TW201720242A - Resin sheet with supporting body - Google Patents

Abstract

To provide a resin sheet with a supporting body which reduces warpage of a substrate and is excellent in component embedding properties. A resin sheet with a supporting body includes a supporting body and a resin sheet provided on the supporting body. The resin sheet has a first resin composition layer provided on the side of the supporting body, and a second resin composition layer which is provided in an opposite side to the supporting body and is formed from a second resin composition having a different composition from that of the first resin composition forming the first resin composition layer. The lowest melting viscosity of the resin sheet is 6,000 poise or less, and an average linear thermal expansion rate between 25 DEG C and 150 DEG C of a cured product layer formed by curing the resin sheet is 17 ppm/DEG C or less.

Description

Resin sheet with support

The present invention relates to a resin sheet with a support, a method of manufacturing a component-embedded circuit board, and a semiconductor device.

In recent years, there has been an increase in the number of small high-performance electronic devices for smartphones and tablets, and this demand has been demanded for higher functionality of small electronic devices and small printed wiring boards.

Mounted parts such as bare wafers, wafer capacitors, and on-wafer sensors are mounted on the printed wiring board.

Although such a component has been mounted only on the surface circuit of a printed wiring board in the past, the mounting amount thereof is limited, and it is difficult to meet the requirements of higher functionality and a small printed wiring board in recent years.

In order to solve the above-mentioned problems, it is proposed to provide a built-in circuit board that is compact (thinned) by increasing the amount of load on the components of the inner circuit board (see Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2015-2295

However, in order to make the concave portion (cavity) of the component in which the component-embedded circuit board is placed, the recessed property of the component is excellent, and it is possible to suppress the flow of the resin and suppress the inorganic filler used in the resin composition in which the component is recessed. When the content of the material is used, a resin having a relatively small molecular weight is used, but the coefficient of thermal expansion is increased and the bending of the substrate is likely to become large. On the other hand, in order to reduce the bending of the substrate of the component-embedded circuit board, it is possible to increase the content of the inorganic filler in the resin composition. However, there is a problem in that the melt viscosity is increased to reduce the concaveness of the cavity. Although the inventors of the present invention have reviewed the melting viscosity of the resin composition in the side of the contact with the circuit board using the plurality of layers of the tree limb composition layer, it has been found that it is difficult to achieve the opposite properties when it is difficult to correspond to the film formation. Accordingly, the object of the present invention is to provide a resin sheet with a support which can reduce the bending of the substrate and which is excellent in the embedding property of the parts.

As a result of careful examination of the above-mentioned problems, the present inventors have found that the lowest melt viscosity of the resin sheet itself is set to 6000 poise by the resin sheet with the support of the first resin composition and the second resin composition having different compositions. In the following, the average linear thermal expansion coefficient of the cured product obtained by curing the resin sheet from 25 ° C to 150 ° C is set to 17 ppm / ° C or less, and the above problems can be solved to complete the present invention. The present invention is based on such novel insights.

That is, the present invention includes the following.

[1] A resin sheet with a support comprising a support sheet and a resin sheet with a support of a resin sheet provided on the support, wherein the resin sheet has a first resin composition layer provided on the support side and The second resin composition formed on the opposite side of the support and formed of the second resin composition having a different composition from the first resin composition forming the first resin composition layer, the lowest melt viscosity of the resin sheet is Below 6000 poise, the average linear thermal expansion coefficient of the cured layer obtained by curing the resin sheet from 25 ° C to 150 ° C is 17 ppm / ° C or less.

[2] The resin sheet with a support according to [1], wherein the thickness of the resin sheet is 30 μm or less.

[3] The resin sheet with a support according to [1] or [2], wherein the thickness of the second resin composition layer is 25 μm or less.

[4] The resin sheet with a support according to any one of [1] to [3] wherein the second resin composition contains an inorganic filler, and the nonvolatile content in the second resin composition is 10% by mass. The content of the inorganic filler in the case is 70% by mass or more.

[5] The resin sheet with a support according to any one of [1] to [4] wherein the lowest melt viscosity of the second resin composition layer is lower than the lowest melt viscosity of the first resin composition layer.

[6] The resin sheet with a support according to any one of [1] to [5], which is used for a cavity.

[7] The resin sheet with a support according to any one of [1] to [6] wherein the first resin composition and the second resin composition respectively contain inorganic filler The average particle diameter of the inorganic filler in the first resin composition is D1 (μm), and when the average particle diameter of the inorganic filler in the second resin composition is D2 (μm), D1 and D2 satisfy D1≦. The relationship of D2.

[8] The resin sheet with a support according to [7], wherein an average particle diameter D1 (μm) of the inorganic filler in the first resin composition and an average particle diameter D2 of the inorganic filler in the second resin composition (μm) satisfies the relationship of D1 ≦ 0.5 ≦ D2.

[9] The resin sheet with a support according to any one of [1] to [8] wherein the second resin composition comprises an inorganic filler and a liquid epoxy resin.

[10] The resin sheet with a support according to [9], wherein, when the inorganic filler is contained in an amount of 100 parts by mass, the liquid epoxy resin is contained in an amount of 5 parts by mass or more.

[11] A method of manufacturing a component-embedded circuit board, comprising the steps of: (A) including a first and second main faces, and forming a cavity penetrating between the first and second main faces; a circuit board, and a temporary material connected to the second main surface of the circuit board; and a component temporarily suspended by the temporary material in the cavity of the circuit board is temporarily connected to the circuit board of the component a first lamination step of the resin sheet with a support according to any one of [1] to [10], and (B) a heat treatment step of heat-treating the circuit board on which the resin sheet with the support is laminated, and (C) peeling the temporary material from the second main surface of the circuit board, and then making the second a resin sheet is connected to the second main surface of the circuit board, and a second lamination step of vacuum-laminating the resin sheet including the second support and the second support connected to the second support is performed, and (D) A step of thermally curing the resin sheet and the second resin sheet of the resin sheet with the support.

[12] The method of manufacturing a component-embedded circuit board according to [11], wherein the thickness of the circuit substrate is 100 μm or more.

[13] The method of manufacturing a component-embedded circuit board according to [11] or [12], wherein the resin sheet with the second support is a resin sheet with a support according to any one of [1] to [10].

[14] A semiconductor device comprising the component-embedded circuit board manufactured by the method of any one of [11] to [13].

According to the present invention, it is possible to provide a resin sheet with a support which can reduce the bending of the substrate while being excellent in the embedability of the part.

1‧‧‧ circuit substrate

1'‧‧‧Parts temporary circuit board

2‧‧‧Substrate

2a‧‧‧cavity

3‧‧‧Circuit wiring

4‧‧‧ Temporary materials

5‧‧‧ parts

10‧‧‧Resin sheet with the first support

11‧‧‧Support

12‧‧‧Resin sheet

12'‧‧‧Resin sheet (heat treatment body)

12"‧‧‧Insulation (hardened layer)

13‧‧‧1st resin composition layer

13'‧‧‧1st resin composition layer (heat treatment body)

13"‧‧‧1st insulation layer (hardened layer)

14‧‧‧Second resin composition layer

14'‧‧‧Second resin composition layer (heat treatment body)

14"‧‧‧2nd insulation layer (hardened layer)

20‧‧‧Resin sheet with the second support

21‧‧‧2nd support

22‧‧‧2nd resin sheet

22"‧‧‧Insulation (hardened layer)

23‧‧‧1st resin composition layer

23"‧‧‧1st insulation layer (hardened layer)

24‧‧‧2nd resin composition layer

24"‧‧‧2nd insulation layer (hardened layer)

100‧‧‧Parts built-in board

[ Fig. 1A] Fig. 1A is a schematic view (1) showing a procedure of a circuit board in which a component is temporarily used in a method of manufacturing a component-embedded circuit board using a resin sheet with a support according to the present invention.

[Fig. 1B] Fig. 1B is a view showing a temporary part used in a method of manufacturing a component-embedded circuit board in which a resin sheet with a support according to the present invention is used. Schematic diagram of the steps of the circuit board (2).

1C] FIG. 1C is a schematic view (3) showing a procedure of a circuit board in which a component is temporarily used in a method of manufacturing a component-embedded circuit board using a resin sheet with a support according to the present invention.

1D] FIG. 1D is a schematic view (4) showing a procedure of a circuit board in which a component is temporarily used in a method of manufacturing a component-embedded circuit board using a resin sheet with a support according to the present invention.

Fig. 2 is a schematic view showing a state of a resin sheet with a support of the present invention.

[ Fig. 3A] Fig. 3A is a schematic view (1) illustrating a method of manufacturing a resin sheet component-embedded circuit board using the support according to the present invention in the first embodiment.

3B] Fig. 3B is a schematic view (2) illustrating a method of manufacturing a resin sheet component-embedded circuit board using the support of the present invention.

3C] Fig. 3C is a schematic view (3) illustrating a method of manufacturing a resin sheet component-embedded circuit board using the support of the present invention.

3D] Fig. 3D is a schematic view (4) illustrating a method of manufacturing a resin sheet component-embedded circuit board using the support of the present invention.

3E] Fig. 3E is a schematic view (5) illustrating a method of manufacturing a resin sheet part built-in circuit board using the support of the present invention.

[ Fig. 3F] Fig. 3F is a schematic view (6) illustrating a method of manufacturing a resin sheet part built-in circuit board using the support of the present invention.

3G] Fig. 3G is a schematic view (7) illustrating a method of manufacturing a resin sheet component-embedded circuit board with a support according to the present invention.

In the resin sheet with a support of the present invention, the first resin composition layer and the second resin composition layer included in the resin sheet are described in detail. 1 resin composition" and "second resin composition".

<First resin composition>

The first resin composition forming the first resin composition layer is not particularly limited as long as it has sufficient hardness and insulating properties for the cured product. The first resin composition may, for example, be a composition containing a curable resin and a curing agent thereof. As the curable resin, a conventionally known curable resin used in forming an insulating layer of a printed wiring board can be used, and an epoxy resin is preferred. Therefore, in the first embodiment, the first resin composition contains (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler. The first resin composition may further contain an additive such as a thermoplastic resin, a curing accelerator, a flame retardant, and an organic filler, as needed.

Hereinafter, an epoxy resin, a curing agent, an inorganic filler, and an additive which can be used as a material of the first resin composition will be described.

(A) Epoxy resin

Examples of the epoxy resin include bisphenol type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, and the like, and bisphenol type epoxy resin, dicyclopentadiene. Epoxy resin, trisphenol epoxy Resin, naphthol novolak type epoxy resin, naphthol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, 蒽 type ring Oxygen resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, butadiene structure with epoxy Resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexane dimethanol epoxy resin, naphthyl ether epoxy resin, trimethylol epoxy resin , tetraphenylethane type epoxy resin, bisphenol type epoxy resin, and the like. Epoxy resins can be used singly or in combination of two or more.

Epoxy resin is selected from bisphenol epoxy resin, fluorine epoxy resin (such as bisphenol AF epoxy resin), dicyclopentadiene epoxy resin, naphthalene epoxy resin, biphenyl epoxy One or two or more epoxy resins in the group of the resin and the mixture of the epoxy resins are preferred.

The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably one or more epoxy epoxy resins per molecule. In addition, an epoxy resin having two or more epoxy groups in one molecule and a liquid at a temperature of 20 ° C (hereinafter referred to as "liquid epoxy resin") has three or more rings in one molecule. A solid epoxy resin (hereinafter referred to as "solid epoxy resin") at a temperature of 20 ° C is preferred. As the epoxy resin, a first epoxy resin composition having excellent flexibility can be obtained by using a liquid epoxy resin and a solid epoxy resin in combination. Further, the breaking strength of the cured product of the first resin composition is also increased.

A liquid epoxy resin is preferred in terms of lowering the melt viscosity. Liquid epoxy resin bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin, naphthalene epoxy resin, glycidyl ester epoxy resin, naphthol novolac ring Oxygen resin, ester backbone alicyclic epoxy resin and butadiene structure, preferably epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin and naphthalene type Epoxy resin is preferred. In particular, the epoxy resin containing an aromatic skeleton also preferably lowers the average linear thermal expansion coefficient. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene epoxy resin) manufactured by DI Co., Ltd., "828US" manufactured by Mitsubishi Chemical Corporation, and "jER828EL" (bisphenol) A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (naphthol novolac type epoxy resin), "ZX1059" (bisphenol A) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemical Co., Ltd., "CEL2021P" manufactured by Daicel Chemical Co., Ltd. Skeleton alicyclic epoxy resin), "PB-3600" (with butadiene-structured epoxy resin). These may be used alone or in combination of two or more.

In terms of lowering the average thermal expansion coefficient, a solid epoxy resin is preferred. Solid epoxy resin naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type ring Oxygen resin, naphthyl ether type epoxy resin, bismuth type epoxy resin, bisphenol A type epoxy tree A fat, tetraphenylethane type epoxy resin is preferred, a naphthalene type tetrafunctional epoxy resin, a naphthol type epoxy resin, and a biphenyl type epoxy resin are preferred. In particular, the polyfunctional epoxy resin has a large number of crosslinking points, and it is preferable to lower the average linear thermal expansion coefficient. Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type 4-functional epoxy resin), and "N" manufactured by DIC Corporation. -690" (cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP-7200HH" "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (stretching naphthyl ether epoxy resin), "EPPN-502H" manufactured by Nippon Kayaku Co., Ltd. (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), Nippon Steel "ESN475V" (naphthol type epoxy resin), "ESN485" (naphthol novolak type epoxy resin), and "YX4000H" and "YL6121" (biphenyl type ring) manufactured by Mitsubishi Chemical Corporation Oxygen resin), "YX4000HK" (dixylenol type epoxy resin), "YX8800" (蒽 type epoxy resin), manufactured by Osaka Gas Chemical Co., Ltd. PG-100", "CG-500", "YL7800" (茀-type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1010" (solid bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Corporation, " jER1031S" (tetraphenylethane type epoxy resin), "YL7760" (bisphenol AF type epoxy resin).

When the epoxy resin contains a solid epoxy resin and a liquid epoxy resin, the ratio of the mass M _{S of the} solid epoxy resin to the mass M _L of the liquid epoxy resin (M _S /M _L ) is 1 to 10 The range is good. By M _S /M _L in its range, the following effects can be obtained: i) having an appropriate adhesiveness when used in the form of a resin sheet, and ii) obtaining sufficient flexibility when used in the form of a resin sheet, and improving The operability, and iii) can obtain effects such as a cured product having sufficient breaking strength.

The content of the (A) epoxy resin in the first resin composition is preferably 0.1% by mass or more, preferably 5% by mass or more, and more preferably 10%, based on the insulating layer which exhibits good mechanical strength and insulation reliability. More than % by mass. The upper limit of the content of the epoxy resin is not particularly limited as long as it exhibits the effects of the present invention, but is preferably 50% by mass or less, preferably 45% by mass or less, and more preferably 42% by mass or less.

Therefore, the content of the (A) epoxy resin in the first resin composition is preferably from 0.1 to 50% by mass, preferably from 10 to 45% by mass, and more preferably from 20 to 42% by mass. In addition, when the content of each component in the resin composition (the first resin composition and the second resin composition) in the present invention is not further indicated, the nonvolatile content in the resin composition is a value of 100% by mass.

The epoxy equivalent of the epoxy resin is preferably from 50 to 5,000, preferably from 50 to 3,000, more preferably from 80 to 2,000, most preferably from 110 to 1,000. In the range of the cured product, the crosslink density of the cured product becomes sufficient to have an insulating layer having a small surface roughness. Further, the epoxy resin can be measured in accordance with JIS K7236, and contains a mass of an epoxy group-containing resin.

The weight average molecular weight of the epoxy resin is preferably from 10 to 5,000, preferably from 250 to 3,000, more preferably from 400 to 1,500. Here, the ring The weight average molecular weight of the oxygen resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

(B) hardener

(B) The curing agent is not particularly limited as long as it has a function of curing the 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, and a cyanate ester. A hardener and a carbodiimide hardener. The curing agent can be used singly or in combination of two or more.

The phenolic curing agent and the naphthol-based curing agent are preferably a phenolic curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure in terms of heat resistance and water resistance. Further, in view of the adhesion to the conductor layer (circuit wiring), a halogen-containing phenol-based curing agent, a triazine-containing phenol resin, and a triazine-containing alkylphenol resin are preferable. Among them, a triazine-based phenol-based curing agent is preferably used in terms of high heat resistance, water resistance, and adhesion to a conductor layer (peeling strength).

Specific examples of the phenolic curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Mingwa Chemical Co., Ltd., and "NHN" manufactured by Nippon Kayaku Co., Ltd. , "CBN", "GPH", Dongfu Chemical Co., Ltd. "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395", DIC shares limited Company system "LA7052", "LA7054", "LA3018" Wait.

The active ester-based curing agent is not particularly limited, and generally, a reactive high ester group having two or more phenol esters, thiophenol esters, N-hydroxylamine esters, or esters of a heterocyclic hydroxy compound in one molecule is used. The compound is preferred. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thio acid compound with a hydroxy compound and/or a thiol compound. In particular, in view of improving heat resistance, an active ester-based curing agent is preferably obtained from a carboxylic acid compound and a hydroxy compound, and an active ester-based curing agent is preferably obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. Examples of the phenol compound or the naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenol naphthalene, methylated bisphenol A, methylated bisphenol F, and methyl group. Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-di Hydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene bisphenol, naphthol novolac Wait.

Specifically, an active ester compound comprising a dicyclopentadiene bisphenol structure, an active ester compound comprising a naphthalene structure, an active ester compound of an acetylated product comprising a naphthol novolac, and a benzamidine containing a naphthol novolac The active ester compound is preferred, and an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene bisphenol structure are preferred.

The commercially available product of the active ester-based curing agent is an active ester compound containing a dicyclopentadiene bisphenol structure, and examples thereof include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" (manufactured by DIC Corporation). And an active ester compound containing a naphthalene structure, such as "EXB9416-70BK" (manufactured by DIC Corporation) and an active ester compound of an acetylated product containing a naphthol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation) The active ester compound of the benzamidine compound containing a naphthol novolak can be exemplified by "YLH1026" (manufactured by Mitsubishi Chemical Corporation).

Specific examples of the benzoxazine-based curing agent include "HFB2006 M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industry Co., Ltd.

Examples of the cyanate-based curing agent include bisphenol A dicyanate and polyphenol isocyanate (oligo(3-methylene-1,5-phenylene), 4,4'-methylene group). Bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4- Cyanate ester) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-double ( 2-functional cyanic acid such as 4-cyanate phenyl-1-(methylethylidene) benzene, bis(4-cyanate phenyl) sulfide, bis(4-cyanate phenyl) ether The ester resin is a polyfunctional cyanate resin derived from a phenol novolak, a cresol novolak, a phenol resin having a dicyclopentadiene structure, or the like, and a triazine-based prepolymer such as a part of the cyanate resin. Specific examples of the cyanate-based curing agent are "PT 30" and "PT 60" manufactured by Lonza Japan Co., Ltd. (any of them are naphthol novolac type polyfunctional cyanate resin), and "BA230" (bisphenol A) Diisocyanate A part or all of the acid ester is triazineated to form a prepolymer of a trimer).

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

In the present invention, the (B) curing agent is preferably one or more selected from the group consisting of a phenolic curing agent, a cyanate curing agent, and an active ester curing agent, and contains a phenol resin selected from the group consisting of a triazine structure and a triazine-containing resin. One or more kinds of the alkylphenol-based resin, the cyanate-based curing agent, and the active ester-based curing agent are preferably selected.

The content of the (B) curing agent in the first resin composition is not particularly limited, and is preferably 0.1% by mass or more, preferably 1% by mass or more, from the viewpoint of obtaining an insulating layer having high peel strength, high fat and low electric induction. More preferably, it is 5% by mass or more. (B) The upper limit of the content of the curing agent is not particularly limited as long as it exhibits the effects of the present invention, and is preferably 30% by mass or less, preferably 25% by mass or less, and more preferably 20% by mass or less.

Therefore, the content of the (B) curing agent in the first resin composition is preferably from 0.1 to 30% by mass, preferably from 1 to 25% by mass, and more preferably from 5 to 20% by mass.

(A) The ratio of the epoxy resin to the (B) hardener is the ratio of [(A) the total number of epoxy groups of the epoxy resin]: [(B) the total number of reactive groups of the hardener], 1:0.2 The range of ~1:2 is better, 1:0.3~1:1.5 is better, and 1:0.4~1:1 is better. Here, the reactive group of the curing agent means an active hydro acid group, an active ester group or the like, which differs depending on the kind of the curing agent. Moreover, the total number of epoxy groups of the epoxy resin means that the epoxy resin is solid. The mass of the body component divided by the value of the epoxy equivalent relative to the total value of the epoxy resin, and the total of the reactive groups of the hardener means that the solid component mass of each hardener is divided by the value of the reactive base equivalent to the total serving. The total value of the hardener. By setting the ratio of the epoxy resin to the hardener to be in this range, the heat resistance of the cured product of the first resin composition is further improved.

(C) inorganic filler

The material of the inorganic filler is not particularly limited, and examples thereof include cerium oxide, aluminum oxide, glass, cordierite, cerium oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, and water soft. Aluminite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, barium carbonate, barium titanate, calcium titanate, magnesium titanate, Barium titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, and the like. Among these, cerium oxide is particularly suitable. Further, cerium oxide-based spherical cerium oxide is preferred. The inorganic filler can be used singly or in combination of two or more. Commercial products of the inorganic fillers include, for example, "SO-C2", "SO-C1", and "SO-C4" manufactured by Admatech Co., Ltd.

The average particle diameter of the inorganic filler is not particularly limited, and 5 μm or less is preferable, and 4 μm or less is preferable, and 3 μm or less is more preferable in terms of obtaining an insulating layer having a small surface roughness or improving fine wiring formation property. 1 μm or less, 0.7 μm or less, 0.5 μm or less, or 0.3 μm or less is most preferable. On the other hand, when a resin varnish is formed using the first resin composition, a resin varnish having good operability with an appropriate viscosity is obtained. In terms of the lacquer, the average particle diameter of the inorganic filler is preferably 0.01 μm or more, and preferably 0.03 μm or more, and 0.05 μm or more, 0.07 μm or more, or 0.1 μm or more in terms of preventing the increase in the melt viscosity of the resin sheet. For better. Therefore, the average particle diameter of the (C) inorganic filler in the first resin composition is preferably 0.5 μm or less or 0.3 μm or less.

The average particle size of the inorganic filler is based on the Mie scattering theory and can be measured by laser diffraction ‧ scattering method. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis by a laser reflection scattering type particle size distribution measuring apparatus, and can be measured by setting the median diameter to an average particle diameter. The measurement sample system can preferably use an inorganic filler to be dispersed in water by ultrasonic waves. As the laser reflection scattering type particle size distribution measuring apparatus, "LA-500" manufactured by Horiba, Ltd., etc. can be used.

The inorganic filler is an amine decane-based coupling agent, an epoxy decane-based coupling agent, a thiol decane-based coupling agent, a decane-based coupling agent, and an alkoxy decane compound in terms of improving moisture resistance and dispersibility. The organic decazane compound or the titanate-based coupler is preferably treated with one or more kinds of surface treatment agents. For example, "KBM403" (3-glycidylpropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-thiolpropyltrimethyl) manufactured by Shin-Etsu Chemical Co., Ltd. can be cited as a commercial product of the surface treatment agent. "Oxyoxane", "KBE903" (3-Aminopropyltriethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethyl) manufactured by Shin-Etsu Chemical Co., Ltd. "Oxyoxane", "SE-31" (hexamethyldioxane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" manufactured by Shin-Etsu Chemical Co., Ltd. (phenyl trimethoprim) "Alkane", "KBM-4803" (long-chain epoxy type decane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and 0.2 mg/m ² or more in terms of improving the dispersibility of the inorganic filler. Better. On the other hand, in order to prevent the melt viscosity of the resin varnish or the increase in the melt viscosity in the form of a sheet, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and more preferably 0.5 mg/m ² or less. good.

The amount of carbon per unit surface area of the inorganic filler can be measured by washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, MEK, which is a sufficient amount of a solvent, is added to an inorganic filler which has been surface-treated with a surface treatment agent, and then ultrasonically washed at 25 ° C for 5 minutes. After removing the supernatant and drying the solid component, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon amount analyzer. For the carbon amount analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

In the first resin composition, the content of the (C) inorganic filler is preferably 70% by mass or less, preferably 60% by mass or less, and 50% by mass in terms of the insulating layer on which the fine wiring is formed. The following or 40% by mass or less. The lower limit of the content of the (C) inorganic filler in the first resin composition is not particularly limited, and may be 0% by mass, and usually 5% by mass or more, 10% by mass or more, 20% by mass or more.

The first resin composition may contain additives such as a thermoplastic resin, a curing accelerator, a flame retardant, and an organic filler in addition to the above (A), (B), and (C).

- Thermoplastic Resin -

The thermoplastic resin can, for example, be a phenoxy resin, a polyvinyl acetal resin, a polyolefin resin, a polybutadiene resin, a polyimine resin, a polyamidimide resin, a polyether phthalimide resin, or a polyfluorene resin. A thermoplastic resin such as a polyether oxime resin, a polyphenylene ether resin, a polycarbonate resin, a polyether ether ketone resin or a polyester resin, and a phenoxy resin is preferred among these. The thermoplastic resin may be used singly or in combination of two or more.

The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 100,000, preferably in the range of 10,000 to 60,000, and more preferably in the range of 20,000 to 60,000. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is LC-9A/RID-6A manufactured by Shimadzu Corporation, and the Shodex K-made by Showa Denko Co., Ltd. can be used as the column. 800P/K-804L/K-804L, the mobile phase can be measured at 40 ° C using chloroform, etc., using a standard polystyrene calibration line.

The phenoxy resin may, for example, be selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, an anthracene skeleton, a dicyclopentadiene skeleton, and a descending structure. Borneene A phenoxy resin having one or more kinds of skeletons of a group consisting of a skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, an anthracene skeleton, and a trimethylcyclohexane skeleton. The terminal group of the phenoxy resin can also be any functional group such as a phenolic hydro acid group or an epoxy group. The phenoxy resin may be used singly or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (all of which contain a phenoxy resin of a bisphenol A skeleton) and "YX8100" (a bisphenol S skeleton contains a phenoxy resin) And "YX6954" (bisphenol acetophenone skeleton containing phenoxy resin), and others "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., "YL6954BH30" and "YX7553" manufactured by Mitsubishi Chemical Corporation , "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7891BH30" and "YL7482".

The polyvinyl acetal resin may, for example, be a polyvinyl formal resin, a polyvinyl butyral resin or a polyvinyl butyral resin. Specific examples of the polyvinyl acetal resin include, for example, "Electrified BUTYRAL 4000-2", "Electrified BUTYRAL 5000-A", "Electrified BUTYRAL 6000-C", "Electrified BUTYRAL 6000-EP", and Sekisui. Chemical Industry Co., Ltd. S-LECBH series, BX series, KS series, BL series, BM series, etc.

Specific examples of the polyimine resin include "Richardt SN20" and "Ricaker PN 20" manufactured by New Japan Physical and Chemical Co., Ltd. Specific examples of the polyimine resin include difunctional hydroxyl groups. A linear polyimine obtained by reacting a terminal polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (polyimine disclosed in JP-A-2006-37083), and a polyoxyalkylene skeleton containing a polyimine A modified polyimine such as polyethylenimine described in JP-A-2002-12667 and JP-A-2000-319386.

Specific examples of the polyamidoximine resin include "VYLOMAXHR 11NN" and "VYLOMAXHR 16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamidoximine resin include modified polyamidoquinone imines such as "KS9100" and "KS9300" (polyoxane skeleton containing polyamidolimine) manufactured by Hitachi Chemical Co., Ltd. .

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

Specific examples of the polybenzazole resin include those of the "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd.

Specific examples of the polyphenylene ether resin include polyphenylene ether styrene resin "OPE-2 St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like.

Among them, in combination with other components, the thermoplastic resin is preferably a phenoxy resin or a polyvinyl acetal resin in terms of obtaining an excellent insulating layer from the adhesion of a conductor layer having a lower surface roughness. Therefore, in one embodiment, the thermoplastic resin component contains one or more selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin.

The content of the thermoplastic resin in the first resin composition is The amount of the melt viscosity of the resin sheet is preferably from 0% by mass to 20% by mass, preferably from 0.5% by mass to 10% by mass, more preferably from 1% by mass to 8% by mass.

- hardening accelerator -

The hardening accelerator is, for example, a phosphorus-based hardening accelerator, an amine-based hardening accelerator, an imidazole-based hardening accelerator, an lanthanum-based hardening accelerator, a metal-based hardening accelerator, a phosphorus-based hardening accelerator, an amine-based hardening accelerator, and an imidazole-based system. A hardening accelerator is preferred, and an amine hardening accelerator and an imidazole hardening accelerator are preferred. The curing accelerator may be used singly or in combination of two or more.

Examples of the phosphorus-based hardening accelerator include triphenylphosphine, bismuth borate compound, tetraphenylphosphonium tetraphenyl borate, n-butyl phosphonium tetraphenyl borate, tetrabutyl citrate, and (4-methylbenzene). Further, triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., preferably triphenylphosphine or tetrabutylphosphonate.

The amine-based hardening accelerator may, for example, be a trialkylamine such as triethylamine or tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6 or -gin (two Methylaminomethyl)phenol, 1,8-dioxabicyclo(5,4,0)-undecene, etc. 4-dimethylaminopyridine, 1,8-dioxinbicyclo(5,4,0 ) - undecene is preferred.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-benzene Imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1 -cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl 2-nonylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazole -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[ 2'-Methylimidazolyl-(1')]-ethyl-s-triazine iso-cyanuric acid adduct, 2-phenylimidazolium isocyanurate adduct, 2-phenyl-4 , 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole [1,2-a]benzimidazole, chlorinated 1- Imidazole compound such as dodecyl-2-methyl-3-benzylimidazole, 2-methylimidazolium, 2-phenylimidazolium, etc., and an adduct of an imidazole compound and an epoxy resin, 2-ethyl-4 -methylimidazole, 1-benzyl-2-phenylimidazole is preferred

A commercially available product can also be used as the imidazole-based hardening accelerator, and, for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation, and the like can be used.

Examples of the lanthanide hardening accelerator include dicyandiamide, 1-methyl hydrazine, 1-ethyl hydrazine, 1-cyclohexyl hydrazine, 1-phenyl fluorene, 1-(o-methylphenyl) fluorene, and dimethyl group. Bismuth, diphenyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, pentamethyl hydrazine, 1,5,7-trioxabicyclo[4.4.0] fluorene-5-ene, 7-methyl-1,5 , 7-triterpene [4.4.0] 癸-5-ene, 1-methyl acetal, 1-ethyl fluorene, 1-n-butyl fluorene, 1-n-octadecyl Diterpenoid, 1,1-dimethyl acetal, 1,1-diethyl fluorene, 1-cyclohexyl hydrazide, 1-allyl acetal, 1-phenyl hydrazine , 1-(o-methylphenyl) hydrazine, etc., dicyandiamide, 1,5,7-triazine Ring [4.4.0] 癸-5-ene is preferred.

The metal-based hardening accelerator may, for example, be an organometallic complex or an organic metal salt of a metal such as cobalt, copper, zinc, iron, nickel, manganese or tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt (II) acetate, cobalt (III) acetate, and copper (II) such as copper (II). The organic zinc complex such as the complex compound, the ethyl acetoacetate zinc (II), the organic iron complex such as the iron (III) acetate, and the organic nickel such as the nickel (II) acetate An organic manganese complex such as acetonitrile, manganese (II) or the like. The organic metal salt may, for example, be zinc octoate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate or zinc stearate.

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

- Flame retardant -

The first resin composition can also contain a flame retardant. Examples of the flame retardant include an organic phosphorus-based flame retardant, an organic nitrogen-phosphorus compound, a halogen compound, a polyoxyalkylene-based flame retardant, and a metal hydrous acid. The flame retardant can be used alone or in combination of two or more.

For the flame retardant, a commercially available product can be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd., and "PX-200" manufactured by Daiba Chemical Industry Co., Ltd., and the like.

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

-Organic filler -

The first resin composition may further contain an organic filler. The organic filler may be any organic filler which can be used when forming an insulating layer of a printed wiring board. For example, rubber particles such as rubber particles, polyamide fine particles, and polyfluorene oxide particles are preferable.

A commercially available product can also be used for the rubber particles, and examples thereof include "AC3816N" manufactured by Aika Kogyo Co. Ltd., and the like.

The content of the organic filler in the first resin composition is preferably from 1% by mass to 20% by mass, and preferably from 2% by mass to 10% by mass, from the viewpoint of appropriately adjusting the melt viscosity of the resin sheet.

The first resin composition may further contain an additive other than the flame retardant and the organic filler, and other additives may, for example, be an organometallic compound such as an organic copper compound, an organic zinc compound or an organic cobalt compound, and An organic filler, a tackifier, an antifoaming agent, a leveling agent, a tackifier, and a resin additive such as a coloring agent.

<Second resin composition>

The second resin composition that forms the second resin composition layer is not particularly limited as long as it is different from the first resin composition, and the second resin composition preferably contains an inorganic filler, and includes an inorganic filler and a liquid. An epoxy resin is preferred.

In the second resin composition, when the non-volatile component in the second resin composition is 100% by mass, the content of the inorganic filler is preferably 60% by mass or more, in terms of the insulating layer having a low thermal expansion coefficient. 70% by mass or more is preferable, and 72% by mass or more, 74% by mass or more, or 76% by mass or more is more preferable. The upper limit of the content of the inorganic filler in the second resin composition is preferably 95% by mass or less, preferably 90% by mass or less. The inorganic filler in the second resin composition can be the same as the inorganic filler described in the column of <First Resin Composition>. When the content of the inorganic filler in the first resin composition is A1 (% by mass), and the content of the inorganic filler in the second resin composition is A2 (% by mass), A1 and A2 satisfy A1 < A2. The relationship is preferably such that the relationship of A1+20≦A2, A1+25≦A2, A1+30≦A2, A1+35≦A2, or A1+40≦A2 is preferable. In addition, when the average particle diameter of the inorganic filler in the first resin composition is D1 (μm), and the average particle diameter of the inorganic filler in the second resin composition is D2 (μm), D1 and D2 It is better to satisfy the relationship of D1≦D2, and the relationship of D1≦0.9D2, D1≦0.8D2, D1≦0.7D2, D1≦0.6D2, or D1≦0.5≦D2 is satisfied. It is better. Therefore, the average particle diameter of the (C) inorganic filler in the second resin composition is preferably 0.5 μm or more in terms of improving the embeddability.

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

The epoxy resin, the curing agent, and the additive contained in the second resin composition are the same as those of the (A) epoxy resin, the (B) curing agent, and the additive described in the <First Resin Composition> column. .

The content of the epoxy resin in the second resin composition is preferably 0.1% by mass or more, preferably 5% by mass or more, and more preferably 10%, in terms of an insulating layer which exhibits good mechanical strength and insulation reliability. More than % by mass. The upper limit of the content of the epoxy resin is not particularly limited as long as it exhibits the effects of the present invention, and is preferably 30% by mass or less, preferably 25% by mass or less, and more preferably 22% by mass or less. Therefore, the content of the (A) epoxy resin in the second resin composition is preferably from 0.1 to 30% by mass, preferably from 5 to 25% by mass, and more preferably from 10 to 22% by mass.

When the epoxy resin in the second resin composition contains a solid epoxy resin and a liquid epoxy resin, the ratio of the mass M _{S of the} solid epoxy resin to the mass M _L of the liquid epoxy resin (M _S / M _L ) is preferably in the range of 1 to 10. By M _S /M _L in its range, the following effects can be obtained: i) having an appropriate adhesiveness when used in the form of a resin sheet, and ii) obtaining sufficient flexibility when used in the form of a resin sheet, and improving The operability, and iii) can obtain effects such as a cured product having sufficient breaking strength. In addition, when the inorganic filler is 100 parts by mass in order to reduce the melt viscosity, it is preferable to contain the liquid epoxy resin in an amount of 5 parts by mass or more.

Further, an appropriate range of the epoxy equivalent of the epoxy resin in the second resin composition and the weight average molecular weight of the epoxy resin is the same as that of the epoxy resin contained in the first resin composition.

The content of the curing agent in the second resin composition is not particularly limited, and is preferably 0.1% by mass or more, preferably 1% by mass or more, and more preferably from the viewpoint of obtaining an insulating layer having high peeling strength and low dielectric constant connection. It is 5% by mass or more. The upper limit of the content of the hardener is as long as it can exhibit The effect of the invention is not particularly limited, but is preferably 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less. Therefore, the content of the curing agent in the second resin composition is preferably from 0.1 to 20% by mass, preferably from 1 to 15% by mass, and more preferably from 5 to 10% by mass.

The ratio of the epoxy resin to the hardener in the second resin composition is the ratio of [(A) the total number of epoxy groups of the epoxy resin]: [(B) the total number of reactive groups of the hardener], The range of 1:0.2~1:2 is better, 1:0.3~1:1.5 is better, and 1:0.4~1:1 is better. By setting the ratio of the epoxy resin to the hardener to be in this range, the heat resistance of the cured product of the second resin composition is further improved.

The content of the thermoplastic resin in the second resin composition is preferably from 0% by mass to 10% by mass, preferably from 0.2% by mass to 8% by mass, more preferably from 0% by mass to 8% by mass, more preferably from the viewpoint of appropriately adjusting the melt viscosity of the resin sheet. 0.5% by mass to 5% by mass.

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

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

The content of the organic filler in the second resin composition is preferably from 0.1% by mass to 20% by mass, and preferably from 0.2% by mass to 10% by mass, from the viewpoint of appropriately adjusting the melt viscosity of the resin sheet.

The second resin composition may contain other additives other than the flame retardant and the organic filler, as needed, similarly to the first resin composition. For example, an organic metal compound such as an organic copper compound, an organic zinc compound or an organic cobalt compound, and a resin additive such as an organic filler, a tackifier, an antifoaming agent, a leveling agent, a tackifier, and a coloring agent.

[Resin sheet with support]

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

The resin sheet with a support according to the present invention includes a support and a resin sheet provided on the support, and the resin sheet has a first resin composition layer provided on the support side opposite to the support, and is formed by The first resin composition of the first resin composition layer is a second resin composition layer formed of the second resin composition having a different composition, and the lowest melt viscosity of the resin sheet is 6000 poise or less, and the resin sheet is hardened by hardening. The average linear thermal expansion of the layer from 25 ° C to 150 ° C is 17 ppm / ° C or less.

Fig. 2 shows an example of a resin sheet with a support of the present invention. The resin sheet 10 with a support in FIG. 2 is provided with the support body 11 and the resin sheet 12 provided in the support body 11. The resin sheet 12 in Fig. 2 is composed of a first resin composition layer 13 provided on the support side and a second resin composition layer 14 provided on the opposite side to the support. Further, as will be described later, in the resin sheet with a support of the present invention, an additional resin composition layer may be contained between the resin sheet-based first resin composition layer and the second resin composition layer.

<support>

The support system is preferably a film made of a plastic material, a metal foil, a release paper, a film made of a plastic material, or a metal foil.

When a film made of a plastic material is used as the support, the plastic material may, for example, be a polyphthalic acid (hereinafter referred to as "PET") or a polyphthalic acid (hereinafter referred to as "PEN"). Poly), polycarbonate (hereinafter referred to as "PC" for short), propylene such as polymethyl methacrylate (PMMA), cyclic polyolefin, cellulose triacetate (TAC), polyether vulcanization (PES), polyether ketone, polyimine, and the like. Among them, polyterephthalic acid and polynaphthalene dicarboxylic acid are preferred, and inexpensive polyterephthalic acid is particularly preferred.

When a metal foil is used as the support, the metal foil may, for example, be a copper foil or an aluminum foil, and a copper foil is preferred. As the copper foil, a foil made of a single metal of copper can be used, and a foil of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, hafnium, titanium, or the like) can be used.

The support system can be subjected to matte treatment or corona treatment on the surface to be connected to the first resin composition layer.

Further, the support may be further provided with a release layer support having a surface release layer connected to the first resin composition layer. The release agent to be used for the release layer of the release layer support may be, for example, one selected from the group consisting of an alkyd resin, a polyolefin resin, a polyurethane resin, and a polyoxyalkylene resin. The above release agent. For the release layer supporting system, a commercially available product can be used, and for example, "SK-1" and "AL-" manufactured by Linke Co., Ltd., which has a release film of a PET film having a main component of an alkyd-based release agent, can be used. 5", "AL-7", etc.

The thickness of the support is not particularly limited, and is preferably in the range of 5 μm to 75 μm, and preferably in the range of 10 μm to 60 μm. Further, when the release layer support is used, the thickness of the entire release mold support is preferably in the above range.

<Resin sheet>

The resin sheet has a first resin composition layer provided on the support side and a second resin composition which is provided on the opposite side of the support and is different in composition from the first resin composition forming the first resin composition layer. A second resin composition layer formed of the object.

In the present invention, the minimum melt viscosity of the resin sheet is 6,000 poise or less, preferably 5,500 poise or less, preferably 5,000 poise or less, in terms of achieving good embeddability of the parts in the cavity. The lower limit of the minimum melt viscosity of the resin sheet can be set to 500 poise or more, 1000 poise or more, in terms of improving the thickness precision of the resin sheet.

Here, the "lowest melt viscosity" of the resin sheet means the lowest viscosity exhibited by the resin sheet when the resin of the resin sheet is melted. Specifically, when the resin sheet is heated at a constant temperature increase rate to melt the resin, the initial stage is lowered in viscosity with a rise in temperature, and then, when the temperature exceeds a certain temperature, the melt viscosity is increased as the temperature rises. "Minimum melt viscosity" means the melt viscosity of such a minimum point. The lowest melt viscosity of the resin sheet can be determined by dynamic viscoelasticity. Specifically, the lowest melt viscosity of the resin sheet is caused by an initial temperature of 60 ° C, a temperature increase rate of 5 ° C / minute, and vibration. It can be obtained by performing dynamic viscoelasticity measurement under conditions of 1 Hz and strain of 1 deg. The dynamic viscoelasticity measuring apparatus can be, for example, "RheoSO1-G3000" manufactured by UBM Corporaion.

The lowest melt viscosity of the first resin composition layer and the second resin composition layer is not particularly limited as long as the minimum melt viscosity of the resin sheet is in a desired range, and the film insertability can be improved and the film thickness control can be improved. The lowest melt viscosity of the second resin composition layer disposed on the substrate side is preferably smaller than the lowest melt viscosity of the first resin composition layer. When the lowest melt viscosity of the first resin composition layer is v1 (poise) and the lowest melt viscosity of the second resin composition layer is v2 (poise), it is preferable that v1 and v2 satisfy the relationship of v2+500≦v1. It is preferable to satisfy the relationship of v2+1000≦v1, v2+1500≦v1, or v2+2000≦v1.

In the present invention, the average linear thermal expansion ratio of the cured layer obtained by hardening the resin sheet from 25 ° C to 150 ° C is 17 ppm / ° C or less in terms of the built-in circuit board for suppressing the problem of bending. Preferably, it is 16 ppm / ° C or less, preferably 15 ppm / ° C or less. The lower limit of the average linear thermal expansion ratio is not particularly limited, and may be usually 1 ppm/° C. or higher, 2 ppm/° C. or higher, or 3 ppm/° C. or higher. The average linear thermal expansion rate can be measured by a well-known method such as thermomechanical analysis. The thermomechanical analysis device is, for example, "Thermo Plus TMA 8310" manufactured by Rigaku Corporation. The average linear thermal expansion ratio of the cured layer in the present invention is an average linear thermal expansion ratio of 25 to 150 ° C in the plane direction when subjected to thermomechanical analysis by the tensile elongation method.

In the resin sheet with a support of the present invention, the thickness of the resin sheet is preferably 3 μm or more, and preferably 5 μm or more. The upper limit of the thickness of the resin sheet is preferably 30 μm or less, and preferably 25 μm or less in terms of thinning of the insulating layer.

The thickness of the first resin composition layer composed of the first resin composition in the present invention is preferably 5 μm or less, and more preferably 3 μm or less. The lower limit of the thickness of the first resin composition layer is not particularly limited, and in the aspect of obtaining an insulating layer which exhibits excellent peeling strength to the conductor layer after the roughening treatment, and the ease of production of the resin sheet with the support, it is usually It is set to 0.05 μm or more, 0.1 μm or more, or the like. By the presence of the first resin composition layer, the penetration of the resin can be suppressed, and the film thickness control property at the time of raising the film can be improved.

In the second resin composition of the present invention, the thickness of the second resin composition layer is not particularly limited, and the thickness of the first resin composition layer and an additional resin composition layer (if any) described later is considered. The thickness of the resin sheet may be determined within a desired range. In one embodiment, the thickness of the second resin composition layer is preferably 3 μm or more, preferably 5 μm or more, more preferably 7 μm or more, 8 μm or more, 9 μm or more, or 10 μm or more. The upper limit of the thickness of the second resin composition layer is preferably 100 μm or less, preferably 80 μm or less, more preferably 60 μm or less, 50 μm or less, 40 μm or less, or 30 μm or less. In particular, in order to improve the embeddability, the melt viscosity tends to be extremely low. In this case, the design is less likely to cause penetration, and the thickness of the second resin composition layer is preferably 25 μm or less. In addition, when the film is affected by the other resin composition layer, it becomes difficult to lower the melt viscosity and the embedability is easily lowered. The constitution of the present invention can improve the embeddability, particularly when it is 25 μm or less.

In the resin sheet of the present invention, the first resin composition layer (support side) and the second resin composition layer (on the side opposite to the support) may be different from the first and second resin composition layers. A resin composition layer (not shown). The resin composition layer thus added may be formed of the same material as the component described in the <First Resin Composition> column.

The resin sheet 10 with a support according to the present invention is a surface that is not connected to the support 11 of the resin sheet 12 (that is, a surface opposite to the support), and can further include a protective film. The protective film is provided to prevent adhesion or scratching of dust or the like on the surface of the resin sheet 12. The material of the protective film can be the same as the material described for the support body 11. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. The resin sheet 10 with a support can be used by peeling a protective film when manufacturing a printed wiring board.

In the manufacture of the resin sheet-based component-embedded circuit board with the support of the present invention, it is possible to realize a good built-in circuit for suppressing the problem of bending while achieving good embeddability of the components inside the cavity. Therefore, in the manufacture of the resin sheet-based component-embedded circuit board with the support of the present invention, it can be particularly suitably used for a component (which can be embedded in a cavity) for embedding into the inside of the cavity. Further, the resin sheet with a support of the present invention can be used for forming an insulating layer (for an insulating layer of a printed wiring board) for forming a printed wiring board. Since the resin sheet with the support of the present invention can impart an insulating layer of the fine wiring formed on the resin sheet with the support, the printing method by the assembly method In the manufacture of the wiring board, it can be suitably used for the formation of an insulating layer (for assembling an insulating layer of a printed wiring board), and can be suitably used for formation of a conductor layer by electroplating (assembly insulation of a conductor layer printed wiring board by electroplating) Layer)).

<Method for Producing Resin Sheet with Support>

In the following, an example of a method for producing a resin sheet with a support according to the present invention, that is, a method for producing a resin sheet with a support comprising a first resin composition layer and a second resin composition layer, will be described. An example.

A first resin composition layer composed of a first resin composition and a second resin composition layer composed of a second resin composition are formed on the support.

The method of forming the first resin composition layer and the second resin composition layer is, for example, a method in which the first resin composition layer and the second resin composition layer are connected to each other and laminated. The method of laminating the first resin composition layer and the second resin composition layer and laminating them, for example,

After coating the first resin composition on the support and drying the coating film to form the first resin composition layer, the second resin composition is applied onto the first resin composition layer, and the coating film is dried and set. A method of the second resin composition layer.

In the first resin composition layer, the first resin composition is dissolved in an organic solvent to prepare a resin varnish, and the resin varnish is applied onto the support by die coating or the like, and the resin varnish is dried. Production.

The organic solvent can exemplify, for example, acetone, methyl ethyl ketone, and a ring. Ketones such as ketones such as ketone, ethyl acetate, butyl acetate, cellulose acetate, propylene glycol monomethyl ether acetate, and glycol butane acetate, such as acetate, cellosolve, and diethylene glycol butyl ether An aromatic hydrocarbon such as an alcohol, toluene or xylene, or a guanamine solvent such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone. The organic solvent may be used singly or in combination of two or more.

The drying of the resin varnish may be carried out by a known drying method such as heating or spraying hot air. Depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, it can be dried on the support by drying at 50 ° C to 150 ° C for 3 minutes to 10 minutes. A first resin composition layer is formed.

In the above method, the second resin composition layer is prepared by dissolving the second resin composition in an organic solvent to prepare a resin varnish, and applying the resin varnish to the first resin composition layer formed on the support by using a die coating. It can be made by drying the resin varnish. By relaxing the drying conditions, the melt viscosity can also be lowered.

The organic solvent used for the preparation of the resin varnish in which the second resin composition is dissolved can be used in the same manner as the resin varnish for dissolving the first resin composition, and the resin varnish in which the second resin composition is dissolved can be used by The method of drying the resin varnish in which the first resin composition is dissolved is dried in the same manner.

Further, the resin sheet may be formed by a tandem coating method in which two types of resin varnishes are sequentially applied on one coating line in addition to the above coating method. Further, the resin sheet is coated on the second resin composition layer. After the first resin composition is applied, the coating film is dried to provide a first resin composition layer, and the first resin composition layer and the second resin composition layer which are separately prepared can be connected to each other. A lamination method or the like is formed.

Further, in the present invention, for example, the second resin composition layer and the first resin composition layer are sequentially formed on the protective film, and then the support is laminated on the first resin composition layer to form a resin sheet with a support.

<Method of manufacturing part built-in circuit board>

Next, a method of manufacturing a component-embedded circuit board using the resin sheet 10 with a support of the present invention will be described. The method for manufacturing a component-embedded circuit board according to the present invention includes (A) a circuit board including a first and second main faces and forming a cavity penetrating between the first and second main faces, and a temporary material connected to the second main surface of the circuit board, and a part temporarily suspended by the temporary material in the cavity of the circuit board, and vacuum laminated on the circuit board of the temporary component as claimed in claim 1~ a resin sheet with a support according to any one of 10, a first lamination step of connecting the second resin composition layer to the first main surface of the circuit board, and (B) a resin obtained by laminating the above-mentioned support a heat treatment step of heat treatment of the circuit board of the sheet, and (C) separating the temporary material from the second main surface of the circuit board, and then connecting the second resin sheet to the second main surface of the circuit board, and vacuum laminating includes a second lamination step of the support sheet and the resin sheet with the second support of the second resin sheet connected to the second support, and (D) A step of thermally curing the resin sheet and the second resin sheet of the resin sheet with the support. Before describing each step, the "parts temporary circuit board" using the resin sheet 10 with a support of the present invention will be described.

(Parts temporary circuit board)

The component temporary circuit board (hereinafter also referred to as "partial temporary circuit board" and "cavity substrate") has first and second main faces, and forms an empty space between the first and second main faces. a circuit board of the cavity, a temporary material connected to the second main surface of the circuit board, and a component temporarily suspended by the temporary material in the cavity of the circuit board.

When the component temporary circuit board is manufactured with a built-in circuit board, it can be prepared in accordance with any conventionally known steps. Hereinafter, an example of the procedure of preparing the component temporary circuit board will be described with reference to FIGS. 1A to 1D. However, the present invention is not limited to the following steps.

First, prepare the circuit board (Fig. 1A). The "circuit board" means a board having a circuit board shape having a first surface and a second main surface facing each other, and one or both of the first and second main surfaces are patterned. The inner wall of the circuit board 1 is schematically illustrated in FIG. 1A, and the circuit board 1 includes the circuit board 3 such as the substrate 2, the via wiring, and the surface wiring. In the following description, the first main surface which is conveniently referred to as a circuit board means the upper main surface of the circuit board shown, and the second main surface of the circuit board means the lower main side of the circuit board shown. surface.

The substrate 2 used in the circuit substrate 1 is, for example, glass epoxy A glass epoxy substrate such as a substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, or a thermosetting polyphenylene ether substrate is preferred. Further, when manufacturing a printed wiring board, the "circuit board" as used in the present invention further includes an inner layer circuit board in which an intermediate layer of an insulating layer and/or a conductor layer is to be formed.

The thickness of the substrate 2 of the circuit board 1 is preferably less than 400 μm, preferably 350 μm or less, more preferably 300 μm or less, and particularly preferably 250 μm or less in terms of thickness reduction of the component-embedded circuit board. More preferably, it is 200 μm or less, 180 μm or less, 170 μm or less, 160 μm or less, or 150 μm or less. The lower limit of the thickness of the substrate 2 is not particularly limited, but is preferably 50 μm or more, preferably 80 μm or more, and more preferably 100 μm or more from the viewpoint of improving workability during transportation.

The size of the circuit wiring 3 included in the circuit board 1 may be determined according to desired characteristics. For example, the thickness of the surface wiring is preferably 40 μm or less, preferably 35 μm or less, more preferably 30 μm or less, particularly preferably 25 μm or less, and particularly preferably 20 μm or less and 19 μm or less. , or below 18μm. The lower limit of the thickness of the surface wiring is not particularly limited, and is usually 1 μm or more, 3 μm or more, 5 μm or more.

Then, a cavity (concave portion) for accommodating the component is placed on the circuit substrate (Fig. 1B). As schematically shown in FIG. 1B, a cavity 2a penetrating between the first and second main faces of the circuit board can be provided at a position specific to the substrate 2. The cavity 2a takes into consideration the characteristics of the substrate 2 by, for example, using a drill hole, Well-known methods such as laser, plasma, and etching medium can be formed.

Only one cavity 2a is shown in Fig. 1B, and the cavity 2a can be pulled apart from each other by a specific distance. The distance between the cavities 2a is short in terms of miniaturization of the built-in circuit board of the parts, and is short. The distance between the cavities 2a is preferably 10 mm or less, preferably 9 mm or less, more preferably 8 mm or less, particularly preferably 7 mm or less, and particularly preferably 6 mm or less, depending on the opening size of the cavity 2a itself. According to the method of the present invention, even when the cavity is set to such a short pitch, the occurrence of bending of the substrate can be suppressed. The lower limit of the distance between the cavities 2a depends on the opening size of the cavity 2a itself, and is usually 1 mm or more, 2 mm or more, or the like. The pitch between the cavities 2a does not need to be the same for the circuit substrate, and can 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 rectangle, or a circle. Further, the opening size of the cavity 2a is designed according to the circuit wiring. For example, when the opening shape of the cavity 2a is rectangular, it is preferably 5 mm × 5 mm or less, preferably 3 mm × 3 mm or less, or 2 mm × 2 mm or less. The lower limit of the opening size depends on the size of the housed parts, but is usually 0.5 mm x 0.5 mm or more. The opening shape and the opening pattern of the cavity 2a do not need to be the same for the circuit board, and can be different.

Then, the temporary material is laminated on the second main surface of the circuit board on which the cavity is provided (FIG. 1C). The temporary material is not particularly limited as long as it has an adhesive surface indicating sufficient adhesiveness, and any conventionally known temporary material can be used for manufacturing the built-in circuit board. In the mode shown in FIG. 1C, the laminated film-like temporary material 4 is connected to the second main surface of the circuit board by the adhesive surface of the temporary material 4. By this, The adhesive surface of the temporary material 4 of the cavity 2a becomes exposed.

For example, the UC series (UV tape for wafer cutting) manufactured by Furukawa Electric Co., Ltd. can be cited as the film-like temporary material.

Then, the cavity is temporarily attached to the exposed surface of the exposed temporary material (Fig. 1D). In the mode shown in Fig. 1D, the part 5 is temporarily attached to the adhesive surface of the exposed temporary material 4 via the cavity 2a.

The component 5 may be an appropriate component selected according to a desired characteristic, and examples thereof include a passive component such as a capacitor, an inductor, and a resistor, and an active component such as a semiconductor bare chip. The same part 5 can be used for all cavities, and different parts 5 can be used for each cavity.

When the component is temporarily connected to the circuit board, the circuit wiring 3 may be provided after the cavity 2a is formed in the substrate 2, for example, and the temporary material 4 may be laminated on the second main surface of the circuit board. The cavity 2a is sufficient.

A method of manufacturing a component-embedded circuit board using the resin sheet with a support of the present invention will be described. In the following description, the resin sheet with the support of the present invention in which the first main surface and the second main surface which are laminated on the component-embedded circuit board are respectively referred to as "resin sheet 10 with the first support" and "The case where the resin sheet 20 of the second support is attached". The resin sheet 10 with the first support and the resin sheet 20 with the second support can be the same or different ones can be used.

<(A) First Lamination Step (Lamination of Resin Sheet with First Support)>

First, the resin sheet with the support of the present invention (with the first support) The resin sheet of the body is laminated on the circuit board of the temporarily attached component (first lamination step). Specifically, the resin sheet 10 of the first support is vacuum-bonded to the circuit board 1' of the temporary component, and the second resin composition layer 14 is connected to the first main surface of the circuit board (see FIG. 3A). Here, when the resin sheet 10 with the first support is provided with a protective film covering the second resin composition layer 14, the protective film is peeled off, and then the circuit board is laminated.

The vacuum lamination of the resin sheet 10 with the first support attached to the component temporary circuit board 1' is performed by, for example, decompressing the resin on the part temporary circuit board 1' from the support 11 side. The sheet 10 can be heated by pressing. A base material (not shown; hereinafter also referred to as "heating and pressing base material") for heating and pressing the resin sheet 10 to which the first support is attached to the component temporary circuit board 1' can be exemplified by a heated metal. Board (SUS mirror plate, etc.) or metal (SUS )Wait. In addition, the resin sheet 10 to which the first support is attached is not directly pressed by the heating and pressing base material, and is heat-pressed via an elastic material such as heat-resistant rubber to temporarily suspend the circuit wiring 3 or the cavity 2a of the circuit board 1'. It is preferable that the resin sheet 10 with the first support attached to the unevenness is preferable.

The heating and pressing temperature is preferably in the range of 80 ° C to 160 ° C, preferably in the range of 100 ° C to 140 ° C, and the heating and pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, preferably 0.29 MPa to 1.47 MPa, and the heating pressure is employed. The time is preferably between 20 seconds and 400 seconds, preferably between 30 seconds and 300 seconds. The vacuum lamination system is preferably carried out under reduced pressure of 26.7 HPa or less.

Vacuum lamination was carried out by a commercially available vacuum laminating machine. city The vacuum laminating machine which is sold, for example, a vacuum press laminator manufactured by Nippon Seisakusho Co., Ltd., a vacuum coater manufactured by Rimalia Co., Ltd., and a 2-stage assembled layer made by Rimalia Co., Ltd. Machine and so on.

After the first laminating step, under normal pressure (at atmospheric pressure), for example, by smoothing and pressing the substrate from the first support 11 side by hot pressing, the smoothing step of smoothing the laminated first bonding film is performed. It is better. The hot pressing conditions of the smoothing step can be the same as the heating and pressing conditions of the vacuum lamination described above.

The smoothing step is carried out by a commercially available laminating machine. Further, the first laminating step and the smoothing step can be continuously performed using the commercially available vacuum laminator.

After the first laminating step, the second resin composition layer 14 is filled in the cavity 2a, and the part 5 temporarily suspended in the cavity 2a is fitted into the second resin composition layer 14 (Refer to Figure 3B).

<(B) Heat treatment step>

Then, the circuit board on which the resin sheet 10 of the first support is laminated is heat-treated (heat treatment step). The heating temperature in this step is preferably 155 ° C or lower, preferably 150 ° C or lower, more preferably 145 ° C or lower, and particularly preferably 140 ° C or lower. The lower limit of the heating temperature is preferably 110 ° C or higher, preferably 115 ° C or higher, more preferably 120 ° C or higher, and particularly preferably 125 ° C or higher.

The heating time in the heat treatment step varies depending on the heating temperature, but is preferably 10 minutes or longer, preferably 15 minutes or longer, more preferably 20 minutes or longer. The upper limit of the heating time is not particularly limited, but is Standing for 60 minutes or less.

The heat treatment of the resin sheet 12 in the heat treatment step is preferably carried out under atmospheric pressure (at normal pressure).

The heat treatment of the resin sheet 12 in the heat treatment step may be carried out in a state in which the support 11 is adhered to the resin sheet 12, or the support 11 may be peeled off to expose the resin sheet 12. In a preferred embodiment, the heat treatment of the resin sheet 12 is carried out in a state in which the support 11 is adhered to the resin sheet 12 (first resin composition layer). This is advantageous in terms of preventing adhesion of foreign matter and preventing damage to the first resin composition layer.

When the heat treatment of the resin sheet 12 in the heat treatment step is performed in the state in which the support 11 is adhered, the support layer 11 is peeled off before the step of providing the conductor layer (circuit line) on the insulating layer (hardened layer) obtained by curing the resin sheet 12 For example, it may be peeled off between the first heat treatment step and the second lamination step described later, and the second lamination step and the thermal curing step (described later) may be peeled off, and the hot curing step may be carried out. . In a preferred embodiment, the support 11 is peeled off after the thermal hardening step. In addition, when a metal foil such as a copper foil is used as the support 11 , a conductor layer (circuit wiring) can be provided using the metal foil as will be described later, so that the support 11 can be not peeled off.

In a preferred embodiment, a process of cooling the circuit board to a normal temperature (room temperature) can be performed between the heat treatment steps of the first lamination step.

In a preferred embodiment, the resin sheet 12 is a resin sheet (heat treatment body) 12' (see Fig. 3C) by a heat treatment step. In addition, the support body 11 in Fig. 3C indicates that the heating portion is in an attached state. In the state in which the resin sheet (heat-treated body) 12' is obtained, 13 is a first resin composition layer (heat treatment body), and 14' is a second resin composition layer (heat treatment body).

<(C) Second Lamination Step (Lamination of Resin Sheet with Second Support)>

After the heat treatment step, the temporary material 4 is peeled off from the second main surface of the circuit board, and the second main surface of the circuit board 2 is exposed. In addition, the resin sheet 20 with the second support is vacuum-laminated, and the second resin composition layer 24 (second resin sheet) is connected to the second main surface (lower side surface) of the circuit board 2 (see the figure). 3D). Here, the resin sheet with the second support includes a second support and a second resin sheet connected to the second support. The resin sheet to which the second support is attached is preferably a resin sheet with a support of the present invention. The structure of the second support or the second resin sheet is the same as that of the above-described support and resin sheet of the present invention. The resin sheet 20 with the second support shown in FIG. 3D is the same as the resin sheet 10 with the first support, and the second resin sheet 22 is composed of the first resin composition layer 23 and the second resin composition layer 24. . In addition, a resin sheet with a second support may be used as a resin sheet with a support (for example, a resin sheet is a resin sheet with a support composed of a single resin composition layer, and the resin sheet includes the first and second sheets). The resin composition layer, but does not satisfy the desired minimum melt viscosity condition and average line thermal expansion condition of the present invention).

The peeling of the temporary material 4 may be performed by a conventionally known method depending on the type of the temporary material 4. For example, as a temporary material 4, use UV adhesive for wafer cutting such as UC series manufactured by Furukawa Electric Co., Ltd. When the belt is irradiated with UV, the temporary material 4 can be peeled off. Conditions such as the amount of UV irradiation can be a well-known condition generally used in the manufacture of a component-embedded circuit board.

When a circuit board having a high cavity density or a circuit board having a small thickness is used, the occurrence of bending of the substrate can be suppressed by the heat treatment step, so that the substrate transfer from the heat treatment step to the second lamination step does not cause an obstacle ( Without hindrance, the second lamination step can be carried out smoothly. Further, since the resin composition layer is heat-treated under specific conditions, it is possible to suppress the positional change (offset) of the components of the vacuum lamination in accordance with the second lamination step, and it is possible to realize a part excellent in the arrangement accuracy of the parts to be produced. Built-in board. The amount of warpage is preferably 90 μm or less, and preferably 80 μm or less.

The vacuum lamination of the resin sheet 20 with the second support in the second lamination step can be carried out in the same manner and under the conditions of vacuum lamination of the resin sheet 10 with the first support in the first lamination step.

In a preferred embodiment, a process of cooling the circuit substrate to a normal temperature (room temperature) between the heat treatment step and the second lamination step can be performed.

In the second laminating step, the second resin sheet (the second resin composition layer 24, the first resin composition layer 23) and the second support 21 are laminated on the second main surface of the circuit board 2 (see FIG. 3E). ).

The second support 21 may be peeled off before the step of providing the conductor layer (circuit wiring) on the insulating layer (cured layer) obtained by curing the second resin sheet 22, for example, between the second lamination step and the hardening step described later. It can be peeled off and peeled off after the hardening step. In a preferred embodiment, the second support 21 is peeled off after the hardening step. In addition, as the second support When a metal foil such as a copper foil is used for the body 21, a conductor layer (circuit wiring) can be provided using the metal foil as will be described later, so that the second support 21 can be prevented from being peeled off.

<(D) hardening step>

In the hardening step, the resin sheet 12 of the resin sheet 10 with the first support and the second resin sheet 22 of the resin sheet 20 with the second support are thermally cured. The first resin layer (heat treatment body) 13' of the first main surface of the circuit board 2 forms the first insulating layer 13" (cured layer), and the second resin composition layer (heat treatment body) 14' A second insulating layer 14" (hardened layer) is formed. Further, in the second main surface of the circuit board 2, the first resin layer 23 is formed as a first insulating layer 23" (cured layer), and the second resin layer 24 is formed as a second insulating layer 24" (hardened layer). (Refer to Figure 3F).

The conditions of the thermosetting are not particularly limited, and the conditions generally used when forming the insulating layer of the component-embedded circuit board may be used.

The thermosetting conditions of the resin sheets 12 and 22 of the resin sheets 10 and 20 of the first and second support members differ depending on the composition of the resin composition for each resin composition layer, etc., but the curing temperature can be set to 120 ° C ~ 240 ° C range (preferably 150 ° C ~ 210 ° C range, preferably 170 ° C ~ 190 ° C range), hardening time can be set to 5 minutes ~ 90 minutes range (good 10 minutes ~ 75 minutes) , preferably 15 minutes to 60 minutes).

Before the heat curing, the first and second resin sheets 12 and 22 may be preheated at a temperature lower than the curing temperature. For example, before thermal curing, the resin sheet can be heated at a temperature of 50 ° C or more and less than 120 ° C (preferably 60 ° C or more and 110 ° C or less, preferably 70 ° C or more and 100 ° C or less). 12, 22 pre-heating for more than 5 minutes (good for 5 minutes to 150 minutes, preferably 15 minutes to 120 minutes). When preheating is performed, the hardening step is set to include the preheating.

It is preferable to thermally harden each of the resin sheets subjected to the hardening step under atmospheric pressure (at normal pressure).

In a preferred embodiment, a process of cooling the circuit substrate to a normal temperature (room temperature) between the second lamination step and the hardening step can be performed.

In the present invention, the average linear thermal expansion ratio of the cured layer (insulating layer 12", 22") obtained by curing the resin sheet 12 and the second resin sheet 22 from 25 ° C to 150 ° C reduces the bending of the substrate. In general, it is preferably 17 ppm/° C. or less, preferably 15 ppm/° C. or less.

Although the embodiment using the temporary material has been described in detail above, it is also possible to use a resin sheet with a support instead of the temporary material to manufacture the component built-in circuit board. The resin sheet with a support can be used instead of the temporary material, and can be the same as the resin sheet with the second support described above, and can be a resin sheet with a support of the present invention, and can be another resin with a support. Sheet. When the temporary material is replaced by a resin sheet with a support, the step of peeling off the material is not required.

<other steps>

Further, the method of manufacturing a component-embedded circuit board of the present invention can further include a step of performing an opening on the insulating layer (opening step), a step of roughening the surface of the insulating layer (roughing step), and a roughened insulating layer The step of forming a conductor layer on the surface (conductor layer forming step). These steps are for zero The manufacture of a built-in circuit board can be carried out by various methods known to those skilled in the art. Further, when the support bodies 11 and 21 of the respective resin sheets 10 and 20 with the support are peeled off after the hardening step, the step of peeling off the support bodies 11 and 21 is between the step of hardening and the opening, between the opening step and the roughening step, Alternatively, it may be carried out between the roughening step and the conductor layer forming step.

The opening step is performed by opening the insulating layers 12", 22" (hardened layer), whereby holes such as through holes can be formed in the insulating layers 12", 22". For example, holes, lasers (carbonated gas lasers, YAG lasers, etc.), plasma equal to the insulating layers 12", 22" can be used to form the holes. In the built-in circuit board of the part, the insulating layers 12", 22" are generally turned on by the through holes.

The roughening step is a step of roughening the insulating layers 12", 22". The steps and conditions of the roughening treatment are not particularly limited, and well-known steps and conditions that are generally used when forming the insulating layers 12" and 22" of the component-embedded circuit board can be employed. For example, the roughening treatment of the insulating layers 12", 22" can be performed by roughening the insulating layer 12 by the swelling treatment of the swelling liquid, the roughening treatment by the oxidizing agent, and the sequential treatment of the neutralizing treatment by the neutralizing liquid. ",twenty two". The swelling liquid is not particularly limited, and an alkali solution, a surfactant solution, or the like is preferably an alkali solution, and the alkali solution is preferably a sodium hydroxide solution or a potassium hydroxide solution. Commercially available swellable liquids include, for example, Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, and the like. The swelling treatment by the swelling liquid is not particularly limited, and the insulating layer 12" is formed by, for example, a swelling liquid of 30 to 90 ° C, 22" immersion can be carried out for 1 minute to 20 minutes. In order to suppress the resin swelling of the insulating layers 12" and 22" to an appropriate extent, the insulating layer 12", 22" is preferably in the swelling liquid of 40 to 80 °C. The immersion is carried out for 5 seconds to 15 minutes. The oxidizing agent is not particularly limited, and for example, potassium permanganate or sodium permanganate may be dissolved in an alkaline permanganic acid solution in an aqueous solution of sodium hydroxide. The roughening treatment of an oxidizing agent such as a permanganic acid solution is performed 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. In addition, it is preferably an alkaline permanganic acid solution. The concentration of the permanganate is 5% by mass to 10% by mass. The commercially available oxidizing agent may, for example, be an alkaline permanganic acid solution such as concentrate compact P or dosing solution Securiganth P manufactured by Attotel Germany Co., Ltd. The liquid acidic aqueous solution is preferred, and a commercially available product can be, for example, a reduction solution Securiganth P manufactured by Attotel Germany Co., Ltd. The treatment by the neutralizing solution can be performed by roughening the solution by the oxidizing agent. Processing surface at 30~80 °C The liquid is immersed for 5 minutes to 30 minutes, and the object to be subjected to roughening by the oxidizing agent solution is immersed in a neutralizing solution at 40 to 70 ° C for 5 minutes to 20 minutes. It is better.

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

The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer can be a single metal layer or an alloy Examples of the layer and the alloy layer include a layer selected from alloys of two or more kinds of metals (for example, nickel ‧ chromium alloy, copper ‧ nickel alloy, and copper ‧ titanium alloy) Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel chrome alloy, is formed in terms of generality of the conductor layer, cost, ease of patterning, and the like. Copper, nickel alloy, copper ‧ titanium alloy alloy layer is preferred, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal layer, or nickel ‧ chromium alloy alloy layer is better, copper The single metal layer is better.

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

The thickness of the conductor layer is generally from 3 μm to 35 μm, preferably from 5 μm to 30 μm, depending on the desired design of the 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 electroplating. For example, the surface of the first and second insulating layers is plated by a conventional technique such as a semi-additive method or a full additive method, whereby a conductor layer (circuit wiring) having a desired pattern can be formed. Hereinafter, an example of a conductor layer formed by a semi-additive method will be described.

First, an electroplated sheet layer is formed on the surface of the two insulating layers 12", 22" by electroless plating. Then, a mask pattern exposed by a part of the plating sheet layer is formed on the formed plating sheet layer corresponding to the desired wiring pattern. Forming on the exposed electroplated sheet by electrolytic plating After the metal layer, the reticle pattern is removed. Thereafter, the electroless plating layer is removed by etching or the like, and a conductor layer having a desired pattern can be formed.

The conductors (via wirings) are also formed in the via holes by the steps, and the circuit wirings 3 provided on the surfaces of the insulating layers 12" and 22" and the circuit wirings of the circuit board are electrically connected to each other, and the component-embedded circuit board 100 can be obtained. (Refer to Figure 3G).

When a metal foil such as a copper foil is used for the support 11 and the second support 21, the conductor layer can be formed by subtraction of the metal foil or the like. Further, it is also possible to form a plated conductor layer by electrolysis using a metal foil as an electroplated sheet layer.

Further, the method of manufacturing the component-embedded circuit board of the present invention can also include the step of individually forming the component-embedded circuit board.

In the individual singulation step, the obtained structure can be individually formed into individual component-embedded circuit board units by, for example, a conventionally known cutting device having a rotary blade.

[semiconductor device]

The semiconductor device of the present invention comprises a component-embedded circuit board manufactured by the above method.

The semiconductor device can be exemplified by various semiconductor devices such as electric products (such as computers, portable telephones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trains, ships, and airplanes).

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples. Further, in the following descriptions, "parts" and "%" are specified separately, and "mass parts" and "% by mass" are respectively indicated.

<Production of Resin Sheet with Support>

A resin sheet with a support of the examples and the comparative examples was produced using the resin varnish (resin composition) prepared in the following procedure.

(Modulation of Resin Varnish 1)

Stirring a naphthyl ether type epoxy resin ("EXA-7311-G4S" manufactured by DIC Co., Ltd., epoxy equivalent 186) in a mixed solvent of 15 parts of solvent oil and 5 parts of cyclohexanone. Phenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxide equivalent: 185) 10 parts, biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288) 20 parts A phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, and a 1:1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass) was dissolved and dissolved in 25 parts. After cooling to room temperature, the mixed triazine skeleton contains a naphthol novolak-based curing agent (hydroxyl equivalent 125, "LA-7054" manufactured by DIC Co., Ltd., and a 60% solid MEK solution), and a naphthol-based system. Hardener ("SN-485" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., hydroxyl equivalent 215, 60% solid solution in MEK) 15 parts, polyvinyl butyral resin (glass transition temperature 105 °C, Sekisui Chemical Industry Co., Ltd.) Co., Ltd. "KS-1") solid solution 15% ethanol and toluene 1:1 mixed solution 10 parts, amine-based hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5% by mass 1 part of the MEK solution, 2 parts of an imidazole-based hardening accelerator ("P200-H50" manufactured by Mitsubishi Chemical Corporation, 50% by mass of propylene glycol monomethyl ether solution), and rubber at room temperature in 20 parts of MEK Particles (AC3816N, manufactured by Aika Kogyo Co., Ltd.), which were subjected to surface treatment of spherical cerium oxide ("MAC2" manufactured by Shin-Etsu Chemical Co., Ltd.) by an amine decane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.). , an average particle diameter of 0.5 μm, a carbon content per unit surface area of 0.38 mg/m ² ), 50 parts, used After the high-speed rotary mixer was uniformly dispersed, it was filtered with a cartridge filter ("SHP050" manufactured by ROKITECHNO) to prepare a resin varnish 1.

(modulation of resin varnish 2)

A bisphenol type epoxy resin (ZX1059, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), an epoxy equivalent of about 169, a bisphenol A type, and a bisphenol F were stirred in a mixed solvent of 20 parts of solvent oil and 10 parts of cyclohexanone. Type 1:1 mixed product) 6 parts, naphthalene type epoxy resin ("HP4032SS" manufactured by DIC Corporation, epoxy equivalent of about 144) 5 parts, naphthalene type epoxy resin (HP-4710 manufactured by DIC Corporation) "Epoxy equivalent of about 170) 5 parts, bisphenol type epoxy resin ("XX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) 6 parts, biphenyl type epoxy resin (Nippon Chemical Co., Ltd.) Co., Ltd. made "NC3000H", epoxy equivalent 288) 10 parts while heating and dissolving. After cooling to room temperature, the mixed triazine skeleton contains a cresol novolak-based curing agent (hydroxy equivalent 151, "LA3018-50P" manufactured by DIC Corporation, and 2-methoxypropanol solution having a solid content of 50%). 20 parts, a naphthol-based curing agent ("SN-495V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., a hydroxyl equivalent of 231, a MEK solution of 60% solid content) 12 parts, an amine-based hardening accelerator (4-dimethyl group) Aminopyridine (DMAP), a solid content of 5% by mass of MEK solution), 1 part, flame retardant (HCA-HQ, manufactured by Sanko Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydrogen- Surface-treated spherical oxidation of 9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm), 4 parts by amine decane-based coupling agent ("MK Corporation", "SKM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 180 parts of 矽 ("SOC4" manufactured by Admatech Co., Ltd., average particle diameter: 1 μm, and carbon content per unit surface area: 0.31 mg/m ² ) were uniformly dispersed by a high-speed rotary mixer, and then subjected to a cartridge filter ("SHP050" manufactured by ROKITECHNO). Filter to prepare resin varnish 2.

(Modulation of Resin Varnish 3)

A bisphenol epoxy resin (ZX1059, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), an epoxy equivalent of about 169, a bisphenol A type, and a bisphenol F were stirred in a mixed solvent of 25 parts of solvent oil and 5 parts of cyclohexanone. Type 1:1 mixture) 5 parts, bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 238) 10 parts, bisphenol type epoxy resin (Mitsubishi Chemical Co., Ltd.) Company-made "YX4000HK", epoxy equivalent of about 185) 5 parts, naphthalene-type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent 330) 20 parts, and phenoxy resin (Mitsubishi Chemical Co., Ltd. Co., Ltd. "YX7553BH30", 30% by mass of cyclohexanone: a 1:1 solution of methyl ethyl ketone (MEK), was dissolved and dissolved in 5 parts. After cooling to room temperature, the mixed triazine skeleton contains a cresol novolak-based curing agent (hydroxy equivalent 151, "LA3018-50P" manufactured by DIC Corporation, and 2-methoxypropanol solution having a solid content of 50%). 15 parts, an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution having a reactive base equivalent of about 223 and a nonvolatile content of 65 mass%), 10 parts, and an amine-based hardening accelerator (4-two) 1 part of methylamine pyridine (DMAP), a solid content of 5% by mass of MEK solution), a flame retardant (HCA-HQ, manufactured by Sanko Co., Ltd., 10-(2,5-dihydroxyphenyl)-10- Hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide, 2 μm of an average particle diameter of 2 parts, and a surface treated ball of an amine decane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 170 parts of cerium oxide ("SOC2" manufactured by Admatech Co., Ltd., average particle diameter: 0.5 μm, carbon content per unit surface area: 0.38 mg/m ² ), and uniformly dispersed by a high-speed rotary mixer, and then a cartridge filter ("SHP050" manufactured by ROKITECHNO) The filtration was carried out to prepare a resin varnish 3.

(Modulation of Resin Varnish 4)

A bisphenol type epoxy resin (ZX1059, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), an epoxy equivalent of about 169, a bisphenol A type, and a bisphenol F were stirred in a mixed solvent of 20 parts of solvent oil and 10 parts of cyclohexanone. Type 1:1 mixed product) 6 parts, naphthalene type epoxy resin ("HP4032SS" manufactured by DIC Corporation, epoxy equivalent of about 144) 5 parts, naphthalene type epoxy resin (HP-4710 manufactured by DIC Corporation) "Epoxy equivalent of about 170) 5 parts, bisphenol type epoxy resin ("XX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) 6 parts, biphenyl type epoxy resin (Nippon Chemical Co., Ltd.) 10 parts of "NC3000H", epoxy equivalent 288), and phenoxy resin ("XX7553BH30" manufactured by Mitsubishi Chemical Corporation, and 30% by mass of cyclohexanone: methyl ethyl ketone (MEK)) : 1 solution) 10 parts while heating to dissolve. After cooling to room temperature, the mixed triazine skeleton contains a naphthol novolak-based curing agent (hydroxy equivalent of 125, "LA7054" manufactured by DIC Co., Ltd., and a 60% solid MEK solution), and a naphthol-based hardener. (10 parts of "SN-495V", hydroxyl equivalent 231, 60% solid content MEK solution manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), amine-based hardening accelerator (4-dimethylaminopyridine (DMAP), solid content) 5 parts by mass of MEK solution) 1 part, flame retardant (HCA-HQ, manufactured by Sanko Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphine 2 parts of phenanthrene-10-oxide, 2 μm of average particle size, and 2 parts of rubber particles ("AC3816N" manufactured by Aika Kogyo Co., Ltd.) were swelled for 12 hours at room temperature in an MEK 10 part, and an amine decane-based coupler was used. The agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was subjected to surface treatment of 180 parts of spherical cerium oxide ("SOC4" manufactured by Admatech Corporation, average particle diameter: 1 μm, carbon content per unit surface area: 0.31 mg/m ² ), and used. After the high-speed rotary mixer was uniformly dispersed, it was filtered with a cartridge filter ("SHP050" manufactured by ROKITECHNO) to prepare a resin varnish 4.

(modulation of resin varnish 5)

A bisphenol type epoxy resin (ZX1059, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), an epoxy equivalent of about 169, a bisphenol A type, and a bisphenol F were stirred in a mixed solvent of 15 parts of solvent oil and 5 parts of cyclohexanone. Type 1:1 mixture) 5 parts, dixylenol type epoxy resin ("XX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 185) 10 parts, biphenyl type epoxy resin (Nippon Chemical Co., Ltd.) 20 parts of "NC3000H", epoxy equivalent 288), and phenoxy resin ("XX7553BH30" manufactured by Mitsubishi Chemical Corporation, and 30% by mass of cyclohexanone: methyl ethyl ketone (MEK)) :1 solution) 15 parts while heating and dissolving. After cooling to room temperature, the mixed triazine skeleton contains a naphthol novolac-based curing agent (hydroxyl equivalent 125, "LA-7054" manufactured by DIC Co., Ltd., and a 60% solid MEK solution), and a naphthol-based system. 12 parts of hardener ("SN-485" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., hydroxyl equivalent 215, 60% solid solution), polyvinyl butyral resin (glass transition temperature 105 °C, Sekisui Chemical Industry Co., Ltd.) Co., Ltd. "KS-1") solid solution 15% ethanol and toluene 1:1 mixed solution 10 parts, amine-based hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5% by mass 1 part of the MEK solution, 0.5 part of an imidazole-based hardening accelerator ("P200-H50" manufactured by Mitsubishi Chemical Corporation, 50% by mass of propylene glycol monomethyl ether solution), and rubber at room temperature in 10 parts of MEK Particles (manufactured by Aika Kogyo Co., Ltd., AC3816N), which were subjected to surface treatment of spherical cerium oxide (manufactured by Admatech Corporation), which was swelled for 2 hours by an amine decane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) SOC1 ", average particle diameter 0.25 m, the carbon amount per unit surface area of 0.36mg / m ²⁾ 30 parts After uniform dispersion using a high speed rotation stirrer, to the filter cartridge (ROKITECHNO manufactured "SHP030") filter to prepare a resin varnish 5.

(modulation of resin varnish 6)

A bisphenol type epoxy resin (ZX1059, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), an epoxy equivalent of about 169, a bisphenol A type, and a bisphenol F were stirred in a mixed solvent of 20 parts of solvent oil and 5 parts of cyclohexanone. Type 1:1 mixture) 5 parts, bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 238) 10 parts, bisphenol type epoxy resin (Mitsubishi Chemical Co., Ltd.) Company-made "YX4000HK", epoxy equivalent of about 185) 5 parts, naphthalene-type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent 330) 20 parts, and phenoxy resin (Mitsubishi Chemical Co., Ltd. Co., Ltd., "YX7553BH30", and a solid component of 30% by mass of cyclohexanone: a 1:1 solution of methyl ethyl ketone (MEK) in 15 parts, was dissolved by heating. After cooling to room temperature, the mixed triazine skeleton contains a cresol novolak-based curing agent (hydroxy equivalent 151, "LA3018-50P" manufactured by DIC Corporation, and 2-methoxypropanol solution having a solid content of 50%). 15 parts, an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution having a reactive base equivalent of about 223 and a nonvolatile content of 65 mass%), 15 parts, and an amine-based hardening accelerator (4- 1 part of dimethylamine pyridine (DMAP), a solid content of 5% by mass of MEK solution), a flame retardant (HCA-HQ, manufactured by Sanko Co., Ltd., 10-(2,5-dihydroxyphenyl)-10 - Hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm) 4 parts, amine decane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 150 parts of cerium oxide ("SOC2" manufactured by Admatech Corporation, average particle diameter: 0.5 μm, carbon content per unit surface area: 0.38 mg/m ² ), and uniformly dispersed in a high-speed rotary mixer, and a cartridge filter ("SHP050" manufactured by ROKITECHNO) The filtration was carried out to prepare a resin varnish 6.

Table 1 shows the materials used for the production of each resin varnish and the blending amount thereof (parts by mass of nonvolatile matter).

(Example 1: Production of Resin Sheet 1 with Support)

In the support system, a PET film ("Lumirror T6AM" manufactured by Toray Industries, Inc., manufactured by Toray Co., Ltd.) having a mold release treatment ("AL-5" manufactured by Linke Co., Ltd.), a thickness of 38 μm, and a softening point of 130 ° C, was prepared. "release PET").

The resin varnish 1 was uniformly applied to the release PET by using a die-coating method, and the thickness of the first resin composition layer after drying was 3 μm, and dried at 80 ° C to 160 ° C for 5 minutes to obtain the first on the release PET. Resin composition layer. Thereafter, the resin varnish 2 is applied onto the first resin composition layer so as to have a total thickness of 25 μm with the dried first resin composition layer, and then dried at 70 ° C to 110 ° C (average 95 ° C) for 4.5 minutes to form two layers. Resin composition layer (resin sheet). Then, a polypropylene film (manufactured by Prince Effort Co., Ltd.) is laminated on the surface of the resin sheet that is not connected to the support (that is, the surface of the second resin composition layer that is not connected to the first resin composition layer). ALPHAN MA-430" and a thickness of 20 μm were used as a protective film to be connected to the second resin composition layer. Thereby, the resin sheet 1 with the support which consists of a support body, a 1st resin composition layer (from resin varnish 1), a 2nd resin composition layer (from resin varnish 2), and a protective film is obtained. Further, in order to measure the melt viscosity of the individual second resin composition layer, a uniform application of the resin varnish 2 to the release PET was carried out by using a die-coating method, and the thickness of the resin composition layer after drying was 22 μm. Dry at °C~110°C (average 95°C) for 4.5 minutes. In this embodiment, the resin varnish 1 was used as the first resin composition, and the resin varnish 2 was used as the second resin composition.

(Example 2: Production of Resin Sheet 2 with Support)

A resin sheet 2 with a support was produced in the same manner as in Example 1 except that the coating was replaced by a tandem coating method twice. Specifically, except that the resin varnish 1 was applied by a nozzle coating to a thickness of 3 μm after drying, and pre-dried at 130 ° C for 0.8 minutes, the resin varnish 2 was applied onto the resin varnish 1 using a nozzle to dry it. A resin sheet 2 with a support was obtained in the same manner as in Example 1 except that the total thickness of the first resin composition layer was 25 μm and the temperature was dried at 80 ° C to 110 ° C (average 100 ° C) for 4 minutes. Further, in order to measure the melt viscosity of each of the individual resin composition layers, the resin varnish 1 was applied to the release PET to a thickness of 3 μm after drying, and pre-dried at 130 ° C for 0.8 minutes, and further 80 ° C to 110 ° C. After drying for 4 minutes (average 100 ° C), and applying to the release PET, the resin varnish 2 was dried to a thickness of 22 μm, and dried at 80 ° C to 110 ° C (average 100 ° C) for 4 minutes.

(Example 3: Production of Resin Sheet 3 with Support)

In the same manner as in Example 1, except that the resin varnish 3 was used instead of the resin varnish 2, the resin sheet 3 with a support was obtained. In this example, the resin varnish 1 was used as the first resin composition, and the resin varnish 3 was used as the second resin composition.

(Example 4: Production of Resin Sheet 4 with Support)

In addition to the use of die-coating on the release PET, uniform coating of resin varnish 5 The thickness of the first resin composition layer after drying was 3 μm, and drying was performed at 75 ° C to 150 ° C for 2.5 minutes to obtain a first resin composition layer on the release PET. Then, the resin varnish 4 is applied onto the first resin composition layer, and after drying, the total thickness of the first resin composition layer is 25 μm, and drying is performed at 70 ° C to 110 ° C (average 95 ° C) for 4.5 minutes. A resin sheet 4 with a support was obtained in the same manner as in Example 1 except for the two-layer resin composition layer. In this embodiment, the resin varnish 5 is used as the first resin composition, and the resin varnish 4 is used as the second resin composition.

(Comparative Example 1: Production of Resin Sheet 5 with Support)

A resin sheet 5 with a support was obtained in the same manner as in Example 1 except that the resin varnish 4 was used instead of the resin varnish 2 in Example 1.

(Comparative Example 2: Production of Resin Sheet 6 with Support)

A resin sheet 6 with a support was obtained in the same manner as in Example 1 except that the resin varnish 6 was used instead of the resin varnish 2 in Example 1.

(measuring the lowest melt viscosity) (1) Determination of the lowest melt viscosity of the first and second resin composition layers (single layer)

In the same manner as in each of the examples and the comparative examples, the resin composition layer of the sample of the first or second resin composition layer of each of the single-layer coatings was peeled off from the release PET, and the measurement was performed by compression molding. Granules (18 mm in diameter, 1.2 to 1.3 g).

Using the particle for measurement by dynamic viscoelasticity measuring device (UBM) "RHeo SO1-G3000" manufactured by the Corporation, 1 g of the resin composition layer, a parallel plate having a diameter of 18 mm, and a temperature rise of 5 ° C / min at an initial temperature of 60 ° C to 200 ° C to measure the temperature interval of 2.5 ° C. The measurement conditions of the vibration number of 1 Hz and the strain of 1 deg were measured for the viscoelasticity of the movement, and the lowest melt viscosity was obtained. The results are shown in Table 2.

(2) Measurement of the lowest melt viscosity of the resin sheet (the first and second resin composition layers are composed of two layers)

Two sheets of the resin sheet with the support produced in each of the examples and the comparative examples were used, and (A) one sheet of the release-release type PET was left in the polypropylene film surface (the second resin composition layer side). In the composition layer, (B) the other release-off polypropylene film has two resin composition layers remaining on the release PET surface (on the first resin composition layer side). Then, the film obtained by bonding the surfaces on the resin composition layer side of (A) and (B) is cut, and the state of the first resin composition layer/second resin composition layer is maintained, and the film is compressed and measured. It was produced using pellets (diameter 18 mm, 1.2 g to 1.3 g). Using the dynamic viscoelasticity measuring device ("RHeo SO1-G3000" manufactured by UBM Corporation), 1 g of the sample resin composition was used, and a parallel plate having a diameter of 18 mm was used, and the initial temperature was raised at a temperature of 60 ° C to 200 ° C. The temperature was raised at ° C/min, and the viscoelasticity of the dynamics was measured under the measurement conditions of a temperature difference of 2.5 ° C, a vibration number of 1 Hz, and a strain of 1 deg, and the lowest melt viscosity was obtained. The results are shown in Table 2.

(Measure the average linear thermal expansion coefficient of the cured product of the resin sheet with the support)

Glass cloth substrate epoxy resin double-sided copper-clad laminate is placed in contact with a glass cloth substrate epoxy double-sided copper-clad laminate ("R5715ES" manufactured by Matsushita Electric Works Co., Ltd., thickness 0.7mm, 255mm square) An untreated surface of a PET film ("501010", thickness 38 μm, 240 mm square) manufactured by Linke Co., Ltd., and four sides of the release PET film were fixed with a polyimide and a tape (width: 10 mm).

A resin sheet (200 mm) of each of the support bodies produced in the examples and the comparative examples was laminated in a central batch using a batch type vacuum pressure laminator (a two-stage assembly laminator CVP700 manufactured by Ritalia Co., Ltd.). The square resin is in contact with the release surface of the release PET film with the second resin composition layer. After the pressure was reduced to 13 HPa or less by depressurization for 30 seconds, the lamination treatment was carried out by pressing at 100 ° C and a pressure of 0.74 MPa for 30 seconds.

Thereafter, the mixture was placed in an oven at 100 ° C for 100 minutes at a temperature of 100 ° C, and was moved to an oven at 175 ° C for 30 minutes at a temperature of 175 ° C. Then, the substrate was taken out at room temperature, and the release PET (support) was peeled off from the resin sheet with the support, and then the resin sheet (the first and second resin composition layers) was further cured at 200 ° C for 90 minutes. Heat hardened.

After the heat curing, the polyimide film was peeled off and the tape was peeled off (removed) from the glass cloth substrate epoxy double-sided copper-clad laminate. Further, the release PET film ("501010" manufactured by Linke Co., Ltd.) of the laminated resin sheet was further peeled off to obtain a sheet-like cured product. The obtained cured product was cut into a test piece having a width of 5 mm and a length of 15 mm, and a thermomechanical analysis device ("Thermo Plus TMA8310" manufactured by Rigaku Corporation) was used. Thermomechanical analysis was carried out by a tensile load method. Specifically, after the test piece was attached to the thermomechanical analyzer, the measurement was continuously performed twice under the measurement conditions of a load of 1 g and a temperature increase rate of 5 ° C/min. and. In the second measurement, the average linear thermal expansion coefficient (ppm/° C.) in the plane direction in the range of 30° C. to 150° C. was determined, and the results are shown in Table 2.

<evaluation test> 1. Evaluation of the embeddability of parts

Using the resin sheet with the support produced in the examples and the comparative examples, the component was temporarily mounted on the circuit board in the following procedure to evaluate the component embeddability.

(1) Preparation of the part temporary circuit board (cavity substrate)

The glass cloth substrate BT resin double-sided copper-clad laminate (the thickness of the copper foil is 18 μm, the substrate thickness is 0.15 mm, and the "HL832NSF LCA" manufactured by Mitsubishi Gas Chemical Co., Ltd.) 255 * 340 mm of the entire surface is 0.7 x at a pitch of 3 mm. 1.1mm cavity. Then, the copper surface was roughened by etching on both sides with a microetching agent ("CZ8100" manufactured by MEC Co., Ltd.) at 1 μm, and further subjected to rustproof treatment ("CL8300" manufactured by MEC Co., Ltd.), and then 180 ° C. Dry for 30 minutes.

(2) Production of parts temporary circuit board

A 25 μm thick adhesive was dispensed on one side of the substrate obtained in (1) using a batch type vacuum pressure laminator (a two-stage assembly laminator "CVP700" manufactured by Ritalia Co., Ltd.). Imine film (polyimine 38 The μm thick and "PFDKE-1525TT" manufactured by Azawa Seisakusho Co., Ltd. are arranged such that the adhesive system is connected to the substrate and laminated on one side. The pressure was set to 13 HPa or less by depressurizing for 30 seconds, and then laminated at 80 ° C and a pressure of 0.74 MPa for 30 seconds. Then, the ceramic capacitor component (1005=1*0.5 mm size and thickness 0.14 mm) was temporarily laminated in one cavity in the cavity to prepare a component temporary circuit board 1 (cavity substrate) (see FIG. 1D).

(3) Evaluation test of the embeddability of parts

The resin sheet peeling protective film from the support body prepared by laminating the examples and the comparative examples was laminated using a batch type vacuum pressure laminator (a two-stage assembly laminator "CVP700" manufactured by Ritalia Co., Ltd.) The exposed second resin composition layer and the surface of the polyimine film disposed with the adhesive attached to the circuit board (cavity substrate) of the component (2) are connected to each other (see FIG. 3A). . After depressurizing for 30 seconds and setting the gas pressure to 13 HPa or less, the laminate was pressed at 100 ° C and a pressure of 0.74 MPa for 30 seconds. Then, the laminated resin sheet was subjected to hot pressing at 100 ° C and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure to be smoothed. The evaluation substrate A (see FIG. 3B) was produced by peeling off the adhesive agent polyimine film from the parts cooled to room temperature. The resin flow (10 cavities) in the cavity was observed from the surface of the evaluation substrate A by peeling off the polyimide film (150 times), and the embedability of the parts was evaluated according to the following criteria. Table 2 shows the results. Judged as

○: The outer peripheral portion of the laminated ceramic capacitor component is laminated to all the cavities Covered with resin.

X: Even if there is a cavity, there is a possibility that the void is generated or the outer peripheral portion of the laminated ceramic capacitor component is not insertable.

2. Evaluation of the amount of bending (1) Hardening of resin sheets

The evaluation substrate A prepared in 1. (3) was placed in an oven at 100 ° C under a temperature condition of 100 ° C, and then heat-treated for 30 minutes, and after cooling to room temperature, the surface of the adhesive polyimide polyimide film was peeled off. The same succeeding sheet is bonded to the same conditions as in 1. (3) (see FIGS. 3D and 3E). Thereafter, it was placed in an oven at 100 ° C for 30 minutes at a temperature of 100 ° C, and then moved to an oven at 175 ° C for 30 minutes at a temperature of 175 ° C to thermally harden to form an insulating layer on both sides of the substrate (refer to the figure). 3F). Thereafter, the substrate on which the insulating layer was formed on both sides was taken out at room temperature, and the release PET on both sides was peeled off, and the resin sheet was further thermally cured by a curing condition of 90 minutes after the input into an oven at 200 ° C for 90 minutes to prepare a built-in board. As the evaluation substrate B (refer to FIG. 3G).

(2) Evaluation test of bending amount

After the evaluation substrate B was cut into individual pieces of a 45 mm square shape (n=5), the reflow soldering apparatus of the reflow soldering temperature at a peak temperature of 260 ° C was once passed ("HAS-6116" manufactured by Aidome Co., Ltd., Japan) (The reflow temperature curve is based on IPC/JEDEC J-STD-020C). Then, use a shadow moiré device ("Ther Moire AXP" by Akrometrix), according to IPC/JEDEC J- The reflow soldering temperature profile of STD-020C (peak temperature: 260 ° C) was heated under the substrate, and the displacement (μm) of the 10 mm square portion in the center of the substrate was measured. The results are shown in Table 2.

In addition, in the table 2, the thickness of the first and second resin composition layers of the resin sheet with the support of the examples and the comparative examples, and the type of the resin varnish used for forming each resin composition layer, The coating method of each resin composition, the minimum melt viscosity of the first and second resin composition layers (single layer), the lowest melt viscosity of the resin sheet (two layers), and the average thermal expansion coefficient of the cured layer.

10‧‧‧Resin sheet with the first support

11‧‧‧Support

12‧‧‧Resin sheet

13‧‧‧1st resin composition layer

14‧‧‧Second resin composition layer

Claims (14)

A resin sheet with a support, comprising a support sheet and a resin sheet with a support of a resin sheet provided on the support, wherein the resin sheet has a first resin composition layer provided on the support side and is disposed on and The second resin composition layer formed of the second resin composition having a different composition from the first resin composition forming the first resin composition layer on the opposite side, the minimum melt viscosity of the resin sheet is 6000 poise or less. The average linear thermal expansion coefficient of the cured product layer obtained by curing the resin sheet from 25 ° C to 150 ° C is 17 ppm / ° C or less, and the lowest melt viscosity of the resin sheet is 6000 poise or less, and the resin sheet is hardened. The average linear thermal expansion coefficient of the cured layer from 25 ° C to 150 ° C is 17 ppm / ° C or less. The resin sheet of the support of claim 1, wherein the thickness of the resin sheet is 30 μm or less. The resin sheet of the support according to claim 1, wherein the thickness of the second resin composition layer is 25 μm or less. The resin sheet of the support of claim 1, wherein the second resin composition contains an inorganic filler, and the content of the inorganic filler when the nonvolatile component in the second resin composition is 100% by mass is 70% by mass. the above. The resin sheet of the support according to claim 1, wherein the lowest melt viscosity of the second resin composition layer is lower than the lowest melt viscosity of the first resin composition layer. The resin sheet with the support of claim 1 is used for Cavity. The resin sheet of the support according to claim 1, wherein the first resin composition and the second resin composition each contain an inorganic filler, and the average particle diameter of the inorganic filler in the first resin composition is D1 (μm). When the average particle diameter of the inorganic filler in the second resin composition is D2 (μm), D1 and D2 satisfy the relationship of D1 ≦ D2. The resin sheet of the support of claim 7, wherein the average particle diameter D1 (μm) of the inorganic filler in the first resin composition and the average particle diameter D2 (μm) of the inorganic filler in the second resin composition It satisfies the relationship of D1≦0.5≦D2. The resin sheet of the support of claim 1, wherein the second resin composition comprises an inorganic filler and a liquid epoxy resin. In the resin sheet with a support of claim 9, wherein the inorganic filler contains 100 parts by mass, the liquid epoxy resin is contained in an amount of 5 parts by mass or more. A method for manufacturing a component-embedded circuit board, comprising: (A) a circuit board including a first and second main faces, forming a cavity penetrating between the first and second main faces, and a temporary material connected to the second main surface of the circuit board, and a part temporarily suspended by the temporary material in the cavity of the circuit board, and vacuum laminated on the circuit board of the temporary component as claimed in claim 1~ The first laminate step of connecting the second resin composition layer to the first main surface of the circuit board, and the resin sheet with the support of any one of 10; (B) a heat treatment step of heat-treating the circuit board on which the resin sheet of the support is laminated, and (C) peeling the temporary material from the second main surface of the circuit board, and then bringing the second resin sheet and the circuit The second main surface of the substrate is connected to each other, and the second lamination step of the resin sheet including the second support and the second support sheet connected to the second support and the second support is vacuum laminated, and (D) heat The step of curing the resin sheet and the second resin sheet of the resin sheet with the support described above. A method of manufacturing a component-embedded circuit board according to claim 11, wherein the thickness of the circuit substrate is 100 μm or more. The method of manufacturing a component-embedded circuit board according to claim 11, wherein the resin sheet with the second support is a resin sheet with a support according to any one of claims 1 to 10. A semiconductor device comprising a component-embedded circuit board manufactured by the method of claim 11.