JP6303320B2 - Manufacturing method of component mounting board - Google Patents

Description

  The present invention relates to a method for producing a component mounting board and a thermosetting resin composition useful for forming an insulating layer of the component mounting board.

  As a technique for manufacturing a multilayer printed circuit board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked on a core substrate is known. In the manufacturing method by the build-up method, the insulating layer is generally formed by curing a resin composition. As such a resin composition, it is known to use an epoxy resin composition (Patent Document 1).

  In recent years, when manufacturing multilayer printed circuit boards, there is a tendency to highly blend inorganic fillers such as silica particles in the resin composition in order to prevent cracks and circuit distortion due to differences in thermal expansion between the insulating layer and the conductor layer. (Patent Document 2).

JP 2007-254709 A JP 2010-202865 A

  While it is desired to further reduce the thickness of the multilayer printed board, the thickness of the core board and the insulating layer tends to be gradually reduced. However, due to the thinning of the core substrate and the insulating layer, the insulating layer is easily affected by heat shrinkage. When manufacturing the component mounting board by mounting the component on the board by the reflow process, the present inventors say that the warpage of the board is likely to be manifested due to the shrinkage of the insulating layer at a high temperature. I found a problem.

  Accordingly, an object of the present invention is to provide a method for manufacturing a component mounting board that is less likely to warp even after a high temperature of component mounting by a reflow process in order to cope with further thinning of the component mounting board. . Furthermore, the subject of this invention is providing the thermosetting resin composition suitable for insulating layer formation of a thin component mounting board | substrate.

  As a result of intensive studies in view of the above problems, the present inventors have determined that a thermosetting step of a thermosetting resin composition layer formed on an inner layer substrate in a thermosetting resin composition used for forming an insulating layer of a component mounting board. Paying attention to the shrinkage rate after the shrinkage, the shrinkage rate after the reflow process of the cured product layer (insulating layer) formed by thermosetting, and the difference between them, the shrinkage rate and the difference between these shrinkage rates are below a certain value. In this case, the present inventors have found that the warpage of the substrate after the reflow process is suppressed even in a thin substrate, thereby completing the present invention. That is, the present invention includes the following contents.

[1] A thermosetting process in which a thermosetting resin composition layer formed on an inner layer substrate is cured by heating to form a cured product layer, and a component is mounted on the substrate having the cured product layer by reflow. A shrinkage rate (S1) in the xy direction after the thermosetting process of the thermosetting resin composition layer is 0.35% or less, and the xy direction after the reflow process of the cured product layer. A shrinkage rate (S2) of 0.4% or less, and S1 and S2 satisfy the relationship of S2-S1 ≦ 0.08.
[2] The method according to [1], wherein the thermosetting resin composition contains an epoxy resin, a curing agent, and an inorganic filler.
[3] The method according to [2], comprising silica as an inorganic filler.
[4] The method according to [2], comprising silica doped with titanium as an inorganic filler.
[5] When the nonvolatile component in the thermosetting resin composition is 100% by mass, the content of the inorganic filler in the thermosetting resin composition is 40% by mass or more, [2] to [4] ] The method in any one.
[6] The method according to any one of [1] to [5], wherein the heating temperature in the thermosetting step is 120 ° C to 240 ° C.
[7] The method according to any one of [1] to [6], wherein the peak temperature in the reflow step is 210 ° C to 330 ° C.
[8] The method according to any one of [1] to [7], wherein the thermosetting resin composition layer is formed of a prepreg formed by impregnating a fiber base material with a thermosetting resin composition.
[9] The thermosetting resin composition layer is formed by laminating an adhesive film in which a thermosetting resin crude composition layer is formed on a carrier film on an inner layer substrate, [1] to [8] ] The method in any one.
[10] The thermosetting resin composition layer is formed by laminating a carrier-prepared prepreg formed on a carrier film by impregnating a fiber base material with a thermosetting resin composition on an inner layer substrate. The method according to any one of [1] to [8].
[11] The method according to any one of [1] to [10], wherein the cured product layer has a thickness of 3 to 200 μm.
[12] The method according to any one of [1] to [11], wherein the component is a semiconductor chip, an interposer, or a passive element.
[13] The method according to [12], wherein the component is a semiconductor chip.
[14] A thermosetting resin composition for forming an insulating layer,
The cured product of the thermosetting resin composition that was thermally cured under the condition that the shrinkage ratio (S1) in the xy direction after thermosetting was 0.35% or less was based on IPC / JEDEC J-STD-020C. The heat shrinkage rate (S2) in the xy direction after heating with the reflow temperature profile is 0.4% or less, and S1 and S2 satisfy the relationship of S2-S1 ≦ 0.08. Curable resin composition.
[15] The thermosetting resin composition according to [14], wherein the reflow peak temperature is 260 ° C.
[16] The thermosetting resin composition according to [15], wherein the thermosetting resin composition contains an epoxy resin, a curing agent, and an inorganic filler.
[17] The thermosetting resin composition according to [16], which contains silica as an inorganic filler.
[18] The thermosetting resin composition according to [16], including silica doped with titanium as an inorganic filler.
[19] When the nonvolatile component in the thermosetting resin composition is 100% by mass, the content of the inorganic filler in the thermosetting resin composition is 40% by mass or more, [16] to [18 ] The thermosetting resin composition in any one.
[20] A prepreg obtained by impregnating a fiber base material with the thermosetting resin composition according to any one of [15] to [19].
[21] A multilayer printed wiring board in which an insulating layer is formed of a cured product of the thermosetting resin composition according to any one of [15] to [19].
[22] A component mounting board in which an insulating layer is formed of a cured product of the thermosetting resin composition according to any one of [15] to [19].
[23] The component mounting board according to [22], wherein the component is a semiconductor chip, an interposer, or a passive element.
[24] The component mounting board according to [23], wherein the component is a semiconductor chip.

  ADVANTAGE OF THE INVENTION According to this invention, even after passing through the high temperature of component mounting by a reflow process, the manufacturing method of the component mounting board | substrate which does not produce the curvature of a board | substrate is provided. Furthermore, according to the present invention, a thermosetting resin composition suitable for forming an insulating layer on a thin component mounting board is provided. The present invention can be suitably used for manufacturing a thin component mounting board that is particularly prone to warping of the board.

FIG. 1 is a diagram showing names between points A, B, C, and D when calculating S1 and S2. FIG. 2 is a diagram illustrating a reflow temperature profile described in IPC / JEDEC J-STD-020C.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

  One embodiment of the present invention includes a thermosetting process in which a thermosetting resin composition layer formed on an inner layer substrate is heated and cured to form a cured product layer, and components are reflowed on the substrate having the cured product layer. A shrinkage rate (S1) in the xy direction after the thermosetting process of the thermosetting resin composition layer is 0.35% or less, and x after the reflow process of the cured product layer. The component mounting board manufacturing method is characterized in that a shrinkage rate (S2) in the -y direction is 0.4% or less, and S1 and S2 satisfy a relationship of S2-S1 ≦ 0.08.

<Thermosetting process>
The production method of the present invention includes a thermosetting process, and in the thermosetting process, the thermosetting resin composition layer formed on the inner layer substrate is cured by heating to form a cured product layer.

  The temperature of thermosetting may vary depending on the composition of the thermosetting resin composition used specifically, but is generally 120 ° C to 240 ° C from the viewpoint of shortening the curing time and the heat resistance balance of the substrate. Yes, 140-210 degreeC is preferable and 150-200 degreeC is more preferable.

  The “inner layer substrate” in the present invention is a substrate that is an intermediate product when manufacturing a printed circuit board such as a component-embedded substrate, and an insulating layer and / or a conductor layer is further formed on the inner layer substrate. A substrate that will form the inner layer. One side or both sides of the inner layer substrate may have circuit wiring that has been patterned. Examples of the substrate used for the inner layer substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and a coreless substrate.

  When the circuit wiring is provided on one or both sides of the substrate, the thickness of the circuit wiring is not particularly limited, but is preferably 70 μm or less, more preferably 30 μm or less, and further preferably from the viewpoint of thinning the layer. 20 μm or less. The lower limit of the thickness of the circuit wiring is not particularly limited, but is preferably 1 μm or more, more preferably 3 μm or more, and further preferably 5 μm or more.

  The line / space ratio of the circuit wiring is not particularly limited, but is preferably 200/200 μm or less, more preferably 100/100 μm or less, still more preferably 40/40 μm or less, and even more preferably to suppress the undulation on the surface of the cured body. It is 20/20 μm or less, particularly preferably 8/8 μm. The lower limit of the line / space ratio of the circuit wiring is not particularly limited, but is preferably 0.5 / 0.5 μm or more, more preferably 1/1 μm or more in order to satisfactorily fill the resin between the spaces.

  The thermosetting resin composition used for the thermosetting resin composition layer of the present invention is not particularly limited as long as the cured product has sufficient hardness and insulation as an insulating layer. For example, it is preferable to use a thermosetting resin composition containing an epoxy resin, a curing agent, and an inorganic filler.

(Epoxy resin)
The epoxy resin used in the present invention is not particularly limited, but is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol. Type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, Epoxy resin having butadiene structure, cycloaliphatic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy Shi resins, halogenated epoxy resins, dicyclopentadiene type epoxy resins. These may be used alone or in combination of two or more.

  Among these, bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy from the viewpoint of improving heat resistance, insulation reliability, and adhesion to metal foil. A resin, an anthracene type epoxy resin, an epoxy resin having a butadiene structure, and a dicyclopentadiene type epoxy resin are preferable. Specifically, for example, bisphenol A type epoxy resin (“Epicoat 828EL”, “YL980” manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (“jER806H”, “YL983U” manufactured by Mitsubishi Chemical Corporation), Bisphenol A type and bisphenol F type 1: 1 mixture (“ZX1059” manufactured by Nippon Steel Chemical Co., Ltd.), naphthalene type bifunctional epoxy resin (manufactured by DIC Corporation “HP4032”, “HP4032D”, “HP4032SS”) , “EXA4032SS”), naphthalene type tetrafunctional epoxy resin (“HP4700”, “HP4710” manufactured by DIC Corporation), naphthol type epoxy resin (“ESN-475V” manufactured by Tohto Kasei Co., Ltd.), epoxy having a butadiene structure Resin ("PB-3600" manufactured by Daicel Chemical Industries, Ltd.), biphenyl Epoxy resin (“NC3000H”, “NC3000L”, “NC3100” manufactured by Nippon Kayaku Co., Ltd., “YX4000”, “YX4000H”, “YX4000HK”, “YL6121”) manufactured by Mitsubishi Chemical Corporation), anthracene type Epoxy resin ("YX8800" manufactured by Mitsubishi Chemical Corporation), naphthylene ether type epoxy resin ("EXA-7310", "EXA-7311", "EXA-7311L", "EXA7311-G3" manufactured by DIC Corporation)) And dicyclopentadiene type epoxy resin (“HP-7200H” manufactured by DIC Corporation).

  Two or more epoxy resins may be used in combination, but it is preferable to contain an epoxy resin having two or more epoxy groups in one molecule. Among them, an aromatic epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C. (hereinafter referred to as “liquid epoxy resin”) and three or more epoxy groups in one molecule. And a solid aromatic epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20 ° C. is more preferable. In addition, the aromatic epoxy resin as used in the field of this invention means the epoxy resin which has an aromatic ring structure in the molecule | numerator. When using a liquid epoxy resin and a solid epoxy resin together as an epoxy resin, when using the resin composition in the form of an adhesive film, the resin composition has an appropriate flexibility and the cured product of the resin composition has an appropriate breaking strength. From the point of having, the blend ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 0.1 to 1: 2 by mass ratio, more preferably in the range of 1: 0.3 to 1: 1.8. The range of 1: 0.6 to 1: 1.5 is more preferable.

  As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, and naphthalene type epoxy resin are preferable, and bisphenol A type epoxy resin and naphthalene type epoxy resin are more preferable. You may use these 1 type or in combination of 2 or more types.

  Examples of solid epoxy resins include tetrafunctional naphthalene type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, biphenyl type epoxy resins, and naphthylene ether type epoxy resins. A tetrafunctional naphthalene type epoxy resin, a biphenyl type epoxy resin, and a naphthylene ether type epoxy resin are more preferable. You may use these 1 type or in combination of 2 or more types.

  In the resin composition suitable for the production method of the present invention, from the viewpoint of improving the mechanical strength and water resistance of the cured product of the resin composition, when the non-volatile component in the resin composition is 100% by mass, the epoxy resin The content of is preferably 3 to 35% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 45% by mass.

(Curing agent)
The curing agent used in the present invention is not particularly limited, but phenolic curing agent, naphthol curing agent, active ester curing agent, benzoxazine curing agent, cyanate ester curing agent, acid anhydride curing agent, etc. Of these, phenolic curing agents, naphtholic curing agents, and active ester curing agents are preferred. These may be used alone or in combination of two or more.

  The phenolic curing agent and the naphtholic curing agent are not particularly limited, and examples thereof include a phenolic curing agent having a novolac structure and a naphtholic curing agent having a novolac structure, such as a phenol novolac resin and a triazine skeleton-containing phenol novolak. Resins, naphthol novolak resins, naphthol aralkyl type resins, triazine skeleton-containing naphthol resins, and biphenyl aralkyl type phenol resins are preferred. Commercially available products include “MEH-7700”, “MEH-7810”, “MEH-7851”, “MEH7851-4H” (Maywa Kasei Co., Ltd.), “GPH” (Nippon Kasei) (Manufactured by Yakuhin Co., Ltd.), as naphthol novolak resin, “NHN”, “CBN” (manufactured by Nippon Kayaku Co., Ltd.), and as naphthol aralkyl type resin, “SN170”, “SN180”, “SN190”, “SN475” , “SN485”, “SN495”, “SN395”, “SN375” (manufactured by Toto Kasei Co., Ltd.), “TD2090” (manufactured by DIC Corporation) as a phenol novolak resin, phenol novolak resin “LA3018” containing a triazine skeleton, “LA7052”, “LA7054”, “LA1356” (manufactured by DIC Corporation), etc. It is. These may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule. A compound having two or more in the above is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, and m-cresol. P-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzene Triol, dicyclopentadiene type diphenol compound (polycyclopentadiene type diphenol compound), phenol novolac And the like. 1 type (s) or 2 or more types can be used for an active ester type hardening | curing agent. As the active ester curing agent, an active ester curing agent disclosed in JP-A-2004-277460 may be used, or a commercially available one may be used. Commercially available active ester curing agents include those containing a dicyclopentadiene-type diphenol condensation structure, acetylated phenol novolac, benzoylation of phenol novolac, etc. Among them, dicyclopentadiene type diphenol condensation structure is preferred. The inclusion is more preferable. Specifically, EXB9451, EXB9460, EXB9460S-65T, HPC8000-65T (manufactured by DIC Corporation, active group equivalent of about 223) as a compound containing a dicyclopentadiene type diphenol condensation structure, and DC808 (as an acetylated product of phenol novolak) Mitsubishi Chemical Corp., active group equivalent of about 149), phenol novolac benzoylated as YLH1026 (Mitsubishi Chemical Corporation, active group equivalent of about 200), YLH1030 (Mitsubishi Chemical Corporation, active group equivalent of about 201) ), YLH1048 (manufactured by Mitsubishi Chemical Co., Ltd., active group equivalent: about 245), and the like. Among them, HPC-8000-65T is preferable from the viewpoint of storage stability of varnish and thermal expansion coefficient of the cured product.

  More specifically, examples of the active ester curing agent containing a dicyclopentadiene type diphenol condensation structure include compounds represented by the following formula.

(In the formula, R is a phenyl group or a naphthyl group, k represents 0 or 1, and n is 0.05 to 2.5 on the average of repeating units.)

  From the viewpoint of reducing the dielectric loss tangent and improving the heat resistance, R is preferably a naphthyl group, while k is preferably 0 and n is preferably 0.25 to 1.5.

  Although there is no restriction | limiting in particular as a benzoxazine type hardening | curing agent, As a specific example, Fa, Pd (made by Shikoku Kasei Co., Ltd.), HFB2006M (made by Showa Polymer Co., Ltd.), etc. are mentioned.

  The cyanate ester-based curing agent is not particularly limited. For example, novolak type (phenol novolac type, alkylphenol novolak type, etc.) cyanate ester-based curing agent, dicyclopentadiene type cyanate ester-based curing agent, bisphenol type (bisphenol A type) , Bisphenol F type, bisphenol S type, etc.) cyanate ester-based curing agents, and prepolymers in which these are partially triazines. Although the weight average molecular weight of a cyanate ester hardening | curing agent is not specifically limited, 500-4500 are preferable and 600-3000 are more preferable. Specific examples of the cyanate ester-based curing agent include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), and 4,4′-methylenebis (2,6-dimethylphenyl cyanate). 4,4′-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3) , 5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether, etc. Resin, phenol novolac Cresol novolac, a polyfunctional cyanate resins derived from dicyclopentadiene structure-containing phenol resin, these cyanate resins and partially triazine of prepolymer. These may be used alone or in combination of two or more.

  As a commercially available cyanate ester resin, a phenol novolac type polyfunctional cyanate ester resin represented by the following formula (Lonza Japan Co., Ltd., PT30S, cyanate equivalent 124)

[In formula, n shows arbitrary numbers (preferably 0-20) as an average value. ]
A prepolymer in which a part or all of bisphenol A dicyanate represented by the following formula is triazine-modified into a trimer (Lonza Japan Co., Ltd., BA230, cyanate equivalent 232)

Dicyclopentadiene structure-containing cyanate ester resin represented by the following formula (Lonza Japan Co., Ltd., DT-4000, DT-7000)

(In formula, n represents the number of 0-5 as an average value.)

Etc.

  The acid anhydride curing agent is not particularly limited, and examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylnadic acid. Anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2 -Dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3 ' -4,4'-diphenylsulfonetetracarboxylic dianhydride, 1 3,3a, 4,5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione, ethylene glycol bis (anhydro) Trimellitate), and polymer-type acid anhydrides such as styrene / maleic acid resin obtained by copolymerization of styrene and maleic acid.

  In the thermosetting resin composition, from the viewpoint of improving the mechanical strength and water resistance of the cured product of the resin composition, (A) the total number of epoxy groups of the epoxy resin and (B) the reactive groups of the curing agent. The ratio with respect to the total number is preferably 1: 0.2 to 1: 2, more preferably 1: 0.3 to 1: 1.5, and still more preferably 1: 0.4 to 1: 1. The total number of epoxy groups of the epoxy resin present in the resin composition is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the reactive group of the curing agent. The total number of is a value obtained by adding the values obtained by dividing the solid mass of each curing agent by the reactive group equivalent for all curing agents.

  In the said resin composition, from the viewpoint of improving the mechanical strength and water resistance of the hardened | cured material of a resin composition, when the non-volatile component in a resin composition is 100 mass%, content of a hardening | curing agent is 3-30. The content is preferably mass%, more preferably 5 to 25 mass%, and still more preferably 10 to 20 mass%.

(Inorganic filler)
The thermosetting resin composition of the present invention preferably contains an inorganic filler from the viewpoint of lowering the coefficient of thermal expansion. The inorganic filler to be used is not particularly limited. For example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, boron Examples include aluminum oxide, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Of these, silica is preferable. Silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, spherical silica, silica doped with titanium, and the like are preferable. Further, the silica is preferably spherical. Examples of the spherical silica include “SOC1” and “SOC2” manufactured by Admatechs Co., Ltd. The inorganic filler may be used alone or in combination of two or more. In the present invention, the coefficient of thermal expansion can be adjusted by adjusting the type and amount of components contained in the thermosetting resin composition. In particular, the inorganic filler greatly contributes to the low thermal expansion of the thermosetting resin composition. Therefore, the coefficient of thermal expansion can be suitably adjusted by adjusting the type and amount of the inorganic filler. Further, since silica doped with titanium tends to have a particularly low thermal expansion among inorganic fillers, it can be particularly suitably used for preparing the value of the coefficient of thermal expansion in the present invention.

“Titanium-doped silica” refers to, for example, TiCl ₄ and SiCl ₄ , which are glass forming raw materials of TiO ₂ —SiO ₂ glass, which are gasified and mixed, and then heated and hydrolyzed in an oxyhydrogen flame ( TiO ₂ —SiO ₂ glass particles obtained by flame hydrolysis). Silica doped with titanium is known, and examples of commercially available products include “AZ filler” manufactured by Asahi Glass Co., Ltd. When compounding silica doped with titanium into the inorganic filler, the amount of inorganic filler contained in the resin composition is 100% by mass, and the amount of silica doped with titanium in the inorganic filler is 10% by mass. % Or more, preferably 20% by weight or more, more preferably 30% by weight or more, more preferably 40% by weight or more, more preferably 50% by weight or more, more preferably 60% by weight or more, and 70% by weight. % Or more is more preferable, 80 mass% or more is more preferable, 90 mass% or more is more preferable, and 100 mass% is particularly preferable.

  Inorganic fillers include silane coupling agents (epoxysilane coupling agents, aminosilane coupling agents, mercaptosilane coupling agents, etc.) and titanate coupling agents to improve moisture resistance and dispersibility. Those that have been surface treated with a surface treating agent such as a silazane compound are preferred. You may use these 1 type or in combination of 2 or more types.

  Examples of the epoxysilane coupling agent include glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, and (3,4-epoxycyclohexyl). Examples include aminotrimethoxysilane, aminopropylmethoxysilane, aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2 (aminoethyl) amino. Examples of the mercaptosilane coupling agent include mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane. You may use these 1 type or in combination of 2 or more types. Examples of commercially available coupling agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. ), “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

  The average particle diameter of the inorganic filler is not particularly limited, but the upper limit of the average particle diameter of the inorganic filler is preferably 5 μm or less from the viewpoint of forming fine wiring on the insulating layer, and 3 μm or less. Is more preferably 1 μm or less, still more preferably 0.7 μm or less, particularly preferably 0.5 μm or less, particularly preferably 0.4 μm or less, and particularly preferably 0.3 μm or less. On the other hand, the lower limit of the average particle size of the inorganic filler is set to 0. 0 from the viewpoint of preventing the viscosity of the varnish from increasing and handling properties from being lowered when the epoxy resin composition is used as a resin composition varnish. 01 μm or more is preferable, 0.03 μm or more is more preferable, 0.05 μm or more is further preferable, 0.07 μm or more is particularly preferable, and 0.1 μm or more is particularly preferable. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction type particle size distribution measuring apparatus, LA-500, 750, 950, etc. manufactured by Horiba, Ltd. can be used.

  The content in the case of blending the inorganic filler is preferably 40% by mass or more, and 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of lowering the thermal expansion coefficient. More preferably, 60% by mass is even more preferable. When there is too little content of an inorganic filler, it exists in the tendency for the thermal expansion coefficient of hardened | cured material to become high. If the content of the inorganic filler is too large, the cured product tends to become brittle or the peel strength tends to decrease. Therefore, the maximum content of the inorganic filler is 90% by mass or less, preferably 85% by mass or less. Is preferred.

  The resin composition of the present invention may further contain other components (for example, additives such as thermoplastic resins, curing accelerators, flame retardants).

-Thermoplastic resin-
Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyethersulfone resin, and polysulfone resin. A thermoplastic resin may be used individually by 1 type, or may use 2 or more types together.

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

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, or may use 2 or more types together. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). In addition, “FX280” and “FX293” manufactured by Toto Kasei Co., Ltd., “YL7553”, “YL6794”, “YL7213” manufactured by Mitsubishi Chemical Corporation, YL7290 "," YL7482 ", etc. are mentioned.

  Specific examples of the polyvinyl acetal resin include: Electric Butyral 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., S-Lec BH Series, BX Series manufactured by Sekisui Chemical Co., Ltd. KS series, BL series, BM series, etc. are mentioned.

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (described in JP-A No. 2002-12667 and JP-A No. 2000-319386).

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

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

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

  When content of the non-volatile component in a resin composition is 100%, it is preferable that content of the thermoplastic resin in a resin composition is 0.1 mass%-20 mass%. By setting the content of the thermoplastic resin within such a range, the viscosity of the resin composition becomes appropriate, and a uniform resin composition having a thickness and a bulk property can be formed. As for content of the thermoplastic resin in a resin composition, when the non-volatile component in a resin composition is 100 mass%, it is more preferable that it is 1 mass%-10 mass%.

-Curing accelerator-
Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like. A hardening accelerator and a metal type hardening accelerator are preferable.

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

  Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo [ 5.4.0] -undecene and the like, and 4-dimethylaminopyridine and 1,8-diazabicyclo [5.4.0] -undecene are preferable.

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

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  Although it does not specifically limit as a metal type hardening accelerator, For example, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used alone or in combination of two or more.

  In the resin composition of the present invention, it is preferable to use an organic cobalt complex as the metal curing accelerator, and it is particularly preferable to use cobalt (III) acetylacetonate. The content of the metal-based curing accelerator is preferably such that the metal content based on the metal-based curing catalyst is in the range of 25 ppm to 500 ppm when the nonvolatile component in the resin composition is 100% by mass. More preferably, it is the range.

  A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type. The content of the curing accelerator in the resin composition is preferably 0.01% by mass to 1% by mass, and 0.02% by mass to 0.5% by mass when the nonvolatile component in the resin composition is 100% by mass. % Is more preferable, and 0.03% by mass to 0.1% by mass is even more preferable.

-Flame retardant-
Examples of the flame retardant include organic phosphorus flame retardant, organic nitrogen-containing phosphorus compound, nitrogen compound, silicone flame retardant, metal hydroxide and the like. 10- (2,5-dihydroxyphenyl) -10- Hydro-9-oxa-10-phosphaphenanthrene-10-oxide (for example, “HCA-HQ” manufactured by Sanko Co., Ltd.) is preferable. A flame retardant may be used individually by 1 type, or may use 2 or more types together. The content of the flame retardant in the resin composition layer is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, 0.5% by mass to 10% by mass is preferable, and 1% by mass to 5%. % By mass is more preferable, and 1.5% by mass to 3% by mass is still more preferable.

<Reflow process>
The manufacturing method of the present invention includes a reflow process, and in the reflow process, components are mounted by reflow on a substrate having a cured product layer manufactured by the thermosetting process.
The component to be mounted is not particularly limited and includes, for example, a semiconductor, an interposer, a passive element, and the like. The manufacturing method of the present invention can be particularly preferably used for mounting a semiconductor.
The heating temperature in the reflow process may vary depending on conditions such as the type of solder used and the type of component to be mounted, but is generally 210 ° C to 330 ° C, preferably 220 ° C to 300 ° C, more preferably 230 ° C to 280 ° C. preferable. The manufacturing method of the present invention is more suitable when a lead-free solder is used as the solder.

The production method of the present invention includes the thermosetting step and the reflow step.
In the component mounting board manufacturing method of the present invention, the shrinkage rate (S1) in the xy direction after the thermosetting process of the thermosetting resin composition layer is higher than that of the thermosetting resin composition layer before the thermosetting process. 0.35% or less, preferably 0.3% or less, more preferably 0.2% or less, and the shrinkage rate (S2) in the xy direction of the cured product layer after the reflow process is the thermosetting process. Compared to the previous thermosetting resin composition layer, 0.4% or less, preferably 0.3% or less, more preferably 0.2% or less, and S1 and S2 are S2-S1 ≦ 0. 08, preferably S2-S1 ≦ 0.05, more preferably S2-S1 ≦ 0.04.

  The measurement of S1 and S2 is performed as follows.

<Measurement of S1>
(1-1) Measurement of initial length Four through-holes are formed by punching in a portion of the thermosetting resin composition layer (thickness 40 μm) of about 200 mm square resin from 4 mm to 20 mm. Tentatively referred to as A, B, C, and D.), length L between the centers of the formed holes (L _AB , L _BC , L _CD , L _DA , L _AC , L _BD ) (see FIG. 1) Is measured with a non-contact type image measuring device.

(1-2) Thermosetting of thermosetting resin composition layer The thermosetting resin composition layer whose length has been measured is heated and thermoset.

(1-3) Measurement of thermosetting shrinkage ratio After thermosetting, in the cured thermoplastic resin composition layer, the length L ′ (L ′) after curing between the centers of the holes formed in (1-1). _AB , L ′ _BC , L ′ _CD , L ′ _DA , L ′ _AC , L ′ _BD ) are measured with a non-contact type image measuring device in the same manner as L.
s1 _AB = (L _AB -L ' _AB ) / L _AB
Is calculated. Similarly, s1 _BC , s1 _CD , s1 _DA , s1 _AC , s1 _DA are converted into L _BC and L ' _BC , L _CD and L' _CD , L _DA and L ' _DA , L _AC and L' _AC , L _BD. And L ′ _BD .
The thermosetting shrinkage is calculated by the following formula.
Thermosetting shrinkage [shrinkage in xy direction: S1] (%)
= {(S1 _AB + s1 _BC + s1 _CD + s1 _DA + s1 _AC + s1 _DA ) / 6} × 100

<Measurement of S2>
(1-4) Reflow process The substrate after the process of (1-3) is reflowed.

(1-5) Measurement of Reflow Shrinkage Ratio After the reflow step, the length L ″ (L ” _AB after reflow between the centers of the holes formed in (1-1) is performed in the same manner as (1-3). , L ″ _BC , L ″ _CD , L ″ _DA , L ″ _AC , and L ″ _BD ) are measured with a non-contact image measuring device in the same manner as L.
s2 _AB = (L _AB -L " _AB ) / L _AB
Is calculated. _{Similarly, s2 BC, s2 CD, s2} DA, s2 AC, the _{s2 DA, L BC} and _{L "BC, L CD} and _{L" CD, L DA} and _{L "DA, L AC} and _{L" AC, L BD} And L " _BD .
The reflow shrinkage rate is calculated by the following formula.
Reflow shrinkage [shrinkage in xy direction: S2] (%)
_{= {(S2 AB + s2 BC} + s2 CD + s2 DA + s2 AC + s2 DA) / 6} × 100

  The above parameters can preferably be satisfied by using a thermosetting resin composition containing an epoxy resin, a curing agent and an inorganic filler as described above. According to such a thermosetting resin composition, the hardened | cured material suitable for the insulating layer which the shrinkage | contraction of an insulating layer was suppressed and the curvature was suppressed and the board | substrate distortion hardly arises can be obtained. The cured product of the thermosetting resin composition is suitable for manufacturing a component mounting substrate (particularly a semiconductor mounting substrate), and particularly suitable for forming an insulating layer of the substrate. The thickness of one cured product layer (one insulating layer) is usually about 3 to 200 μm, but when multilayered, the thickness of the entire insulating layer is thicker than this, usually about 10 to 300 μm. Become.

<Thermosetting resin composition>
One embodiment of the present invention provides a thermosetting resin composition for forming an insulating layer.
In the thermosetting resin composition, a cured product of the thermosetting resin composition that has been thermoset under the condition that the shrinkage rate (S1) in the xy direction after thermosetting is 0.35% or less is IPC / Relationship of shrinkage (S2) in the xy direction after heating with a reflow temperature profile according to JEDEC J-STD-020C is 0.4% or less, and S1 and S2 are S2-S1 ≦ 0.08 It satisfies.

  The cured product of the thermosetting resin composition that was thermally cured under the condition that the shrinkage ratio (S1) in the xy direction after thermosetting was 0.35% or less was based on IPC / JEDEC J-STD-020C. If the shrinkage (S2) in the xy direction after heating with the reflow temperature profile is 0.4% or less and S1 and S2 satisfy the relationship of S2-S1 ≦ 0.08, the thermoplasticity The resin composition is less likely to warp the substrate even after the high temperature of component mounting in the reflow process, and is suitable for forming an insulating layer on a thin component mounting substrate.

The suitable example of the raw material which can be used for a thermoplastic resin composition is as having mentioned above.
The measuring method of S1 and S2 is as described above.

The reflow temperature profile described in IPC / JEDEC J-STD-020C is cited in FIG. For the time, any condition within the range described in the table may be used. For example, for Sn—Pb eutectic solder, ts = 90 seconds, t _L = 105 seconds, tp = 20 seconds, and for Pb-free solder, ts. = 120 seconds, t _L = 105 seconds, and tp = 30 seconds. In the present invention, the package here corresponds to a substrate before component mounting by reflow. The package thickness is preferably less than 2.5 mm for Sn—Pb eutectic solder, less than 2.5 mm for Pb-free solder, more preferably less than 2.5 mm to 1.6 mm, and less than 1.6 mm. Is even more preferred.

  The said thermosetting resin composition can be used conveniently as a resin composition (resin composition for insulating layers on an inner layer board | substrate) for forming the insulating layer of a multilayer printed wiring board. By forming the insulating layer of the multilayer printed wiring board using the thermosetting resin composition, it is possible to realize an insulating layer in which shrinkage of the insulating layer is suppressed and the substrate is less likely to be distorted. The problem can be improved significantly. Among them, in the production of multilayer printed wiring boards by the build-up method, it can be suitably used as a resin composition for forming an insulating layer (resin composition for build-up insulating layers of multilayer printed wiring boards). It can be more suitably used as a resin composition for forming an insulating layer in which a conductor layer is formed by plating (a resin composition for a build-up insulating layer of a multilayer printed wiring board in which a conductor layer is formed by plating). . Moreover, the said thermosetting resin composition can be used conveniently also when a multilayer printed wiring board is a component built-in circuit board. That is, the resin composition of the present invention can be suitably used as a resin composition for embedding components on a component-embedded circuit board (resin composition for embedding components). The core substrate used for manufacturing the component built-in circuit board has a cavity for incorporating the component, and the cavity density tends to increase due to a demand for miniaturization of the component built-in circuit board itself. The problem of warping due to insufficient rigidity of the steel tends to become more serious, but by using the thermosetting resin composition as a resin composition for embedding parts, a core substrate having a high cavity density and a thin thickness is used. Even in this case, the problem of warping can be relieved remarkably.

<Prepreg>
The said thermosetting resin composition is good also as a prepreg by impregnating a sheet-like fiber base material. The prepreg is obtained by impregnating the thermosetting resin composition in a sheet-like fiber base material.

The sheet-like fiber base material used for a prepreg is not specifically limited, What is used normally as base materials for prepregs, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, can be used. When used for forming an insulating layer of a multilayer printed wiring board, a thin sheet-like fiber substrate having a thickness of 50 μm or less is preferably used, and particularly a sheet-like fiber substrate having a thickness of 10 μm to 40 μm is preferable. A sheet-like fiber substrate of 10 μm to 30 μm is more preferable, and a sheet-like fiber substrate of 10 to 20 μm is more preferable. Specific examples of the glass cloth base material used as the sheet-like fiber base material include “Style 1027MS” (warp density 75/25 mm, weft density 75/25 mm, fabric weight 20 g / m ² ) manufactured by Asahi Schwer Corporation. , Thickness 19 μm), “Style 1037MS” manufactured by Asahi Schubel Co., Ltd. (warp density 70/25 mm, weft density 73/25 mm, fabric weight 24 g / m ² , thickness 28 μm), manufactured by Arisawa Manufacturing Co., Ltd. "1078" (warp density 54 / 25mm, weft density 54 / 25mm, fabric weight 48g / m ² , thickness 43μm), "1037NS" manufactured by Arizawa Seisakusho (warp density 72 / 25mm, weft Density 69/25 mm, fabric weight 23 g / m ² , thickness 21 μm), “1027NS” manufactured by Arisawa Manufacturing Co., Ltd. (warp density 75/25 mm, weft density 7 5/25 mm, fabric weight 19.5 g / m ² , thickness 16 μm), “1015NS” manufactured by Arisawa Manufacturing Co., Ltd. (warp density 95/25 mm, weft density 95/25 mm, fabric weight 17.5 g / m ² , thickness 15 μm), “1000NS” manufactured by Arisawa Manufacturing Co., Ltd. (warp density 85/25 mm, weft density 85/25 mm, fabric weight 11 g / m ² , thickness 10 μm), and the like. Specific examples of the liquid crystal polymer nonwoven fabric include “Veculus” (weight per unit area: 6 to 15 g / m ² ) and “Vectran” manufactured by Kuraray Co., Ltd., which are produced by the melt blow method of an aromatic polyester nonwoven fabric.

  The prepreg may be produced by a known method such as a hot melt method or a solvent method.

  In one embodiment of the present invention, a thermosetting resin composition layer is obtained by laminating a carrier-prepared prepreg with a carrier formed by impregnating a fiber base material with the thermosetting resin composition onto an inner layer substrate. The component mounting board formed in this way is preferable.

<Multilayer printed wiring board using prepreg>
Next, an example of a method for producing a multilayer printed wiring board using the prepreg produced as described above will be described. One or several prepregs of the present invention are stacked on a circuit board, sandwiched between metal plates through a release film, and vacuum press laminated under pressure and heating conditions. The pressurizing / heating conditions are preferably a pressure of 5 to 40 kgf / cm ² (49 × 10 ^{4 to} 392 × 10 ⁴ N / m ² ) and a temperature of 120 to 200 ° C. for 20 to 100 minutes. Similarly to the adhesive film, the prepreg can be laminated on a circuit board by a vacuum laminating method and then cured by heating. Thereafter, in the same manner as described above, the surface of the cured prepreg is roughened, and then a conductor layer is formed by plating to produce a multilayer printed wiring board.

<Adhesive film>
An adhesive film can be formed using the thermosetting resin composition.

  In one embodiment, the adhesive film of the present invention includes a support and a resin composition layer bonded to the support, and the resin composition layer is made of the thermosetting resin composition.

  The adhesive film is prepared, for example, by preparing a resin varnish obtained by dissolving the thermosetting resin composition in an organic solvent, applying the resin varnish on a support using a die coater, and drying the resin varnish. Can be formed.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (hereinafter also referred to as “MEK”) and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, Examples thereof include carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, or may use 2 or more types together.

  The resin varnish may be dried by a known drying method such as heating or hot air blowing. Depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the adhesive film is dried at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes. Can be formed.

  Examples of the support used for forming the adhesive film include a film made of a plastic material, a metal foil (copper foil, aluminum foil, etc.), and release paper. A film made of a plastic material is preferably used. Examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”), polycarbonate (hereinafter referred to as “PC”). And acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, and the like. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable. In a preferred embodiment, the support is a polyethylene terephthalate film.

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

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. .

  In the present invention, a commercially available product may be used as the support with a release layer. Commercially available products include, for example, “SK-1”, “AL-5”, and “AL-7” manufactured by Lintec Corporation, which are PET films having a release layer mainly composed of an alkyd resin release agent. Or the like.

  Although the thickness of a support body is not specifically limited, Preferably it is 5 micrometers-75 micrometers, More preferably, it is 10 micrometers-60 micrometers. In addition, when a support body is a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  As described above, in the adhesive film manufactured using the thermosetting resin composition, the thickness of the resin composition layer is not particularly limited, but is preferably 100 μm or less from the viewpoint of thinning the multilayer printed wiring board. More preferably, it is 80 micrometers or less, More preferably, it is 60 micrometers or less, More preferably, it is 50 micrometers or less. The lower limit of the thickness of the resin composition layer is usually 15 μm or more.

  In the adhesive film manufactured using the thermosetting resin composition as described above, the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support) is supported. A protective film according to the body can be further laminated. Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can be wound and stored in a roll shape, and can be used by peeling off the protective film when forming an insulating layer in the production of a multilayer printed wiring board.

  In one embodiment of the present invention, a component mounting board in which the thermosetting resin composition layer is formed by laminating an adhesive film in which a thermosetting resin crude composition layer is formed on a carrier film on an inner layer board is preferable. .

<Multilayer printed wiring board using adhesive film>
An example of a method for producing a multilayer printed wiring board using the adhesive film produced as described above will be described.

  First, an adhesive film is laminated on one side or both sides of a circuit board using a vacuum laminator. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Also, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, one of the outermost layers of the multilayer printed wiring board is a conductor layer (circuit) in which one or both sides are patterned. It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

In the above laminate, when the adhesive film has a protective film, after removing the protective film, the adhesive film and the circuit board are preheated as necessary, and the adhesive film is pressed and heated to the circuit board. Crimp. In the adhesive film of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used. Lamination conditions are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., and the pressure bonding pressure is preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107). 9.9 × 10 ⁴ N / m ² ), and lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using a roll. The vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho Co., Ltd., a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.

Moreover, the lamination process which heats and pressurizes under reduced pressure can also be performed using a general vacuum hot press machine. For example, it can be performed by pressing a metal plate such as a heated SUS plate from the support layer side. The pressing condition is that the degree of vacuum is usually 1 × 10 ⁻² MPa or less, preferably 1 × 10 ⁻³ MPa or less. Although heating and pressurization can be carried out in one stage, it is preferable to carry out the conditions separately in two or more stages from the viewpoint of controlling the oozing of the resin. For example, the first stage press has a temperature of 70 to 150 ° C. and the pressure is in a range of 1 to 15 kgf / cm ² , and the second stage press has a temperature of 150 to 200 ° C. and a pressure of 1 to 40 kgf / cm ² It is preferable to carry out within a range. The time for each stage is preferably 30 to 120 minutes. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho Co., Ltd.), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

  It is preferable that the thermosetting resin composition layer is formed by laminating an adhesive film in which a thermosetting resin crude composition layer is formed on a carrier film to an inner layer substrate. After laminating the adhesive film on the circuit board, it is cooled to around room temperature, and when the support is peeled off, the insulating film can be formed on the circuit board by peeling and thermosetting. The thermosetting conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. to 210 ° C. It is selected in the range of 30 to 120 minutes at ° C.

  If the support is not peeled off after the insulating layer is formed, it is peeled off here. Next, if necessary, holes are formed in the insulating layer formed on the circuit board to form via holes and through holes. Drilling can be performed, for example, by a known method such as drilling, laser, or plasma, or by combining these methods as necessary. However, drilling by a laser such as a carbon dioxide gas laser or a YAG laser is the most common method. is there.

  Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. In the case of wet plating, the surface of the insulating layer is subjected to a swelling treatment with a swelling solution, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution in this order to form an uneven anchor. The swelling treatment with the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 to 80 ° C. for 5 to 20 minutes. Examples of the swelling liquid include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securigans P (Swelling Dip Securigans SBU) and Swelling Dip Securigans SBU manufactured by Atotech Japan Co., Ltd. be able to. The roughening treatment with an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 ° C. to 80 ° C. for 10 minutes to 30 minutes. Examples of the oxidizing agent include alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. it can. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by weight. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan. Neutralization treatment with a neutralizing solution is performed by immersing in a neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes. As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, Reduction Solution / Secligant P manufactured by Atotech Japan Co., Ltd. may be mentioned.

  Next, a conductor layer is formed by combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. As a subsequent pattern formation method, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.

By using the multilayer printed wiring board manufactured using the thermosetting resin composition, a substrate on which components such as a semiconductor chip, an interposer, and a passive element are mounted can be manufactured.
An example of the manufacturing method of a semiconductor mounting substrate is shown.

<Semiconductor mounting substrate>
A semiconductor mounting board can be manufactured by mounting a semiconductor chip in the conduction | electrical_connection part of the multilayer printed wiring board manufactured using the said thermosetting resin composition. The “conduction location” is a “location where an electrical signal is transmitted in a multilayer printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor mounting substrate is not particularly limited as long as the semiconductor chip functions effectively. Specifically, the wire bonding mounting method, the flip chip mounting method, and the bumpless build are used. Examples thereof include a mounting method using an up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In the following description, “part” means “part by mass”.

  First, measurement methods and evaluation methods in the physical property evaluation in this specification will be described.

(Measurement of shrinkage rate)
(1-1) Preparation of polyimide film with resin The resin sheet (200 mm square) produced in the following production example was used using a batch-type vacuum pressurization laminator (manufactured by Nichigo Morton 2-stage buildup laminator CVP700). Lamination was performed on one side so that the resin composition layer was in contact with the center of the smooth surface of the polyimide film (Upilex 25S, 25 μm thickness, 240 mm square, manufactured by Ube Industries, Ltd.). Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing the film at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(1-2) Measurement of initial length The obtained polyimide film with resin is punched from the support of the resin sheet into a portion of about 4 mm to 20 mm of 200 mm square resin by punching a through hole (diameter of about 6 mm). Four holes are formed (the holes are tentatively referred to as A, B, C, and D in the clockwise direction), and the length L between the centers of the formed holes (L _AB , L _BC , L _CD , L _DA , L _AC , L _BD ) (see FIG. 1) was measured with a non-contact image measuring device (manufactured by Mitutoyo Corporation, Quick Vision model: QVH1X606-PRO III_BHU2G).

(1-3) Thermosetting of resin composition layer A polyimide film surface of a polyimide film with a resin whose length has been measured is a glass cloth base epoxy resin double-sided copper-clad laminate (0.7 mm thickness, Matsushita) of 255 mm × 255 mm size. Installed on "R5715ES" manufactured by Denko Co., Ltd.), fixed on the four sides with a polyimide adhesive tape (width 10 mm), heated at 150 ° C for 90 minutes to thermally cure the resin composition layer, Obtained. Similarly, it heated at 190 degreeC for 90 minutes and 200 degreeC for 90 minutes, and obtained the hardened | cured material layer, respectively.

(1-4) Measurement of thermosetting shrinkage rate After thermosetting, the polyimide adhesive tape is peeled off, the polyimide film with a cured product layer is removed from the laminate, and the cured product layer is further removed from the polyimide film. The length L ′ (L ′ _AB , L ′ _BC , L ′ _CD , L ′ _DA , L ′ _AC , L ′ _BD ) after curing between the centers of the holes formed in the above is non-contact like L Measured with a mold image measuring instrument.
s1 _AB = (L _AB -L ' _AB ) / L _AB
Was calculated. Similarly, s1 _BC , s1 _CD , s1 _DA , s1 _AC , s1 _DA are converted into L _BC and L ' _BC , L _CD and L' _CD , L _DA and L ' _DA , L _AC and L' _AC , L _BD. And L ′ _BD .
The thermosetting shrinkage was calculated by the following formula.
Thermosetting shrinkage [shrinkage in xy direction: S1] (%)
= {(S1 _AB + s1 _BC + s1 _CD + s1 _DA + s1 _AC + s1 _DA ) / 6} × 100

(1-5) Reflow process The base material in which the process of (1-3) is completed is a reflow apparatus having a peak temperature of 260 ° C. -Compliant with -020C).

(1-6) Measurement of Reflow Shrinkage Ratio After the reflow process, the length L ″ (L ” _AB after reflow between the centers of the holes formed in (1-2) is performed in the same manner as (1-4). , L ″ _BC , L ″ _CD , L ″ _DA , L ″ _AC , and L ″ _BD ) were measured with a non-contact image measuring device in the same manner as L.
s2 _AB = (L _AB -L " _AB ) / L _AB
Was calculated. _{Similarly, s2 BC, s2 CD, s2} DA, s2 AC, the _{s2 DA, L BC} and _{L "BC, L CD} and _{L" CD, L DA} and _{L "DA, L AC} and _{L" AC, L BD} And L " _BD .
The reflow shrinkage was calculated by the following formula.
Reflow shrinkage [shrinkage in xy direction: S2] (%)
_{= {(S2 AB + s2 BC} + s2 CD + s2 DA + s2 AC + s2 DA) / 6} × 100

[Preparation of substrate for evaluation of reflow behavior]
(2-1) Preparation of Inner Layer Substrate As the inner layer substrate, glass cloth base epoxy resin laminated plate [copper foil etched-out unclad plate, 0.06 mm thickness, “LaXY-4785TH-B” manufactured by Sumitomo Bakelite Co., Ltd. ] Was prepared.

(2-2) Lamination of resin sheet Using a batch type vacuum pressure laminator (manufactured by Nichigo Morton Co., Ltd., 2-stage buildup laminator CVP700), the resin composition layer is an inner layer. Lamination was performed on both sides of the inner layer substrate so as to be in contact with the substrate. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing the film at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. Next, hot pressing was performed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds.

(2-3) Thermosetting of resin composition layer After peeling the support of the resin sheet from the substrate on which the resin sheet was laminated, the resin composition layer was thermally cured by heating at 150 ° C for 90 minutes, A cured product layer was obtained. Similarly, it heated at 190 degreeC for 90 minutes and 200 degreeC for 90 minutes, and obtained the hardened | cured material layer, respectively.

(2-4) Evaluation of reflow behavior After cutting into 45 mm square pieces (n = 5), the sample was passed once through a reflow apparatus (“HAS-6116” manufactured by Nippon Antom Co., Ltd.) having a peak temperature of 260 ° C. Conditions also conform to IPC / JEDEC J-STD-020C). Next, using a shadow moire device (Thermoire AXP manufactured by Akrometrix), the substrate is heated from the bottom of the substrate with a temperature profile conforming to IPC / JEDEC J-STD-020C (peak temperature 260 ° C.), and warpage of the 10 mm square portion at the center of the substrate The behavior was measured.
The difference between the maximum height and the minimum height of the obtained displacement data was evaluated as “x” when even one sample was 40 μm or more in all temperature ranges, and “less than 40 μm” in all samples.

  Resin sheets 1, 2, 3, and 4 used in Examples and Comparative Examples were prepared by the following procedure.

<Production Example 1 (Production of Resin Sheet 1)>
12 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation "828EL", epoxy equivalent of about 185), 3 parts of naphthalene type epoxy resin (DIC Corporation "HP4032SS", epoxy equivalent of about 144), biphenyl type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent of about 185) 6 parts, biphenyl type epoxy resin (Nippon Kayaku "NC3000H", epoxy equivalent of about 288) 25 parts, phenoxy resin (Mitsubishi Chemical Corporation ) “YX6954BH30”, MEK / cyclohexanone = 1/1 solution having a solid content of 30% by mass) was dissolved in 15 parts of solvent naphtha with stirring. After cooling to room temperature, 20 parts of a triazine skeleton-containing phenol novolac curing agent (“LA-7054” manufactured by DIC Corporation, MEK solution having a hydroxyl equivalent of 125 and a solid content of 60%), a naphthol curing agent ( "SN485" manufactured by Nippon Steel Chemical Co., Ltd., 10 parts of a hydroxyl equivalent 215, 60% solid content MEK solution), curing accelerator (4-dimethylaminopyridine (DMAP), 5% solid content MEK solution) 0 .4 parts flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average Spherical silica (average particle size of 0.25 μm, Admate Corporation) surface-treated with 3 parts of an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) "SOC1" manufactured by Ax, 40 parts of carbon per unit surface area 0.36mg / m ² , spherical glass filler (average particle size) surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) A resin varnish 1 was prepared by mixing 10 parts of a 0.2 μm diameter, “AZ filler” manufactured by Asahi Glass Co., Ltd., and a carbon amount of 0.38 mg / m ² per unit surface area, and uniformly dispersing with a high-speed rotary mixer. .
Next, on the release layer side of the PET film with an alkyd resin release layer (“AL5” manufactured by Lintec Corporation, thickness 38 μm), the resin varnish is so formed that the thickness of the resin composition layer after drying is 40 μm. 1 was applied uniformly and dried at 80 to 120 ° C. (average 100 ° C.) for 5 minutes to prepare a resin sheet 1.

<Production Example 2 (Production of Resin Sheet 2)>
Bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent of about 169), 5 parts, biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Corporation) "YX4000HK", epoxy equivalent of about 185) 12 parts, dicyclopentadiene type epoxy resin (DIC Corporation "HP-7200H", epoxy equivalent of about 275) 9 parts, phenoxy resin (Mitsubishi Chemical Corporation "YL7553BH30") 16 parts of MEK / cyclohexanone = 1/1 solution having a solid content of 30% by mass was dissolved in 30 parts of solvent naphtha with stirring. After cooling to room temperature, 40 parts of an active ester curing agent (“HPC8000-65T” manufactured by DIC Corporation, a toluene solution having an active group equivalent of about 223 and a nonvolatile content of 65% by mass), a curing accelerator (4 -3 parts of dimethylaminopyridine, MEK solution having a solid content of 5% by mass), spherical silica (average particle size of 0.5 μm, (Sheetetsu Chemical Industry Co., Ltd. “KBM573”) surface-treated with an aminosilane-based coupling agent ( Spherical glass filler surface-treated with “SOC2” manufactured by Admatechs Co., Ltd., 100 parts of carbon amount per unit surface area 0.39 mg / m ² , aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle size 0.2 [mu] m, manufactured by Asahi Glass Co., Ltd. "AZ filler", carbon content 0.38 mg ^/ m 2 per unit surface area) 40 parts were mixed, high-speed Uniformly dispersed in the rolling mixer to prepare a resin varnish 2.
Subsequently, the resin sheet 2 was produced in the same procedure as in Production Example 1 using the resin varnish 2.

<Production Example 3 (Production of Resin Sheet 3)>
6 parts of naphthalene type epoxy resin (DIC Corporation "HP4032SS", epoxy equivalent of about 144), biphenyl type resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent of about 185), biphenyl type epoxy resin (Japan) 20 parts of “NC3000H” manufactured by Kayaku Co., Ltd., about 288 epoxy equivalent, and 8 parts of phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK solution with a solid content of 30% by mass) are stirred into 15 parts of solvent naphtha. The solution was dissolved while heating. After cooling to room temperature, 20 parts of a prepolymer of bisphenol A dicyanate (“BA230S75” manufactured by Lonza Japan Co., Ltd., MEK solution having a cyanate equivalent of about 232 and a nonvolatile content of 75% by mass), a phenol novolac type polyfunctional cyanate Ester resin (Lonza Japan Co., Ltd. “PT30S”, cyanate equivalent of about 133, MEK solution with non-volatile content of 85% by mass), active ester hardener (DIC Corporation “HPC8000-65T”, active group equivalent About 223 non-volatile content 65% by weight toluene solution) 8 parts, curing accelerator (4-dimethylaminopyridine, solid content 5% by weight MEK solution) 0.4 parts, curing accelerator (manufactured by Tokyo Chemical Industry Co., Ltd.) 3 parts of cobalt (III) acetylacetonate, MEK solution having a solid content of 1% by mass, flame retardant (“HC” manufactured by Sanko Co., Ltd.) -HQ ", 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm), 3 parts, aminosilane coupling agent (Shin-Etsu 50 parts of spherical silica (average particle size 0.5 μm, “SOC2” manufactured by Admatechs Co., Ltd., carbon amount 0.39 mg / m ² per unit surface area) surface-treated with “KBM573” manufactured by Chemical Industry Co., Ltd. , Spherical glass filler (average particle size 0.2 μm, “AZ filler” manufactured by Asahi Glass Co., Ltd.) surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), carbon amount per unit surface area 0.38 mg / m ² ) was mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish 3.
Subsequently, the resin sheet 3 was produced in the same procedure as in Production Example 1 using the resin varnish 3.

<Production Example 4 (Production of Resin Sheet 4)>
12 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation "828EL", epoxy equivalent of about 185), 3 parts of naphthalene type epoxy resin (DIC Corporation "HP4032SS", epoxy equivalent of about 144), biphenyl type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent of about 185) 6 parts, biphenyl type epoxy resin (Nippon Kayaku "NC3000H", epoxy equivalent of about 288) 25 parts, phenoxy resin (Mitsubishi Chemical Corporation ) 20 parts of “YX6954BH30”, MEK / cyclohexanone = 1/1 solution having a solid content of 30% by mass) was dissolved in 10 parts of solvent naphtha with stirring. After cooling to room temperature, 20 parts of a triazine skeleton-containing phenol novolac curing agent (“LA-7054” manufactured by DIC Corporation, MEK solution having a hydroxyl equivalent of 125 and a solid content of 60%), a naphthol curing agent ( "SN485" manufactured by Nippon Steel Chemical Co., Ltd., 10 parts of a hydroxyl equivalent 215, 60% solid content MEK solution), curing accelerator (4-dimethylaminopyridine (DMAP), 5% solid content MEK solution) 0 .4 parts flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average Spherical silica (average particle size of 0.25 μm, Admate Corporation) surface-treated with 3 parts of an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) “SOC1” manufactured by OX, 40 parts of carbon per unit surface area 0.36 mg / m ² ) were mixed and dispersed uniformly with a high-speed rotary mixer to prepare resin varnish 4.
Subsequently, the resin sheet 4 was produced in the same procedure as in Production Example 1 using the resin varnish 4.

<Production Example 5 (Production of Resin Sheet 5)>
6 parts of naphthalene type epoxy resin (DIC Corporation "HP4032SS", epoxy equivalent of about 144), biphenyl type resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent of about 185), biphenyl type epoxy resin (Japan) 20 parts of “NC3000H” manufactured by Kayaku Co., Ltd., about 288 epoxy equivalent, 16 parts of phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Co., Ltd., MEK solution having a solid content of 30% by mass) are stirred into 5 parts of solvent naphtha. The solution was dissolved while heating. After cooling to room temperature, 20 parts of a prepolymer of bisphenol A dicyanate (“BA230S75” manufactured by Lonza Japan Co., Ltd., MEK solution having a cyanate equivalent of about 232 and a nonvolatile content of 75% by mass), a phenol novolac type polyfunctional cyanate Ester resin (Lonza Japan Co., Ltd. “PT30S”, cyanate equivalent of about 133, MEK solution with non-volatile content of 85% by mass), active ester hardener (DIC Corporation “HPC8000-65T”, active group equivalent About 223 non-volatile content 65% by weight toluene solution) 8 parts, curing accelerator (4-dimethylaminopyridine, solid content 5% by weight MEK solution) 0.4 parts, curing accelerator (manufactured by Tokyo Chemical Industry Co., Ltd.) 3 parts of cobalt (III) acetylacetonate, MEK solution having a solid content of 1% by mass, flame retardant (“HC” manufactured by Sanko Co., Ltd.) -HQ ", 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm), 3 parts, aminosilane coupling agent (Shin-Etsu 40 parts of spherical silica (average particle size 0.25 μm, “SOC1” manufactured by Admatechs Co., Ltd., carbon amount 0.36 mg / m ² per unit surface area) surface-treated with “KBM573” manufactured by Chemical Industry Co., Ltd. Were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish 5.
Subsequently, the resin sheet 5 was produced in the same procedure as in Production Example 1 using the resin varnish 5.

  Table 4 shows the composition of the resin composition layers of the resin sheets 1 to 5.

  The evaluation results are shown in Table 5.

  As is apparent from the results in Table 2, even when the same resin sheet 1 is used, when the temperature of the thermosetting process is 190 ° C. (Test Example 1) × 90 minutes, a composition satisfying the provisions of the present invention is obtained. On the other hand, in the case of 150 ° C. (Test Example 5) × 90 minutes, a composition satisfying the provisions of the present invention was not obtained. Moreover, even if the same resin sheet 2 is used, when the temperature of the thermosetting process is 200 ° C. (Test Example 2) × 90 minutes, a composition satisfying the provisions of the present invention is obtained, whereas 150 In the case of C (Test Example 6) x 90 minutes, a composition satisfying the provisions of the present invention was not obtained.

  Although the resin sheet 1 and the resin sheet 4 have similar compositions, the test example 1 provides a composition satisfying the provisions of the AZ filler according to the present invention despite the same thermosetting process. In the case of Test Example 4, a composition satisfying the definition of the present invention has not been obtained.

  Although the resin sheet 3 and the resin sheet 5 have similar compositions, the resin sheet 3 (Test Example 3) can be obtained as a composition satisfying the provisions of the present invention, regardless of the same thermosetting process. On the other hand, in the case of the resin sheet 5 (Test Example 7), a composition satisfying the definition of the present invention was not obtained. Moreover, in the case of the resin sheet 5, even if it changed the temperature of the thermosetting process, the composition which satisfy | fills the prescription | regulation of this invention was not obtained (Test Example 8).

Claims (21)

Thermosetting resin composition layer formed on the inner layer substrate (excluding prepregs in which the thermosetting resin composition is impregnated into the fiber base) is heat-cured to form a cured product layer. A shrinkage rate (S1) in the xy direction after the thermosetting process of the thermosetting resin composition layer is 0. .35% or less, the shrinkage rate (S2) in the xy direction after the reflow process of the cured product layer is 0.4% or less, and S1 and S2 satisfy the relationship of S2-S1 ≦ 0.08. A method for manufacturing a component mounting board, wherein:   The method of Claim 1 in which a thermosetting resin composition contains an epoxy resin, a hardening | curing agent, and an inorganic filler.   The method of Claim 2 which contains a silica as an inorganic filler.   The method according to claim 2, comprising silica doped with titanium as an inorganic filler.   The content of the inorganic filler in a thermosetting resin composition is 40 mass% or more, when the non-volatile component in a thermosetting resin composition is 100 mass%, Any one of Claims 2-4 The method described in 1.   The method of any one of Claims 1-5 whose heating temperature in a thermosetting process is 120 to 240 degreeC.   The method of any one of Claims 1-6 whose peak temperature in a reflow process is 210 to 330 degreeC. The thermosetting resin composition layer is formed by laminating an adhesive film in which a thermosetting resin composition layer is formed on a carrier film to an inner layer substrate, according to any one of claims 1 to 7. The method described. The method according to any one of claims 1 to 8 , wherein the thickness of the cured product layer is 3 to 200 µm. Component is a semiconductor chip, an interposer, or a passive device, method according to any one of claims 1-9. The method of claim 10 , wherein the component is a semiconductor chip. A thermosetting resin composition for forming an insulating layer (excluding a heat-cured prepreg formed by impregnating a fiber base material with a thermosetting resin composition),
The cured product of the thermosetting resin composition that was thermally cured under the condition that the shrinkage ratio (S1) in the xy direction after thermosetting was 0.35% or less was based on IPC / JEDEC J-STD-020C. The heat shrinkage rate (S2) in the xy direction after heating with the reflow temperature profile is 0.4% or less, and S1 and S2 satisfy the relationship of S2-S1 ≦ 0.08. Curable resin composition. Peak temperature of reflow is 260 ° C., according to claim 1 2 thermosetting resin composition. Thermosetting resin composition, an epoxy resin, a curing agent and an inorganic filler, according to claim 12 or 1 3 thermosetting resin composition. Comprising silica as an inorganic filler, according to claim 1 4 thermosetting resin composition. Titanium as the inorganic filler comprises a doped silica, according to claim 1 4 thermosetting resin composition. If the non-volatile components of the thermosetting resin composition is 100 mass%, the content of the inorganic filler in the thermosetting resin composition is 40 mass% or more, in any one of claims 1 4-16 1 The thermosetting resin composition according to item. Claim 1 by 2-1 7 cured thermosetting resin composition according to any one insulating layer is formed, the multilayer printed wiring board. The cured product of claim 1 2-1 7 thermosetting resin composition according to any one being insulating layer is formed, the component mounting board. The component mounting board according to claim 19 , wherein the component is a semiconductor chip, an interposer, or a passive element. 21. The component mounting board according to claim 20 , wherein the component is a semiconductor chip.