon amount per unit surface area 0.35 mg / m2) instead of 140 parts of silica 3 of Resin Varnish 3 was used instead of the resin varnish 3 Resin Varnish 7 was prepared.

(Preparation of resin varnish 8)

, 10 parts of a naphthalene type epoxy resin ("ESN475V" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent weight: about 330), 5 parts of a naphthalene type epoxy resin (HP-4710 manufactured by DIC Corporation, epoxy equivalent weight: about 170) , 12 parts of biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: about 272) and 12 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Kagaku K.K .; cyclohexanone: 5 parts of a 1: 1 solution of methyl ethyl ketone (MEK) were dissolved by heating in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone with heating. After cooling to room temperature, 8 parts of a triazine skeleton-containing phenol novolac curing agent ("LA-7054" manufactured by DIC Corporation, a hydroxyl group equivalent of about 125, and a solid content of 60% 12 parts of an imidazole-based curing accelerator (&quot; 1B2PZ &quot; manufactured by Shinko Chemical Industry Co., Ltd., SN-485, hydroxyl group equivalent of about 212 and a solid content of 60% 1 part of a flame retardant (HCA-HQ manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9- (Average particle diameter: 2 mu m), 4 parts of an aminosilane coupling agent (&quot; KBM573 &quot; manufactured by Shin-Etsu Chemical Co., (Diameter: 1.06 mu m, specific surface area: 3.01 m &lt; 2 &gt; / g, carbon content per unit surface area: 0.31 mg / m 2) were mixed and uniformly dispersed with a high speed rotary mixer. SHP050 &quot;) to prepare resin varnish 8.

Table 1 shows the materials used in the production of each resin varnish and the blending amount thereof (mass parts of nonvolatile matter). Table 1 also shows the content (mass%) of the liquid epoxy resin (a1) and the inorganic filler (c) in the nonvolatile component.

(Examples 1 to 4 and Comparative Examples 1 to 4: Production of resin sheet)

(Lumirra T6AM manufactured by Toray Co., Ltd., thickness 38 탆, softening point 130 캜, "release PET") which had been subjected to release treatment with an alkyd resin releasing agent (AL-5, Prepared.

Each of the resin varnishes was uniformly coated on the release PET with a die coater so that the thickness of the curable resin composition layer after drying was 25 占 퐉 and dried at 80 占 폚 to 110 占 폚 for 4 minutes to obtain a curable resin composition layer on the release PET . Then, a polypropylene film ("ALPAN MA-430" manufactured by OUFAFEX Co., Ltd., thickness 20 μm) was bonded as a protective film to the surface of the curable resin composition layer not bonded with the support to the curable resin composition layer Respectively. Thus, a resin sheet in the order of a support, a curable resin composition layer, and a protective film was obtained.

(Measurement of Minimum Melting Viscosity of Curable Resin Composition Layer)

(1) Measurement of the lowest melt viscosity

Only the curable resin composition layer was peeled off from the release type PET and compressed by a mold to produce measurement pellets (diameter 18 mm, 1.2 to 1.3 g).

A 18 mm diameter parallel plate was used for 1 g of the sample resin composition layer using a pellet for measurement and a dynamic viscoelasticity measuring apparatus (&quot; Rheosol-G3000 &quot; The temperature was raised from 60 ° C to 200 ° C at a heating rate of 5 ° C / min. The dynamic viscoelasticity was measured under the measurement conditions of a measurement temperature interval of 2.5 ° C, a frequency of 1Hz and an elasticity of 1deg, and the lowest melt viscosity poise was calculated. 2.

(Measurement of the average linear heat expansion coefficient of the cured product (insulating layer) of the curable resin composition layer)

The untreated surface of a release PET film ("501010" manufactured by Lintec Corporation, thickness 38 탆, 240 mm square) was laminated on a glass cloth base epoxy resin double-side copper-clad laminate ("R5715ES" manufactured by Matsushita Denko K.K., And the four sides of the release PET film were fixed with a polyimide adhesive tape (width 10 mm).

Each resin sheet (200 mm square) produced in the examples and the comparative examples was subjected to heat treatment using a batch type vacuum pressure laminator (CVP700, 2 stage build-up laminator manufactured by Nichigo Morton Co., Ltd.) And laminated at the center so as to contact with the release surface of the film. The lamination treatment was carried out by reducing the pressure for 30 seconds to bring the air pressure to 13 hPa or less, followed by compression at 100 DEG C and a pressure of 0.74 MPa for 30 seconds.

Subsequently, the mixture was placed in an oven at 100 ° C and then thermally cured in an oven at 175 ° C for 30 minutes and then at 175 ° C for 30 minutes. Thereafter, the substrate was taken out under a room temperature atmosphere, and the releasing PET (support) was peeled from the resin sheet. Thereafter, the substrate was further put into an oven at 190 캜, and the curing resin composition layer was thermally cured under the curing condition for 90 minutes.

After thermosetting, the polyimide adhesive tape was peeled off and the curable resin composition layer was peeled from the glass cloth substrate epoxy resin double-sided copper-clad laminate. Further, a release PET film ("501010" manufactured by LINTEC CO., LTD.) In which the curable resin composition layer was laminated was peeled off to obtain a sheet-like cured product. The resulting cured product was cut into test pieces each having a width of 5 mm and a length of 15 mm and thermomechanical analysis was carried out by a tensile weighting method using a thermomechanical analyzer ("Thermo Plus TMA8310" manufactured by Rigaku Corporation). Specifically, after the test piece was mounted on the thermomechanical analyzer, the test piece was continuously measured twice under the measurement conditions of a load of 1 g and a temperature raising rate of 5 캜 / minute. In the two measurements, the average linear heat expansion coefficient (ppm / DEG C) in the plane direction in the range from 30 DEG C to 150 DEG C was calculated and is shown in Table 2.

&Lt; Evaluation test >

1. Assessment of Part Fillability

Using the resin sheets prepared in the examples and the comparative examples, a component-adhered circuit board was manufactured in accordance with the following procedures, and the component embeddability was evaluated.

(1) Preparation of circuit board (cavity substrate) with components attached

On a front surface of a glass forging substrate BT resin double-sided copper-clad laminate (thickness of copper foil of 18 탆, substrate thickness of 0.15 mm, HL832NSF LCA manufactured by Mitsubishi Gas Kagaku Co., Ltd.) size of 255 x 340 mm, The conductor pattern was formed by the design of the attached data. Subsequently, the both surfaces were subjected to 1 占 퐉 etching with a microetching agent (&quot; CZ8100 &quot;, manufactured by MEC Corporation) to conduct a roughening treatment on the surface of the copper surface. Further, a rustproofing treatment (&quot; CL8300 &quot;Lt; / RTI &gt; for 30 minutes.

(2) Fabrication of circuit board with components attached

(Polyimide 38 μm thick, "PFDKE-1525TT", manufactured by ARISAWA SEISAKUSHO Co., Ltd.) having a thickness of 25 μm was laminated on one surface of the substrate obtained in the above (1) using a batch type vacuum laminator Using a two stage build-up laminator &quot; CVP700 &quot; manufactured by Nichigo Morton Co., Ltd.), the pressure-sensitive adhesive was disposed so as to be bonded to the substrate, and laminated on one side. The lamination was carried out by reducing the pressure for 30 seconds to bring the air pressure to 13 hPa or less, followed by compression at 80 DEG C and a pressure of 0.74 MPa for 30 seconds. Subsequently, a multilayer ceramic capacitor component (1005 = 1 * 0.5 mm in size, 0.14 mm in thickness) was attached one by one in the cavity to manufacture a component circuit board (cavity substrate).

(3) Evaluation test of the parts filling property

A protective film was peeled off from the resin sheet produced in Examples and Comparative Examples using a batch-type vacuum laminator (CVP700, 2 stage build-up laminator manufactured by Nichigo Morton Co., Ltd.) And (2) were stacked so that the surface of the mounting circuit board (cavity substrate) opposite to the adhesive-coated polyimide film placement surface was bonded to each other. The lamination was carried out by reducing the pressure for 30 seconds to bring the air pressure to 13 hPa or less, followed by compression at 120 DEG C and a pressure of 0.74 MPa for 30 seconds. Subsequently, the laminated resin sheet was subjected to heat pressing under atmospheric pressure at 120 DEG C and a pressure of 0.5 MPa for 60 seconds to be smoothed. The parts cooled to room temperature were peeled off the adhesive-coated polyimide film from the adhesive circuit board to prepare the evaluation board A for evaluation. From the surface of the evaluation substrate A on which the polyimide film had been peeled off, the resin flow in the cavity was observed with an optical microscope (10 times) (10 cavities), and the parts filling property was evaluated according to the following criteria. Respectively.

A: In all the cavities, the outer peripheral portion of the multilayer ceramic capacitor component is covered with resin.

C: Even one of the cavities may be voided or the resin may not be embedded in the outer peripheral portion of the multilayer ceramic capacitor component.

.

2. Evaluation of bending amount

(1) Curing of resin sheet

1. Evaluation substrate A prepared in (3) was put into an oven at 100 ° C. at a temperature of 100 ° C., followed by heat treatment for 30 minutes. After cooling to room temperature, a polyimide film with a pressure- , The same resin sheet was attached under the same conditions as in (3). Thereafter, the substrate was placed in an oven at 100 ° C for 30 minutes, then transferred to an oven at 175 ° C for 30 minutes and then thermally cured for 30 minutes at a temperature of 100 ° C to form an insulating layer on both sides of the substrate Respectively. Thereafter, the substrate on which the insulating layer was formed on both sides was taken out under a room temperature atmosphere, the releasing PET on both sides was peeled off, the thermosetting resin composition layer was heated in an oven at 190 deg. And cured to produce an internal circuit board for an evaluation board.

(2) Evaluation test of warping amount

("HAS-6116" manufactured by Nihon Anthom Co., Ltd.) which reproduces a solder reflow temperature at a peak temperature of 260 ° C after cutting the evaluation board B into 45-mm pieces (n = 5) (Reflow temperature profile is in accordance with IPC / JEDEC J-STD-020C). Subsequently, the lower surface of the substrate was heated with a reflow temperature profile conforming to IPC / JEDEC J-STD-020C (peak temperature 260 ° C) using a shadow moire apparatus (TherMoire AXP manufactured by Akrometrix) The displacement (탆) of each 10 mm square at the center of the substrate was measured, and the results are shown in Table 2.

Table 2 shows, in addition to the evaluation results, the type of the resin varnish used in the formation of each curable resin composition layer, the kind and content (mass%) of the inorganic filler, the average particle diameter ), The specific surface area (m 2 / g), the true density (g / cm 3), the product of the true density and the specific surface area, the lowest melt viscosity (poise) of the curable resin composition layer and the average linear thermal expansion coefficient Together.

One… Circuit board
2… Board
2a ... Cavity
3 ... Conductor layer (circuit wiring)
4… The attachment material
5 ... part
10 ... The resin sheet (first resin sheet)
11 ... The support (first support)
12 ... Curable resin composition layer
12 '... The curable resin composition layer (heat treated product)
12 "... insulation layer
20 ... The second resin sheet
21 ... The second support
22 ... The second curable resin composition layer
22 '... The second curable resin composition layer (heat treated product)
22 "... insulation layer
100 ... Wiring Board (Internal Circuit Board)

Claims (10)

A resin sheet comprising a support and a curable resin composition layer provided on the support,
The curable resin composition layer contains an inorganic filler,
The content of the inorganic filler in the curable resin composition layer is 74 mass% or more,
Wherein the inorganic filler has an average particle diameter of 1.6 占 퐉 or less and a product of a specific surface area [m2 / g] of the inorganic filler and a true density [g / cm3] of 6 to 8,
Wherein a minimum melt viscosity of the curable resin composition layer is 12000 poise or less. The resin sheet according to claim 1, wherein the inorganic filler is silica. The curable resin composition according to claim 1, wherein the curable resin composition layer comprises (a) an epoxy resin,
Wherein the epoxy resin contains a liquid epoxy resin,
Wherein the content of the liquid epoxy resin in the curable resin composition layer is 1% by mass or more. 4. The epoxy resin composition according to claim 3, wherein (a) the epoxy resin further contains a solid epoxy resin,
Wherein the ratio (M _S / M _L ) of the mass (M _S ) of the solid epoxy resin to the mass (M _L ) of the liquid epoxy resin in the curable resin composition layer is 0.6 to 10. The resin sheet according to claim 3, wherein (a) the epoxy resin is (a ') an epoxy resin having an aromatic structure. The curable resin composition according to claim 3, wherein the curable resin composition layer further comprises a component (d): at least one resin selected from a resin having a functional group having a glass transition temperature of 25 占 폚 or lower and a resin having a functional group liquid at 25 占 폚
And a resin sheet. The positive resist composition according to claim 6, wherein the component (d) has at least one functional group selected from a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group,
(Meth) acrylate structural unit, an alkyleneoxy structural unit, a butadiene structural unit, an isoprene structural unit, an isobutylene structural unit, a chloroprene structural unit, a urethane structural unit, a polycarbonate structural unit, And at least one structural unit selected from the following structural units. The resin sheet according to claim 1, which is for a component internal circuit board. An insulating layer formed by curing the curable resin composition layer of the resin sheet described in any one of claims 1 to 8,
A wiring board comprising a conductive layer. A semiconductor device comprising the wiring board according to claim 9.

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