TW201518024A - Manufacturing process of component mounting substrate - Google Patents

Abstract

The present invention provides a manufacturing process of component mounting substrate, which can suppress the warpage of a substrate even after going through the component mounting at a high temperature by a reflow process to correspond to new thinning of the component mounting substrate, and to a thermosetting resin composition suitable for formation of an insulating layer of a thin component mounting substrate. The feature of the manufacturing process of component mounting substrate of the present invention comprises the following steps: a thermal curing process of forming a cured layer by heating and curing a thermosetting resin composition layer formed on an internal layer substrate; and a reflow process of mounting a component on the substrate having the cured layer by reflow, wherein the shrinkage rate (S1) in the x-y direction after the thermal curing process of the thermosetting resin composition layer is 0.35% or smaller, the shrinkage rate (S2) in the x-y direction after the reflow process of the cured layer is 0.4% or smaller, and S1 and S2 satisfies the relation: S2 - S1 ≤ 0.08, and the thermosetting resin composition of the present invention is a thermosetting resin composition for formation of an insulating layer, whose feature is that the shrinkage rate (S2) in the x-y direction after heating a cured thermosetting resin composition, which is thermally cured under the condition that the shrinkage rate (S1) in the x-y direction after thermal curing is 0.35% or smaller, at a reflow temperature profile based on IPC/JEDEC J-STD-020C is 0.4% or smaller, and S1 and S2 satisfies the relation: S2 - S1 ≤ 0.08.

Description

Method for manufacturing component mounting substrate

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

A manufacturing method of a multilayer printed substrate is known to be advantageous in a method of forming a layered layer in which an insulating layer and a conductor layer are alternately overlapped on a core substrate. In the production method using the build-up method, generally, the insulating layer is formed by curing the resin composition. An epoxy resin composition is known as the resin composition (Patent Document 1).

In recent years, in order to prevent cracking or circuit deformation caused by the difference in thermal expansion between the insulating layer and the conductor layer, a large amount of inorganic filler such as cerium oxide particles tends to be formulated in a resin composition (Patent Document) 2).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-254709

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-202865

In the multilayer printed substrate, it is desired to further reduce the thickness of the core substrate or the insulating layer. However, due to the thinning of the core substrate or the insulating layer, the insulating layer is susceptible to heat shrinkage. When the inventors of the present invention manufactured the component mounting substrate by mounting the component on the substrate by the reflow step, it was found that the thin substrate was particularly likely to be warped due to shrinkage of the insulating layer at a high temperature.

Accordingly, the problem of the present invention is to provide a method of manufacturing a component mounting substrate which is less likely to cause warpage of the substrate even after the high temperature of the component mounted by the reflow step is applied, in order to further reduce the thickness of the component mounting substrate. Further, an object of the present invention is to provide a thermosetting resin composition suitable for forming an insulating layer of a thin component mounting substrate.

In the thermosetting resin composition used for forming the insulating layer of the component mounting substrate, the inventors of the present invention have been focusing on the above-mentioned problems, and have focused on the thermosetting resin composition layer formed on the inner substrate. The shrinkage ratio after the step, the shrinkage ratio after the reflow step of the cured layer (insulating layer) formed by thermal hardening, and the difference between the above, and the difference between the shrinkage ratios and the shrinkage ratios are found to be constant values. In the following, even if the thin substrate can suppress the warpage of the substrate after the reflow step, the present invention has been completed. That is, the present invention includes the following contents.

[1] A method of manufacturing a component mounting substrate, comprising the steps of: heat-hardening a thermosetting resin composition layer formed on an inner layer substrate, forming a hardening step of the cured layer, and utilizing reflow a reflowing step of mounting a component on a substrate having the cured layer; and a shrinkage ratio (S1) in the xy direction after the thermosetting step of the thermosetting resin composition layer is 0.35% or less, and reflowing of the cured layer The shrinkage ratio (S2) in the xy direction after the step is 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], which comprises cerium oxide as an inorganic filler.

[4] The method according to [2], which comprises titanium-doped cerium oxide as an inorganic filler.

[5] The method according to any one of [2] to [4] wherein, when the nonvolatile component in the thermosetting resin composition is 100% by mass, the inorganic component in the thermosetting resin composition The content of the filler is 40% by mass or more.

[6] The method according to any one of [1] to [5] wherein the heating temperature in the thermosetting step is from 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 impregnated with a fiber base by a thermosetting resin composition Formed from a prepreg formed in the material.

[9] The method according to any one of [1] to [8] wherein the thermosetting resin composition layer is laminated on the inner substrate and then formed by a film formed on the carrier film. It is made of a layer of a thermosetting resin coarse composition.

[10] The method according to any one of [1] to [8] wherein the thermosetting resin composition layer is formed by laminating a prepreg to the carrier on the inner substrate, and the carrier is pretreated In the impregnation system, a prepreg obtained by impregnating a fibrous substrate with a thermosetting resin composition is formed on a carrier film.

[11] The method according to any one of [1] to [10] wherein the thickness of the cured layer is from 3 to 200 μm.

[12] The method according to any one of [1] to [11] wherein the component is a semiconductor wafer, an interposer or a passive component.

[13] The method of [12], wherein the part is a semiconductor wafer.

[14] A thermosetting resin composition which is a thermosetting resin composition for forming an insulating layer, which is characterized in that the shrinkage ratio (S1) in the xy direction after heat curing is 0.35% or less The cured product of the thermosetting resin composition which is thermally hardened has a shrinkage ratio (S2) of 0.4% or less in the xy direction after heating according to the reflow temperature distribution of IPC/JEDEC J-STD-020C, and S1 and S2 satisfy S2. -S1≦0.08 relationship.

[15] The thermosetting resin composition according to [14], wherein the peak temperature of the reflow is 260 °C.

[16] The thermosetting resin composition as described in [15], wherein the thermosetting resin The chemical resin composition contains an epoxy resin, a hardener, and an inorganic filler.

[17] The thermosetting resin composition according to [16], which comprises cerium oxide as an inorganic filler.

[18] The thermosetting resin composition according to [16], which contains titanium-doped cerium oxide as an inorganic filler.

[19] The thermosetting resin composition according to any one of [16], wherein the thermosetting resin is a non-volatile component in the thermosetting resin composition of 100% by mass. The content of the inorganic filler in the composition is 40% by mass or more.

[20] A prepreg obtained by impregnating a thermosetting resin composition according to any one of [15] to [19] into a fibrous base material.

[21] A multilayer printed wiring board obtained by forming an insulating layer of a cured product of the thermosetting resin composition according to any one of [15] to [19].

[22] A component mounting substrate obtained by forming an insulating layer of a cured product of the thermosetting resin composition according to any one of [15] to [19].

[23] The component mounting substrate as recited in [22], wherein the component is a semiconductor wafer, an interposer, or a passive component.

[24] The component mounting substrate according to [23], wherein the component is a semiconductor wafer.

According to the present invention, it is provided that even if it is subjected to a reflow step After the high temperature of the component mounting, it is also difficult to produce a method of manufacturing the component mounting substrate in which the substrate warps. Further, according to the present invention, there is provided a thermosetting resin composition suitable for forming an insulating layer of a thin component mounting substrate. The present invention is particularly suitably used for the manufacture of a thin component mounting substrate which is prone to warpage of the substrate.

Fig. 1 is a diagram showing the names between points A, B, C, and D when S1 and S2 are calculated.

Fig. 2 is a view showing the reflow temperature distribution described in IPC/JEDEC J-STD-020C.

Hereinafter, the present invention will be described in detail based on preferred embodiments of the present invention.

An embodiment of the present invention provides a method of manufacturing a component mounting substrate, comprising the steps of thermally hardening a thermosetting resin composition layer formed on an inner layer substrate, forming a cured layer, and reflowing a reflowing step of mounting a component on a substrate having the cured layer, and a shrinkage ratio (S1) in the xy direction after the thermosetting step of the thermosetting resin composition layer is 0.35% or less, and reflowing of the cured layer The shrinkage ratio (S2) in the xy direction after the step is 0.4% or less, and S1 and S2 satisfy the relationship of S2-S1 ≦ 0.08.

<Thermal hardening step>

The manufacturing method of the present invention includes a thermosetting step of thermally curing the thermosetting resin composition layer formed on the inner layer substrate to form a cured layer.

The temperature of the heat curing may be different depending on the composition of the thermosetting resin composition to be used, but it is generally 120 ° C to 240 ° C, preferably 140, based on the viewpoint that the hardening time is shortened and the heat resistance of the substrate is balanced. °C~210°C, more preferably 150°C~200°C.

In the present invention, the "inner substrate" is a substrate which is an intermediate product when a printed circuit board such as a component built-in substrate is manufactured, and an insulating layer and/or a conductor layer are formed on the inner substrate, and constitute a printed circuit board. The substrate of the layer. One or both sides of the inner substrate may also have patterned circuit wiring. The substrate used for the inner layer substrate is exemplified by, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, a coreless substrate, or the like.

When the circuit wiring is provided on one surface or both surfaces of the substrate, the thickness of the circuit wiring is not particularly limited. However, from the viewpoint of thinning the layer, it is preferably 70 μm or less, more preferably 30 μm or less, and still more preferably 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 still more preferably 5 μm or more.

The line/space ratio of the circuit wiring is not particularly limited. However, in order to suppress the undulation of the surface of the hardened body, it 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 20/20 μm or less, preferably 8/8 μm. The lower limit of the line/space ratio of the circuit wiring is not particularly limited. However, in order to facilitate the embedding of the resin between the spaces, it is preferably 0.5/0.5 μm or more, more preferably 1/1 μm or more.

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 is used as an insulating layer and has sufficient hardness and insulation properties. For example, a thermosetting resin composition containing an epoxy resin, a curing agent, and an inorganic filler is preferably used.

(epoxy resin)

The epoxy resin used in the present invention is not particularly limited, and is exemplified by bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac varnish. Epoxy resin, t-butyl-catechol epoxy resin, naphthol epoxy resin, naphthalene epoxy resin, naphthalene ether epoxy resin, glycidylamine epoxy resin, cresol novolac Epoxy resin, biphenyl type epoxy resin, bismuth type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, A spiro ring-containing epoxy resin, a cyclohexanedimethanol type epoxy resin, a trimethylol type epoxy resin, a halogenated epoxy resin, a dicyclopentadiene type epoxy resin, or the like. These may be used alone or in combination of two or more.

Among these, bisphenol A type epoxy resin, naphthol type epoxy resin, drug type epoxy resin, and biphenyl type are used in view of improving heat resistance, improving insulation reliability, and improving adhesion to metal foil. Epoxy resin, naphthalene ether type epoxy resin, bismuth type epoxy resin, epoxy having butadiene structure A resin or a dicyclopentadiene type epoxy resin is preferred. Specifically, bisphenol A type epoxy resin ("EPICOTE 828EL" and "YL980" manufactured by Mitsubishi Chemical Corporation) and bisphenol F type epoxy resin ("jER 806H" manufactured by Mitsubishi Chemical Corporation) , "YL983U"), a 1:1 mixture of bisphenol A and bisphenol F ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd.), and a naphthalene type 2-functional epoxy resin (made by DIC) HP4032", "HP4032D", "HP4032SS", "EXA4032SS"), naphthalene type 4-functional epoxy resin ("HP4700", "HP4710" made by DIC), naphthol type epoxy resin (Dongdu Huacheng) "ESN-475V"), epoxy resin with butadiene structure ("PB-3600" manufactured by Daicel Chemical Industry Co., Ltd.), epoxy resin with biphenyl structure (Nippon Chemical Co., Ltd.) "NC3000H", "NC3000L", "NC3100", "YX4000", "YX4000H", "YX4000HK" and "YL6121" made by Mitsubishi Chemical Corporation, and 蒽-type epoxy resin (Mitsubishi Chemical Co., Ltd.) "YX8800"), naphthalene ether type epoxy resin ("EXA-7310", "EXA-7311", "EXA-7311L", "EXA-7311-G3" made by DIC), and dicyclopentylene Ethylene type epoxy resin ("DIC" P-7200H") and so on.

Epoxy resins may be used in combination of two or more kinds, but an epoxy resin having two or more epoxy groups in one molecule is preferred. In particular, it is more preferably an aromatic epoxy resin (hereinafter referred to as "liquid epoxy resin") having two or more epoxy groups in one molecule and liquid at a temperature of 20 ° C, and one molecule Three or more epoxy resins and aromatic epoxy resins (hereinafter referred to as "solid epoxy resins") which are solid at a temperature of 20 ° C state. Moreover, the aromatic epoxy resin in the present invention means an epoxy resin having an aromatic ring structure in its molecule. When a liquid epoxy resin and a solid epoxy resin are used as the epoxy resin, the resin composition is used in the form of a film, and the resin composition has moderate flexibility or a cured product of the resin composition has moderate burst strength. The blending ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1:0.1 to 1:2, more preferably in the range of 1:0.3 to 1:1.8, and more preferably in terms of mass ratio. 1:0.6~1:1.5 range.

As for the liquid epoxy resin, it is preferably a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, and a naphthalene type epoxy resin, more preferably a bisphenol A type epoxy resin. And naphthalene type epoxy resin. These may be used alone or in combination of two or more.

The solid epoxy resin is preferably a 4-functional naphthalene epoxy resin, a cresol novolak epoxy resin, a dicyclopentadiene epoxy resin, a trisphenol epoxy resin, a naphthol novolac epoxy resin. The biphenyl type epoxy resin or the naphthene ether type epoxy resin is more preferably a tetrafunctional naphthalene type epoxy resin, a biphenyl type epoxy resin or a naphthalene ether type epoxy resin. These may be used alone or in combination of two or more.

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

(hardener)

The curing agent to be used in the present invention is not particularly limited, and examples thereof include a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, a cyanate-based curing agent, and an acid anhydride-based curing agent. Among the agents, a phenolic curing agent, a naphthol curing agent, and an active ester curing agent are preferred. These may be used alone or in combination of two or more.

The phenolic curing agent and the naphthol-based curing agent are not particularly limited, and examples thereof include a phenolic curing agent having a novolac structure or a naphthol curing agent having a novolac structure, preferably a phenol novolac resin and a triazine-containing curing agent. Skeletal phenol novolak resin, naphthol novolak resin, naphthol aralkyl type resin, naphthol resin containing triazine skeleton, biphenyl aralkyl type phenol resin. The commercially available biphenyl aralkyl phenol resins are "MEH-7700", "MEH-7810", "MEH-7851", "MEH-7851-4H" (Mingwa Kasei Co., Ltd.), " GPH" (Nippon Chemical Co., Ltd.), naphthol novolac resin is "NHN", "CBN" (made by Nippon Kayaku Co., Ltd.), and naphthol aralkyl type resin is "SN170", " SN180", "SN190", "SN475", "SN485", "SN495", "SN395", "SN375" (made by Tohto Kasei Co., Ltd.), and phenol novolak resin is "TD2090" (DIC system) ), phenol novolac resin "LA3018", "LA7052", "LA7054", "LA1356" (made by DIC), etc. containing a triazine skeleton. These may be used alone or in combination of two or more.

The active ester-based curing agent is preferably one or more reactive in one molecule, such as a general phenolic ester, a thiophenolic ester, an N-hydroxylamine ester, or an ester of a heterocyclic hydroxy compound. High ester group Compound. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. Particularly, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Agent. The carboxylic acid compound is exemplified by, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. Phenolic compounds or naphthol compounds are exemplified by, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 , 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene diphenol compound (polycyclopentadiene type diphenol compound), phenol novolak, and the like. One or two or more kinds of the active ester-based curing agents can be used. As the active ester-based curing agent, an active ester-based curing agent disclosed in JP-A-2004-277460 may be used, and a commercially available one may also be used. The commercially available active ester-based curing agent is preferably a dicyclopentadiene-type diphenol condensation structure, an acetal of a phenol novolac, a benzamidine of a phenol novolac, and the like, and more preferably a dicyclopentane. Diene type diphenol condensation structure. Specifically, as a dicyclopentadiene-type diphenol condensation structure, it is exemplified as EXB9451, EXB9460, EXB9460S-65T, and HPC-8000-65T" (manufactured by DIC, having an active base equivalent of about 223) as a phenol novolac. The acetate of varnish is listed as DC808 (Mitsubishi Chemical Co., Ltd., active base) Approximately 149), the benzamidine compound as a phenol novolac is exemplified by YLH1026 (manufactured by Mitsubishi Chemical Corporation, active base equivalent of about 200), YLH1030 (manufactured by Mitsubishi Chemical Corporation, active base equivalent of about 201), and YLH1048 ( Mitsubishi Chemical Co., Ltd., active base equivalent of about 245), etc., based on the preservation stability of the paint and the thermal expansion rate of the cured product, HPC-8000-65T is preferred.

The active ester-based curing agent containing a dicyclopentadiene-type diphenol condensation structure is more specifically listed as a compound of the following formula.

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

From the viewpoint of lowering the dielectric tangent and improving the heat resistance, R is preferably a naphthyl group, and on the other hand, k is preferably 0, and n is preferably 0.25 to 1.5.

The benzoxazine-based curing agent is not particularly limited, and specific examples thereof include F-a, P-d (manufactured by Shikoku Chemicals Co., Ltd.), and HFB2006M (manufactured by Showa Polymer Co., Ltd.).

The cyanate-based curing agent is not particularly limited, and examples thereof include a novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanide. An acid ester curing agent, a dicyclopentadiene type cyanate curing agent, a bisphenol type (bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate type curing agent, and the like Partially triazineated prepolymers and the like. The weight average molecular weight of the cyanate-based curing agent is not particularly limited, but is preferably from 500 to 4,500, more preferably from 600 to 3,000. Specific examples of the cyanate-based curing agent are, for example, bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene)), 4, 4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl 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-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl) sulfide, bis(4-cyanate) a bifunctional cyanate resin such as an ester phenyl) ether, a polyfunctional cyanate resin derived from a phenol novolak, a cresol novolak, a phenol resin having a dicyclopentadiene structure, or the like, and the cyanate ester A part of the resin is subjected to a triazine-based prepolymer or the like. These may be used alone or in combination of two or more.

The commercially available cyanate resin is a phenol novolac type polyfunctional cyanate resin (PT30S, cyanate equivalent 124 manufactured by LONZA Co., Ltd.) represented by the following formula or the like.

[In the formula, n is an average value and represents an arbitrary number (preferably 0 to 20)].

a prepolymer of a triazine-formed trimer which is a part or all of a bisphenol A dicyanate represented by the following formula (BA230, cyanate equivalent 232, manufactured by LONZA Co., Ltd., Japan)

The cyanate resin containing a dicyclopentadiene structure (DT-4000, DT-7000, manufactured by LONZA Co., Ltd.) is represented by the following formula.

(where n is the average value, indicating the number of 0 to 5).

The acid anhydride-based curing agent is not particularly limited, and examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydroorthophenylene. Dicarboxylic anhydride, nadic acid anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dicarboxylate Acid tetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, biphenyltetracarboxylic acid Anhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,3,3a,4,5,9b - hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride), Styrene copolymerized with styrene and maleic acid. A polymer type acid anhydride such as a maleic acid resin.

In the thermosetting resin composition, (A) the total number of epoxy groups of the epoxy resin and the total of the reactive groups of the (B) hardener are based on the viewpoint of improving the mechanical strength or water resistance of the cured product of the resin composition. The ratio of the number is preferably 1:0.2 to 1:2, more preferably 1:0.3 to 1:1.5, and even more preferably 1:0.4 to 1:1. The epoxy group count of the epoxy resin present in the resin composition is a total value of all the epoxy resins of the solid content of each epoxy resin divided by the epoxy equivalent value, and the reaction group of the hardener The total count is the sum of all the hardeners for which the solid content of each hardener is divided by the value of the reactive base equivalent.

In the above resin composition, based on the viewpoint of improving the mechanical strength or water resistance of the cured product of the resin composition, the resin composition is not When the volatile component is 100% by mass, the content of the curing agent is preferably from 3 to 30% by mass, more preferably from 5 to 25% by mass, even more preferably from 10 to 20% by mass.

(inorganic filler)

The thermosetting resin composition of the present invention preferably contains an inorganic filler based on the viewpoint of lowering the coefficient of thermal expansion. The inorganic filler to be used is not particularly limited and is exemplified by, for example, cerium oxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride. , aluminum borate, barium titanate, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium zirconate, calcium zirconate and the like. Among these, cerium oxide is preferred. In addition, the oxidation of amorphous cerium oxide, pulverized cerium oxide, molten cerium oxide, crystalline cerium oxide, synthetic cerium oxide, hollow cerium oxide, spherical cerium oxide, titanium doped cerium oxide, and the like矽 is better. And the cerium oxide is preferably spherical. Examples of the spherical cerium oxide are "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 adjustment of the coefficient of thermal expansion can be carried out by adjusting the type and amount of the components contained in the thermosetting resin composition. However, since the inorganic filler particularly contributes to the low thermal expansion of the thermosetting resin composition, By adjusting the type and amount of the inorganic filler, the thermal expansion rate can be adjusted well. Further, the titanium-doped cerium oxide has a tendency to have a low thermal expansion in the inorganic filler, and is particularly suitable for adjusting the value of the coefficient of thermal expansion in the present invention.

The "titanium-doped cerium oxide" is, for example, a mixture of TiCl ₄ and SiCl _{4 in which a} glass forming raw material of TiO ₂ -SiO ₂ glass is vaporized, and is heated and hydrolyzed (flame-heated and hydrolyzed) in an oxyhydrogen flame. _{2 -} SiO ₂ glass microparticles. Titanium dioxide doped with titanium is conventionally known as an example of a commercially available product, and is described as "AZ Filler" manufactured by Asahi Glass Co., Ltd. When the titanium-doped cerium oxide is blended in the inorganic filler, the amount of the inorganic filler contained in the resin composition is set to 100% by mass, and the amount of the cerium oxide doped with titanium in the inorganic filler is preferably 10% by mass. More than %, more preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, and more preferably It is 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and most preferably 100% by mass.

Further, as the inorganic filler, in order to improve moisture resistance and dispersibility, a decane coupling agent (epoxy decane coupling agent, amino decane coupling agent, mercapto decane coupling agent, etc.) or titanate is preferably used. A surface treatment agent such as a coupling agent or a guanidinium compound is surface-treated. These may be used alone or in combination of two or more.

The epoxy decane coupling agent is exemplified by, for example, glycidoxypropyltrimethoxydecane, glycidoxypropyltriethoxydecane, glycidoxypropylmethyldiethoxydecane, glycidyl group. Butyl trimethoxy decane, (3,4-epoxycyclohexyl)ethyltrimethoxy decane, etc., and the amino decane coupling agent is exemplified by, for example, an aminopropyl methoxy decane, an aminopropyl hydride Ethoxy decane, N-phenyl-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)aminopropyltrimethoxydecane, and the like. The mercapto decane coupling agent is exemplified by, for example, mercaptopropyltrimethoxydecane, mercaptopropyltriethoxydecane, and the like. These may be used alone or in combination of two or more. city For example, "KBM403" (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyl) manufactured by Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" manufactured by Shin-Etsu Chemical Co., Ltd. (N-phenyl-3-) Aminopropyltrimethoxydecane) 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, more preferably 3 μm or less, and more preferably from the viewpoint of forming fine wiring on the insulating layer. It is 1 μm or less, more preferably 0.7 μm or less, still more preferably 0.5 μm or less, more preferably 0.4 μm or less, and still more preferably 0.3 μm or less. On the other hand, when the epoxy resin composition is used as a resin composition paint, the lower limit of the average particle diameter of the inorganic filler is preferably 0.01 μm or more from the viewpoint of preventing the viscosity of the paint from rising and the workability from being lowered. More preferably, it is 0.03 μm or more, more preferably 0.05 μm or more, still more preferably 0.07 μm or more, and most preferably 0.1 μm or more. The average particle size of the above inorganic filler can be based on the Mie scattering theory, by laser diffraction. Determined by scattering method. Specifically, the particle size distribution of the inorganic filler can be determined on a volume basis by a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter can be measured as an average particle diameter. The measurement sample can be preferably used in which the inorganic filler is dispersed in water by ultrasonic waves. The laser diffraction scattering type particle size distribution measuring apparatus can use LA-500, 750, 950, etc., manufactured by Horiba, Ltd.

When the content of the inorganic filler is adjusted, the nonvolatile content in the resin composition is set to 100% by mass based on the viewpoint of lowering the coefficient of thermal expansion. The amount is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass. When the content of the inorganic filler is too small, the thermal expansion coefficient of the cured product tends to be high. When 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 preferably 90% by mass or less, more preferably 85% by mass or less.

Further, other components (for example, additives such as a thermoplastic resin, a hardening accelerator, and a flame retardant) may be further formulated in the resin composition of the present invention.

- Thermoplastic Resin -

The thermoplastic resin is exemplified by, for example, a phenoxy resin, a polyvinyl acetal resin, a polyimide resin, a polyamidoximine resin, a polyether oxime resin, and a polyfluorene resin. 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 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, still 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 weight average molecular weight of the thermoplastic resin in terms of polystyrene is LC-9A/RID-6A manufactured by Shimadzu Corporation, and the Shodex K-800P/K manufactured by Showa Denko Co., Ltd. is used. -804L/K-804L was used as a column, and chloroform was used as a mobile phase, and the column temperature was measured at 40 ° C, and was calculated using a calibration line of standard polystyrene.

The phenoxy resin is exemplified by, for example, having a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolak skeleton, a biphenyl skeleton, an anthracene skeleton, a dicyclopentadiene skeleton, and a descending A phenoxy resin having one or more kinds of skeletons selected from the group consisting of a borneol skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any one of a phenolic hydroxyl group, an epoxy group and the like. The phenoxy resin may be used singly or in combination of two or more. Specific examples of the phenoxy resin are "1256" and "4250" (all are phenoxy resins containing a bisphenol A skeleton) and "YX8100" (phenoxy resin containing a bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation. And "YX6954" (phenoxy resin containing bisphenol acetophenone skeleton), including "FX280" and "FX293" manufactured by Dongdu Chemical Co., Ltd., "YL7553" and "YL6794" manufactured by Mitsubishi Chemical Corporation. ", YL7213", "YL7290" and "YL7482".

Specific examples of the polyethylene acetal resin are electro-chemical butyraldehyde 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Electrochemical Industry Co., Ltd., S-LEC BH manufactured by Sekisui Chemical Industry Co., Ltd. Series, BX series, KS series, BL series, BM series, etc.

Specific examples of the polyimine resin are "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Nippon Chemical and Chemical Co., Ltd. Specific examples of the polyimine resin include a linear polyimine obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (Japanese Patent Laid-Open Publication No. Hei. No. 2006-37083) Polyimine containing a polyoxyalkylene skeleton (Japanese Patent Laid-Open Publication No. 2002-12667 and Japanese Patent Laid-Open The poly-imine is modified such as those described in JP-A-2000-319386.

Specific examples of the polyamidoximine resin are "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamidoximine resin are modified polyamines such as polyacrylamide skeletons "KS9100" and "KS9300" manufactured by Hitachi Chemical Co., Ltd. amine.

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

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

When the content of the nonvolatile component in the resin composition is 100%, the content of the thermoplastic resin in the resin composition is preferably from 0.1% by mass to 20% by mass. By setting the content of the thermoplastic resin to such a range, the viscosity of the resin composition can be made moderate, and a uniform resin composition having a thickness or a bulk property can be formed. When the content of the nonvolatile component in the resin composition is 100%, the content of the thermoplastic resin in the resin composition is more preferably from 1% by mass to 10% by mass.

- hardening accelerator -

Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, an lanthanum-based curing accelerator, and a metal-based curing accelerator, and are preferably an amine-based curing accelerator or an imidazole-based accelerator. A hardening accelerator and a metal-based hardening accelerator.

Phosphorus-based hardening accelerators are exemplified by, for example, triphenylphosphine and barium borate. Compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenyl The thiocyanate, butyltriphenylphosphonium thiocyanate or the like is preferably triphenylphosphine or tetrabutylphosphonate.

The amine-based hardening accelerator is exemplified by a trialkylamine such as triethylamine or tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6-gin(dimethylaminomethyl). Phenol, 1,8-diazabicyclo[5.4.0]-undecene, etc., preferably 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]-undecylene Alkene.

The imidazole-based hardening accelerator is exemplified by, for example, 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-methyl Imidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitic acid Salt, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ten Monoalkylimidazolyl-(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- Phenyl imidazoisocyanuric 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-3- Benzyl imidazolium chloride, 2-methylimidazoline, 2-phenylimidazole An imidazole compound such as a porphyrin and an adduct of an imidazole compound and an epoxy resin are preferably 2-ethyl-4-methylimidazole or 1-benzyl-2-phenylimidazole.

The lanthanide hardening accelerator is exemplified by, for example, dicyandiamide, 1-methyl hydrazine, 1-ethyl hydrazine, 1-cyclohexyl hydrazine, 1-phenyl fluorene, 1-(o-tolyl) fluorene, and dimethyl Base, diphenyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, pentamethyl hydrazine, 1,5,7-triazabicyclo[4.4.0]non-5-ene, 7-methyl-1 ,5,7-triazabicyclo[4.4.0]non-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1, 1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allyl biguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc., preferably two Cyanamide, 1,5,7-triazabicyclo[4.4.0]non-5-ene.

The metal-based hardening accelerator is not particularly limited, and examples thereof include organometallic complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex are organic cobalt complexes such as cobalt (II) acetylacetonate, cobalt (III) acetylate, and copper (II) acetylacetate. Organic zinc complex such as zinc acetyl phthalate (II), organic iron complex such as iron (III) acetylate pyruvate, and organic nickel complex such as nickel (II) acetyl phthalate An organic manganese complex such as manganese (II) acetate. The organic metal salt is exemplified by zinc octoate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like. These may be used alone or in combination of two or more.

In the resin composition of the present invention, an organo-cobalt accelerator is preferably used as the metal-based hardening accelerator, and cobalt(III) acetylacetate is preferably used. The content of the metal-based hardening accelerator is as a non-volatile component in the resin composition When 100% by mass, the metal content based on the metal-based curing catalyst is preferably in the range of 25 ppm to 500 ppm, more preferably in the range of 30 ppm to 200 ppm.

The curing accelerator may be used singly or in combination of two or more. When the content of the hardening accelerator in the resin composition is 100% by mass based on the nonvolatile content in the resin composition, it is preferably 0.01% by mass to 1% by mass, more preferably 0.02% by mass to 0.5% by mass, and more preferably It is 0.03 mass% to 0.1 mass%.

- Flame retardant -

The flame retardant is exemplified by, for example, an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a polyoxygenated flame retardant, a metal hydroxide, or the like. It is preferably 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (for example, "HCA-HQ" manufactured by Sanguang Co., Ltd.) . The flame retardant may be used singly or in combination of two or more. The content of the flame retardant in the resin composition layer is not particularly limited. However, when the nonvolatile content in the resin composition is 100% by mass, it is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass. ~5 mass%, and more preferably 1.5 mass% to 3% mass%.

<Reflow step>

The manufacturing method of the present invention includes a reflow step of mounting the component on the substrate having the cured layer produced by the above-described thermosetting step by reflow soldering.

The mounted components are not particularly limited and are exemplified by, for example, a semiconductor, an interposer, a passive component, etc., but the manufacturing method of the present invention can be particularly preferably used. Semiconductor installation.

The heating temperature in the reflow step may vary depending on the type of solder used or the type of parts to be mounted, but is generally 210 ° C to 330 ° C, preferably 220 ° C to 300 ° C, more preferably 230 ° C to 280 ° C. . The manufacturing method of the present invention is more suitable for the case where lead-free solder is used as the solder.

The manufacturing method of the present invention comprises the above-described heat hardening step and the above-described reflow step.

The method for producing a component mounting substrate of the present invention is characterized in that the shrinkage ratio (S1) in the xy direction after the thermosetting step of the thermosetting resin composition layer is higher than that of the thermosetting resin composition layer before the thermosetting step. 0.35% or less, preferably 0.3% or less, more preferably 0.2% or less, the shrinkage ratio (S2) of the cured layer after the reflow step is higher than that of the thermosetting resin composition before the thermosetting step It is 0.4% or less, preferably 0.3% or less, more preferably 0.2% or less, and S1 and S2 satisfy the relationship of S2-S1 ≦ 0.08, preferably S2-S1 ≦ 0.05, more preferably S2-S1 ≦ 0.04.

The measurement of the above S1 and S2 was carried out as follows.

<Measurement of S1>

(1-1) Determination of initial length

A through hole is formed in a portion of a 200 mm square resin having a thermosetting resin composition layer (thickness: 40 μm) at a distance of about 4 mm from a punch (the hole is temporarily referred to as A, B, C, and D in a clockwise direction), and is non-contacted. The image measuring device measures the length L (L _AB , L _BC , L _CD , L _DA , L _AC , L _BD ) between the centers of the formed holes (see Fig. 1).

(1-2) Thermal hardening of the thermosetting resin composition layer

The thermosetting resin composition layer having the measured length is heated to be thermally cured.

(1-3) Determination of thermosetting shrinkage rate

After heat curing, in the cured thermoplastic resin composition layer, the length L between the centers of the respective holes formed in (1-1) is measured by a non-contact type image measuring device in the same manner as L. '(L' _AB , L' _BC , L' _CD , L' _DA , L' _AC , L' _BD ). And calculate s1 _AB = (L _AB -L' _AB ) / L _AB

Similarly, s1 _BC , s1 _CD , s1 _DA , s1 _{AC are} calculated for 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 . , s1 _DA .

The heat curing shrinkage ratio was calculated by the following formula.

Thermal hardening 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 step

The substrate of the completion step (1-3) is reflowed.

(1-5) Determination of reflow shrinkage

After the reflow step, exactly the same as (1-3), the length L after reflow between the centers of the respective holes formed in (1-1) is measured by a non-contact type image measuring device in the same manner as L. (L" _AB , L" _BC , L " _CD , L " _DA , L " _AC , L " _BD ) and calculate s2 _AB = (L _{AB -} L" _AB ) / L _AB

Similarly, s2 _BC , s2 _CD , s2 _DA , s2 _{AC are} calculated for 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 . , s2 _DA .

The reflow shrinkage ratio is calculated by the following formula.

Reflow shrinkage rate [ shrinkage rate in xy direction: S2] (%) = {(s2 _AB + s2 _BC + s2 _CD + s2 _DA + s2 _AC + s2 _DA ) / 6} × 100

The above parameters are preferably satisfied by using a thermosetting resin composition containing an epoxy resin, a curing agent, and an inorganic filler as described above. According to the thermosetting resin composition, shrinkage of the insulating layer can be suppressed and warpage can be suppressed, and a cured product suitable for an insulating layer which is less likely to cause deformation of the substrate can be obtained. The cured product of the thermosetting resin composition is suitable for the manufacture of a component mounting substrate (particularly a semiconductor mounting substrate), and is particularly suitable for forming an insulating layer of a substrate. The thickness of a cured layer (an insulating layer) is usually about 3 to 200 μm. However, when the multilayer is formed, the thickness of the entire insulating layer is thicker than usual, and is usually about 10 to 300 μm.

<thermosetting resin composition>

An embodiment of the present invention provides a thermosetting resin composition for forming an insulating layer.

The cured product of the thermosetting resin composition which is thermally cured under the condition that the shrinkage ratio (S1) in the xy direction after thermosetting is 0.35% or less is based on IPC/JEDEC J-STD- In 020C, the shrinkage ratio (S2) in the xy direction after heating by the reflow temperature distribution is 0.4% or less, and S1 and S2 satisfy the relationship of S2-S1 ≦ 0.08.

The cured product of the thermosetting resin composition which is thermally cured under the condition that the shrinkage ratio (S1) in the xy direction after thermosetting is 0.35% or less is based on IPC/JEDEC J-STD-020C, and the reflow temperature distribution is used. After the heating, the shrinkage ratio (S2) in the xy direction is 0.4% or less, and S1 and S2 satisfy the relationship of S2-S1 ≦ 0.08, the thermoplastic resin composition is subjected to the high temperature of the component mounted by the reflow step. It is not easy to cause warpage of the substrate, but is an insulator layer formed for a thin component mounting substrate.

Preferred examples of the raw materials which can be used in the thermoplastic resin composition are as described above.

The measurement methods of S1 and S2 are as described above.

The reflow temperature distribution described in IPC/JEDEC J-STD-020C is quoted in Figure 2 and Tables 1-3. The time may be any of the conditions described in the table, and is, for example, a condition of t _S = 90 seconds, t _L = 105 seconds, and t _P = 20 seconds if the Sn-Pb eutectic solder is used. When there is no Pb solder, it is set to a condition of t _S = 120 seconds, t _L = 105 seconds, and t _P = 30 seconds. The package referred to herein is equivalent to the substrate before component mounting by reflow soldering. If the thickness of the package is Sn-Pb eutectic solder, it is preferably less than 2.5 mm, and if it is no Pb solder, it is preferably less than 2.5 mm, more preferably less than 2.5 mm to 1.6 mm, and even less than 1.6. Mm.

The thermosetting resin composition can be preferably used as a resin composition for forming an insulating layer of a multilayer printed wiring board (resin composition for an insulating layer on an inner layer substrate). By forming the insulating layer of the multilayer printed wiring board using the above-mentioned thermosetting resin composition, shrinkage of the insulating layer can be suppressed, and an insulating layer which is less likely to cause deformation of the substrate can be realized, and the problem of warpage of the substrate can be remarkably improved. Among them, a resin composition for forming an insulating layer in a multilayer printed wiring board by a build-up method (a resin composition for a build-up insulating layer of a multilayer printed wiring board) can be preferably used, and it is more preferably used as a resin composition for forming an insulating layer of a multilayer printed wiring board. A resin composition for forming an insulating layer on which a conductor layer is formed by plating (a resin composition for a build-up insulating layer of a multilayer printed wiring board on which a conductor layer is formed by plating). Further, the above-mentioned thermosetting resin composition can also be preferably used in the case where a circuit board is built in a multilayer printed wiring board component. In other words, the resin composition of the present invention can be preferably used as a resin composition (resin composition for filling a part) for a part for embedding a built-in circuit board of a part. The core substrate used for the manufacture of the built-in circuit board has a hole for the built-in component, and has a tendency to increase the density of the hole based on the miniaturization of the built-in circuit board itself, and is caused by the core. The warpage problem due to insufficient rigidity of the substrate tends to be deeper, but the thermosetting resin composition is used as a resin group for filling a part. The object can significantly alleviate the warpage problem even in the case of using a core substrate having a high hole density and a thin core.

<Prepreg>

The thermosetting resin composition may be impregnated into a sheet-like fibrous base material to form a prepreg. The prepreg system is obtained by impregnating the above-mentioned thermosetting resin composition into a sheet-like fibrous base material.

The sheet-like fibrous base material used for the prepreg is not particularly limited, and can be used as a base material for a prepreg such as glass cloth, linaloamine nonwoven fabric, or liquid crystal polymer nonwoven fabric. When forming an insulating layer for a multilayer printed wiring board, it is preferable to use a thin sheet-like fibrous base material having a thickness of 50 μm or less, preferably a sheet-like fibrous base material having a thickness of 10 μm to 40 μm, more preferably a sheet of 10 μm to 30 μm. The fibrous substrate is preferably a sheet-like fibrous substrate of 10 to 20 μm. A specific example of the glass cloth substrate used as the sheet-like fiber base material is "Style 1027MS" manufactured by Asahi-Schwebel Co., Ltd. (the warp density is 75 pieces / 25 mm, the weft density is 75 pieces / 25 mm, and the cloth weight is 20 g / m ² , thickness 19 μm), "Style 1037MS" made by Asahi-Schwebel (manufactured by Shisha, 70 pieces / 25 mm, weft density 73 pieces / 25 mm, cloth weight 24 g / m ² , thickness 28 μm), Azawa Manufacturing Co., Ltd. "1078" (filament density 54 pieces / 25mm, weft density 54 pieces / 25mm, cloth weight 48g / m ² , thickness 43μm), "1037NS" made by Yoshizawa Seisakusho Co., Ltd. Strip / 25mm, weft density 69 / 25mm, cloth weight 23g / m ² , thickness 21μm), "1027NS" made by Azawa Manufacturing Co., Ltd. (the warp density is 75 strips / 25mm, the weft density is 75 strips / 25mm, Cloth weight 19.5g/m ² , thickness 16μm), "1015NS" made by Azawa Seisakusho Co., Ltd. (haze density 95 strips / 25mm, weft density 95 strips / 25mm, cloth weight 17.5g / m ² , thickness 15μm) "1000NS" (mantle density 85 pieces / 25mm, weft density 85 pieces / 25mm, cloth weight 11g / m ² , thickness 10μm) made by Azawa Seisakusho Co., Ltd. Specific examples of the liquid crystal polymer nonwoven fabric include "VECRUS" (unit area: 6 to 15 g/m ² ) or "VECTRAN" manufactured by a melt blow molding method of an aromatic polyester nonwoven fabric manufactured by KURARAY Co., Ltd.

The prepreg is preferably produced by a conventional method such as a hot melt method or a solvent method.

According to an embodiment of the present invention, the thermosetting resin composition layer is laminated on the inner layer substrate to form a prepreg of the prepreg obtained by impregnating the thermosetting resin composition onto the fiber substrate. A component mounting substrate formed by the prepreg.

<Multilayer printed wiring board using prepreg>

Next, an example of a method of manufacturing a multilayer printed wiring board using the prepreg manufactured as described above will be described. 1 piece or as many pieces of the prepreg of the present invention are superimposed on the circuit substrate, and the release film is sandwiched by a metal plate, under pressure. The laminate was vacuum-pressed under heating. Pressurized. The 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. Further, similarly to the adhesive film, the prepreg may be laminated on the circuit board by vacuum lamination, and then heat-hardened. Subsequently, similarly to the method 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.

<Continue film>

The adhesive film can be formed using the above thermosetting resin composition.

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

Then, the film can be prepared by dissolving the thermosetting resin composition in an organic solvent to prepare a resin paint, applying the resin paint to a support using a die coater or the like, and drying the resin paint. form.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (hereinafter also referred to as "MEK") and cyclohexanone, ethyl acetate, butyl acetate, fibrin acetate, and propylene glycol monomethyl ether. Acetate such as acetate and carbitol acetate, carbitol such as cellulolytic and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethyl A guanamine-based solvent such as acetamide or N-methylpyrrolidone. The organic solvent may be used singly or in combination of two or more.

The drying of the resin paint can be carried out by a conventional drying method such as heating or blowing hot air. As the boiling point of the organic solvent in the resin paint is different, for example, when a resin paint containing 30% by mass to 60% by mass of an organic solvent is used, it can be dried at 50 ° C to 150 ° C for 3 minutes to 10 minutes. A follow-up film is formed.

Then, the support used for the formation of the film can preferably use a film made of a plastic material, a metal foil (copper foil, aluminum foil, etc.), and a mold release. For paper, it is preferred to use a film made of a plastic material. The plastic material is exemplified by polyester such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") or polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), and polycarbonate ( Hereinafter, it may be simply referred to as "PC"), acrylic acid such as polymethyl methacrylate (PMMA), cyclic polyolefin, triethyl fluorenyl cellulose (TAC), polyether thioether (PES), polyether ketone, Polyimine and the like. Among them, polyethylene terephthalate or polyethylene naphthalate is preferred, and polyethylene terephthalate is preferably inexpensive. In a preferred embodiment, the support is a polyethylene terephthalate film.

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

Further, as the support, a support having a release layer having a release layer on the surface joined to the resin composition layer may be used. The release agent used in the release layer of the support with the release layer is exemplified by, for example, one or more selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a polyoxymethylene resin. Moulding agent.

In the present invention, a commercially available product can also be used as the support for the release layer. Commercially available products are, for example, a PET film having a release layer containing an alkyd resin release agent as a main component, and "SK-1", "AL-5", "AL-7" manufactured by LINTEC Co., Ltd., and the like. .

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

In the adhesive film produced by using the above-mentioned thermosetting resin composition, the thickness of the resin composition layer is not particularly limited, but is preferably 100 μm or less, more preferably 80 μm or less, from the viewpoint of thickness reduction of the multilayer printed wiring board. Further, it is preferably 60 μm or less, and more preferably 50 μm or less. The lower limit of the thickness of the resin composition layer is usually 15 μm or more.

In the adhesive film produced by using the above-mentioned thermosetting resin composition, the protective film may be further laminated according to the support on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). . The thickness of the protective film is not particularly limited, but may be, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dirt or the like from adhering to the surface of the resin composition layer or to prevent scratches. Then, the film can be wound up in a roll shape, and when an insulating layer is formed in the production of the multilayer printed wiring board, it can be used by peeling off the protective film.

In one embodiment of the present invention, the thermosetting resin composition layer is preferably a component mounting substrate formed by laminating a film on the inner layer substrate and forming a thermosetting resin composition layer on the carrier film.

<Multilayer printed wiring board using a film followed by a film>

An example of a method of producing a multilayer printed wiring board using the adhesive film manufactured as described above will be described.

First, the adhesive film is laminated on one or both sides of the circuit substrate using a vacuum laminator. The substrate used for the circuit board is exemplified by, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether plate, or the like. Again, here The circuit board refers to a conductor layer (circuit) formed by patterning on one or both sides of the substrate as described above. In the multilayer printed wiring board in which the conductor layer and the insulating layer are alternately laminated, the conductor layer (circuit) which is patterned on one or both sides of the outermost layer of the multilayer printed wiring board is also included herein. In the circuit board. Further, the surface of the conductor layer may be subjected to a pre-roughening treatment by a blackening treatment, a copper etching treatment, or the like.

In the above lamination, when the protective film is removed after the film has the protective film, the film and the circuit substrate may be preheated as needed, and the film may be pressed against the circuit substrate by pressurization and heating. In the adhesive film of the present invention, a method of laminating to a circuit substrate under reduced pressure by vacuum lamination is preferably used. The lamination conditions are not particularly limited, but it is preferred to set the pressing temperature (laminating temperature) to 70 to 140 ° C and the pressing pressure to preferably 1 to 11 kgf / cm ² (9.8 × 10 ⁴ to 107.9). ×10 ⁴ N/m ² ), lamination under reduced pressure at an air pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch type or a continuous type using a roll. In addition, vacuum lamination can also be carried out using a commercially available vacuum laminator. Commercially available vacuum laminating machines are, for example, vacuum coating machines manufactured by Nichigo Morton Co., Ltd., vacuum pressure laminating machines manufactured by Nimko Seisakusho Co., Ltd., and roll drying coatings manufactured by Hitachi Industrial Co., Ltd. , a vacuum laminator made by Hitachi AIC Co., Ltd., etc.

Further, the laminating step of heating and pressurizing under reduced pressure can also be carried out using a general vacuum hot press. For example, it can be performed by pressurizing a metal plate such as a heated SUS plate from the side of the support layer. The pressurization condition is such that the degree of pressure reduction is 1 × 10 ^-2 MPa or less, preferably 1 × 10 ^-3 MPa or less. Heating and pressurization can also be carried out in one stage, but it is preferably carried out in two or more stages from the viewpoint of controlling resin bleeding. For example, it is preferred that the pressure in the first stage is in the range of 70 to 150 ° C and the pressure is 1 to 15 kgf/cm ² , and the pressure in the second stage is in the range of 150 to 200 ° C and a pressure of 1 to 40 kgf / cm ² . get on. The time of each stage is preferably carried out in 30 to 120 minutes. Commercially available vacuum hot presses are exemplified by, for example, MNPC-V-750-5-200 (manufactured by Nago Seiki Co., Ltd.), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

The thermosetting resin composition layer is preferably formed by laminating a film formed by laminating a thermosetting resin composition layer on a carrier film on an inner layer substrate. After laminating the film on the circuit board and cooling to the vicinity of room temperature, the support layer can be peeled off and thermally cured to form an insulating layer on the circuit board. The heat curing condition may be appropriately selected depending on the type and content of the resin component in the resin composition, but it is preferably from 150 ° C to 220 ° C for 20 minutes to 180 minutes, more preferably from 160 ° C to 210 ° C for 30 minutes. 120 minutes range.

After the insulating layer is formed, the support is not peeled off before the hardening. Then, if necessary, a hole is formed in the insulating layer formed on the circuit board to form a through hole and a through hole. The opening can be carried out by a conventional method such as a drill, a laser, a plasma, and the like, and the same method is used, but the use of a carbon dioxide gas laser, a YAG laser or the like for opening the hole is the most common method.

Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, a conventional method such as vapor deposition, sputtering, or ion plating can be used. In the case of wet plating, the swelling treatment with the swelling liquid, the roughening treatment with the oxidizing agent, and the neutralization of the neutralizing liquid are performed in sequence. The anchoring of the surface of the insulating layer is formed by irregularities. The swelling treatment by the swelling liquid is carried out by immersing the insulating layer in a swelling liquid at 50 to 80 ° C for 5 to 20 minutes. The swelling solution may, for example, be an alkali solution, a surfactant solution or the like, preferably an alkali solution, and the alkali solution is exemplified by a sodium hydroxide solution, a potassium hydroxide solution or the like. Commercially available swelling liquids are exemplified by Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, etc., manufactured by ATOTECH Co., Ltd., Japan. The roughening treatment by the oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 to 80 ° C for 10 minutes to 30 minutes. The oxidizing agent is, for example, an alkaline permanganic acid solution, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid or the like obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. Further, the concentration of the permanganate in the alkaline permanganic acid solution is preferably from 5 to 10% by weight. Commercially available oxidizing agents are listed, for example, as Concentrate manufactured by ATOTECH Co., Ltd. of Japan. Alkaline permanganic acid solution such as Compact CP, Doesing Solution Securiganth P, etc. The neutralization solution and the treatment system are immersed in 30 to 50 ° C and in the liquid for 3 to 10 minutes. The neutralizing liquid is preferably an acidic aqueous solution, and the commercial product is exemplified by Reduction Solution Securigant P manufactured by ATOTECH Co., Ltd., Japan.

Next, electroless plating and electrolytic plating are combined to form a conductor layer. Further, the conductor layer forms a plating resist of the opposite pattern, and the conductor layer may be formed only by electroless plating. As for the subsequent pattern forming method, for example, a subtractive method, a semi-additive method, or the like which is conventionally known to those skilled in the art can be used.

By using a multilayer printed wiring board manufactured using the above thermosetting resin composition, it is possible to manufacture a semiconductor wafer, an interposer, and a semiconductor wafer. A substrate for a component such as a moving component.

An example of a method of manufacturing a semiconductor package substrate is exemplified.

<Semiconductor Mounting Substrate>

A semiconductor package substrate can be manufactured by mounting a semiconductor wafer on a conductive portion of a multilayer printed wiring board manufactured using the above-described thermosetting resin composition. The "conduction portion" is a "portion for transmitting an electric signal in a multilayer printed wiring board", and the site may be a surface or a buried portion. Further, the semiconductor wafer is not particularly limited as long as it is a circuit element made of a semiconductor.

The method of mounting the semiconductor wafer in the case of manufacturing the semiconductor package substrate is not particularly limited as long as the semiconductor wafer can function effectively, and specifically, it is a wire bonding mounting method, a flip chip mounting method, and a bump-added layer (BBUL). The mounting method, the mounting method using an anisotropic conductive film (ACF), the mounting method using a non-conductive thin film (NCF), and the like.

[Examples]

Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, the "parts" in the following description means "parts by mass".

First of all, the measurement method in the physical property evaluation of this specification. The evaluation method will be explained.

[Measurement of shrinkage rate]

(1-1) Modulation of polyimide film with resin

A batch vacuum lamination machine (Nichigo Morton Co., Ltd., 2nd-stage build-up laminator CVP700) was used to form a resin composition layer and a polyimide film (UPILEX 25S manufactured by Ube Industries, Ltd.). A resin sheet (200 mm square) produced in the following production example was laminated on one surface so as to be in contact with the center of the smooth surface of 25 μm thick and 240 mm square. The lamination system was carried out by depressurizing for 30 seconds to bring the gas pressure to 13 hPa or less, and then pressing it at 100 ° C and a pressure of 0.74 MPa for 30 seconds.

(1-2) Determination of initial length

The obtained polyimine film of the resin is formed on the support of the resin sheet by forming four through holes (about 6 mm in diameter) by punching at a portion of about 200 mm from a square of 200 mm square resin (the hole is temporarily called a clockwise direction). After the support of the resin sheet was peeled off by A, B, C, and D), the center of each of the formed holes was measured by a non-contact type image measuring device (manufactured by Mitsu Toyo Co., Ltd., Quick Vision model: QVH1X606-PRO III_BHU2G). The length L (L _AB , L _BC , L _CD , L _DA , L _AC , L _BD ) (see Fig. 1).

(1-3) Thermal hardening of the resin composition layer

The polyimide film of the polyimide film of the length of the resin was set to a 255 mm × 255 mm glass cloth substrate epoxy resin double-sided copper laminate (0.7 mm thick, manufactured by Matsushita Electric Works Co., Ltd.) It On the "R5715ES"), the four sides were fixed with a polyimide and a tape (width: 10 mm), and heated at 150 ° C for 90 minutes to thermally cure the resin composition layer to obtain a cured layer. Similarly, the cured layer was obtained by heating at 190 ° C for 90 minutes and heating at 200 ° C for 90 minutes.

(1-4) Determination of thermosetting shrinkage rate

After heat hardening, the polyimide and the tape are peeled off, the polyimine film with the cured layer is removed from the laminate, and the cured layer is peeled off from the polyimide film, and is non-contacted in the same manner as L. The image measuring device measures the length L' after hardening between the centers of the holes formed in (1-2) (L' _AB , L' _BC , L' _CD , L' _DA , L' _AC , L' _BD ) . And calculate s1 _AB = (L _AB -L' _AB ) / L _AB

Similarly, s1 _BC , s1 _CD , s1 _DA , s1 _{AC are} calculated for 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 . , s1 _DA .

The heat curing shrinkage ratio was calculated by the following formula.

Thermal hardening shrinkage [shrinkage in xy direction: S1] (%) = {(s1 _AB + s1 _BC + s1 _CD + s1 _DA + s1 _AC + s1 _DA ) / 6} × 100

(1-5) Reflow step

The substrate of the finishing step (1-3) is passed through a reflow soldering apparatus having a peak temperature of 260 ° C ("HAS-6116" manufactured by ANTOM Co., Ltd., Japan, and the temperature distribution is based on IPC/JEDEC J-STD-020C) is performed once.

(1-6) Determination of reflow shrinkage rate

After the reflow step, exactly the same as (1-4), the length L after reflow between the centers of the respective holes formed in (1-2) is measured by a non-contact type image measuring device in the same manner as L. (L" _AB , L" _BC , L " _CD , L " _DA , L " _AC , L " _BD ) and calculate s2 _AB = (L _{AB -} L" _AB ) / L _AB

Similarly, s2 _BC , s2 _CD , s2 _DA , s2 _{AC are} calculated for 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 . , s2 _DA .

The reflow shrinkage ratio is calculated by the following formula.

Reflow shrinkage rate [ shrinkage rate in xy direction: S2] (%) = {(s2 _AB + s2 _BC + s2 _CD + s2 _DA + s2 _AC + s2 _DA ) / 6} × 100

[Modulation of substrate for evaluation of reflow behavior]

(2-1) Preparation of the inner substrate

A glass cloth substrate epoxy resin laminate (a unclad-board having a copper foil etched, 0.06 mm thick, "LaXY-4785TH-B" manufactured by SUMITOMO BAKELITE Co., Ltd.) was prepared as an inner substrate.

(2-2) Lamination of resin sheets

A resin sheet layer produced in the following production example was used in such a manner that a resin composition layer was brought into contact with the inner layer substrate by using a batch vacuum pressure laminator (Nichigo Morton Co., Ltd. second-order build-up laminator CVP700). Cooperate on both sides of the inner substrate. The lamination system was carried out by depressurizing for 30 seconds to bring the gas pressure to 13 hPa or less, and then pressing it at 100 ° C under 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) Thermal hardening of the resin composition layer

After the support of the resin sheet was peeled off from the substrate of the laminated resin sheet, it was heated at 150 ° C for 90 minutes to thermally cure the resin composition layer to obtain a cured layer. Similarly, the cured layer was obtained by heating at 190 ° C for 90 minutes and heating at 200 ° C for 90 minutes.

(2-4) Evaluation of reflow behavior

After cutting a 45mm square piece (n=5), pass a reflow soldering device with a peak temperature of 260 °C ("HAS-6116" made by ANTOM Co., Ltd. (this condition is also based on IPC/JEDEC J-STD-020C). Then, using a flat/warm moire device (TherMoire AXP manufactured by Akrometrix), the temperature is distributed from the lower portion of the substrate according to IPC/JEDEC J-STD-020C (peak temperature 260 ° C). The warping behavior of the 10 mm square portion of the center of the substrate.

The difference between the maximum height and the minimum height of the obtained displacement data was evaluated as × in the case of 40 μm or more in one sample in all temperature ranges, and was evaluated as ○ in all samples which did not reach 40 μm.

The resin sheets 1, 2, 3, and 4 used in the examples and the comparative examples were produced in the following order.

<Production Example 1 (Production of Resin Sheet 1)>

A bisphenol A type epoxy resin ("828EL" manufactured by Mitsubishi Chemical Corporation, an epoxy equivalent of about 185) 12 parts, a naphthalene type epoxy resin ("HD4032SS" manufactured by DIC), an epoxy equivalent of about 144 3 parts, biphenyl type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 185), 6 parts, biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd." Epoxy equivalent of about 288) 25 parts, and phenoxy resin ("XX6954BH30" manufactured by Mitsubishi Chemical Corporation, MEK/cyclohexanone = 1/1 solution of solid content 30% by mass) 20 parts in solvent petroleum brain (solvent) Naphtha) 15 parts of the mixture were heated and dissolved while stirring. After cooling to room temperature, a triazine-containing phenol novolak-based curing agent ("LA-7054" manufactured by DIC Co., Ltd., a hydroxyl group equivalent of 125, and a solid component 60% MEK solution) was mixed therein, and a naphthol system was added. Hardener ("SN485" made by Nippon Steel Chemical Co., Ltd., hydroxyl equivalent 215, 60% solid solution MEK solution) 10 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5 mass % MEK solution) 0.4 parts, flame retardant ("HCA-HQ", 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphonium, manufactured by Sanguang Co., Ltd. 3 parts of phenanthrene-10-oxide, an average particle diameter of 2 μm, and a spherical cerium oxide (average particle diameter of 0.25 μm) surface-treated with an amine decane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) "SOC1" manufactured by ADMATECHS Co., Ltd., having a carbon content per unit surface area of 0.36 mg/m ² ), 40 parts, and surface-treated with an amine-based decane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) Spherical glass filler (average particle size 0.2 μm, "AZ Filler" manufactured by Asahi Glass Co., Ltd., 10 parts per unit surface area of carbon (0.38 mg/m ² )), uniformly dispersed by a high-speed rotary kneading machine to prepare a resin paint 1 .

Then, the release layer side of the PET film ("AL5" manufactured by LINTEC Co., Ltd., thickness: 38 μm) having an alkyd-based release layer was made uniform so that the thickness of the dried resin composition layer was 40 μm. The resin paint 1 was applied 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) made 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 ring Oxygen resin (YX4000HK) manufactured by Mitsubishi Chemical Corporation, 12 parts epoxy equivalent: 185), dicyclopentadiene type epoxy resin (HP-7200H, manufactured by DIC), epoxy equivalent of approximately 275 9 parts, phenoxy resin ("755755BH30" manufactured by Mitsubishi Chemical Corporation, MEK/cyclohexanone = 1/1 solution of solid content 30% by mass), 16 parts, dissolved in 30 parts of solvent petroleum brain while stirring . After cooling to room temperature, 40 parts of an active ester-based curing agent ("HPC8000-65T" manufactured by DIC Co., Ltd., a toluene solution having a reactive base equivalent of about 223 and a nonvolatile content of 65% by mass), and a hardening accelerator (40 parts) were mixed therein. 3 parts of 4-dimethylaminopyridine, a solid content of 5% by mass of MEK solution), spherical cerium oxide surface-treated with an amine decane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) The particle size is 0.5 μm, the "SOC2" manufactured by ADMATECHS Co., Ltd., the amount of carbon per unit surface area is 0.39 mg/m ² ), 100 parts, and the amine decane-based coupling agent (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) A spherical glass filler (having an average particle diameter of 0.2 μm, "AZ Filler" manufactured by Asahi Glass Co., Ltd., having a carbon content per unit surface area of 0.38 mg/m ² ) 40 parts, and uniformly dispersed by a high-speed rotary kneading machine. Modification of resin paint 2.

Next, the resin sheet 2 was produced in the same manner as in Production Example 1 using the resin paint 2.

<Production Example 3 (Production of Resin Sheet 3)>

6 parts of naphthalene type epoxy resin ("HP4032SS" manufactured by DIC Co., Ltd., epoxy equivalent: 144), biphenyl type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 185) 6 parts, biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288) 20 parts, and phenoxy resin ("LM7553BH30" manufactured by Mitsubishi Chemical Corporation), solid content 30 8 parts by mass of MEK solution) 8 parts of the solvent petroleum brain 15 parts were heated and dissolved while stirring. After cooling to room temperature, a prepolymer of bisphenol A dicyanate ("BA230S75" manufactured by LONZA Co., Ltd., a cyanate equivalent of about 232, and a nonvolatile matter of MEK solution of 20 mass%) was mixed therein. A portion, a phenol novolac type polyfunctional cyanate resin ("PT30S" manufactured by LONZA Co., Ltd., a acetonitrile ester equivalent of about 133, a nonvolatile matter of 8 mass% of MEK solution), 8 parts, an active ester-based hardener ( "HPC8000-65T" manufactured by DIC Co., Ltd., a toluene solution having a non-volatile content of about 223 and a non-volatile content of 223), 8 parts, a hardening accelerator (4-dimethylaminopyridine, a solid content of 5% by mass of MEK) 0.4 parts of the solution, a hardening accelerator (cobalt (III) acetyl sulfacetate (III), a solid content of 1% by mass of MEK solution), 3 parts, and a flame retardant (HCA, manufactured by Sanguang Co., Ltd.) -HQ", 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 2 μm) 3 parts, with amine decane A coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) is a surface-treated spherical cerium oxide (average particle diameter: 0.5 μm, "SOC2" manufactured by ADMATECHS Co., Ltd.), and the amount of carbon per unit surface area is 0.39 mg / m ² ) 50 parts, with an amine decane series A spherical glass filler (having an average particle diameter of 0.2 μm, "AZ Filler" manufactured by Asahi Glass Co., Ltd.) having a surface treatment of "KBM573" manufactured by Shin-Etsu Chemical Co., Ltd., has a carbon content per unit surface area of 0.38 mg/m. ² ) 50 parts, uniformly dispersed by a high-speed rotary kneading machine to prepare a resin paint 3.

Next, the resin sheet 3 was produced in the same manner as in Production Example 1 using the resin paint 3.

<Production Example 4 (Production of Resin Sheet 4)>

A bisphenol A type epoxy resin ("828EL" manufactured by Mitsubishi Chemical Corporation, an epoxy equivalent of about 185) 12 parts, a naphthalene type epoxy resin ("HD4032SS" manufactured by DIC), an epoxy equivalent of about 144 3 parts, biphenyl type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 185), 6 parts, biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd." Epoxy equivalent of about 288) 25 parts, phenoxy resin ("XX6954BH30" manufactured by Mitsubishi Chemical Corporation, MEK/cyclohexanone = 1/1 solution of solid content 30% by mass) 20 parts in 10 parts of solvent petroleum brain Heat and dissolve while stirring. After cooling to room temperature, a triphenyl skeleton-containing phenol novolak-based curing agent ("LA-7054" manufactured by DIC Co., Ltd., a hydroxyl group equivalent of 125, a solid component 60% MEK solution), and naphthol were mixed therein. Hardening agent ("SN485" manufactured by Nippon Steel Chemical Co., Ltd., hydroxyl equivalent 215, 60% solid solution of MEK solution) 10 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5 Mass % of MEK solution) 0.4 parts, flame retardant ("HCA-HQ", 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphine" Spherical cerium oxide (average particle size 0.25 μm) surface-treated with an amino decane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) in an amount of 3 parts by mass of phenanthrene-10-oxide "SOC1" manufactured by ADMATECHS Co., Ltd., having a carbon content per unit surface area of 0.36 mg/m ² ), was uniformly dispersed by a high-speed rotary kneading machine to prepare a resin paint 4 .

Next, the resin sheet 4 was produced in the same manner as in Production Example 1 using the resin paint 4.

<Production Example 5 (Production of Resin Sheet 5)>

6 parts of naphthalene type epoxy resin ("HP4032SS" manufactured by DIC Co., Ltd., epoxy equivalent: 144), biphenyl type epoxy resin ("XX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 185) 6 parts, biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288) 20 parts, phenoxy resin ("755755BH30" manufactured by Mitsubishi Chemical Corporation), solid content 30 mass 16 parts of MEK solution) 16 parts of the solvent petroleum brain 5 parts were heated and dissolved while stirring. After cooling to room temperature, a prepolymer of bisphenol A dicyanate ("BA230S75" manufactured by LONZA Co., Ltd., a cyanate equivalent of about 232, and a nonvolatile matter of MEK solution of 20 mass%) was mixed therein. A portion, a phenol novolac type polyfunctional cyanate resin ("PT30S" manufactured by LONZA Co., Ltd., a acetonitrile ester equivalent of about 133, a nonvolatile matter of 8 mass% of MEK solution), 8 parts, an active ester-based hardener ( "HPC8000-65T" manufactured by DIC Co., Ltd., a toluene solution having a non-volatile content of about 223 and a non-volatile content of 223), 8 parts, a hardening accelerator (4-dimethylaminopyridine, and a solid content of 5% by mass of MEK) 0.4 parts of the solution, a hardening accelerator (cobalt (III) acetyl sulfacetate (III), a solid content of 1% by mass of MEK solution), 3 parts, and a flame retardant (HCA, manufactured by Sanguang Co., Ltd.) -HQ", 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 2 μm) 3 parts, with amine decane A coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) is a surface-treated spherical cerium oxide (average particle size 0.25 μm, "SOC1" manufactured by ADMATECHS Co., Ltd.), and the carbon amount per unit surface area is 0.36 mg / m ²⁾ 40 parts of a high speed rotating mixing Homogeneously dispersed to prepare a resin varnish 5.

Next, the resin sheet 5 was produced in the same manner as in Production Example 1 using the resin paint 5.

The composition of the resin composition layers of the resin sheets 1 to 5 is shown in Table 4.

The evaluation results are shown in Table 5.

As is understood from the results of Table 2, even when the same resin sheet 1 was used, when the temperature of the thermosetting step was 190 ° C (Test Example 1) × 90 minutes, a composition satisfying the requirements of the present invention was obtained, whereas At 150 ° C (Test Example 5) × 90 minutes, a composition satisfying the requirements of the present invention could not be obtained. Further, in the same manner as in the case of using the same resin sheet 2, when the temperature of the heat curing step was 200 ° C (Test Example 2) × 90 minutes, a composition satisfying the requirements of the present invention was obtained, whereas at 150 ° C (Test Example 6) × At 90 minutes, the composition satisfying the requirements of the present invention could not be obtained.

The resin sheet 1 and the resin sheet 4 have a similar composition, but the test piece 1 is AZ Filler, and the composition satisfying the requirements of the present invention can be obtained, although the thermal curing step is the same condition. On the other hand, in the case of the test example 4, the same cannot be obtained. A composition that satisfies the requirements of the present invention.

The resin sheet 3 has a similar composition to the resin sheet 5, but the resin sheet 3 (Test Example 3) can obtain a composition satisfying the requirements of the present invention, although the thermosetting step is the same condition, whereas the resin sheet 5 (Test Example 7) In the case of the present invention, a composition satisfying the provisions of the present invention cannot be obtained. Further, in the case of the resin sheet 5, even if the temperature of the thermosetting step was changed, the composition satisfying the present invention could not be obtained (Test Example 8).

Claims (24)

A method of manufacturing a component mounting substrate, comprising the steps of: heat-hardening a thermosetting resin composition layer formed on an inner layer substrate, forming a hardening step of the cured layer, and mounting the component by reflow soldering a reflow step on the substrate having the cured layer; and a shrinkage ratio (S1) in the xy direction after the thermosetting step of the thermosetting resin composition layer is 0.35% or less, and after the reflow step of the cured layer The shrinkage ratio (S2) in the xy direction is 0.4% or less, and S1 and S2 satisfy the relationship of S2-S1 ≦ 0.08. The method of claim 1, wherein the thermosetting resin composition contains an epoxy resin, a hardener, and an inorganic filler. The method of claim 2, which comprises cerium oxide as an inorganic filler. The method of claim 2, which comprises titanium doped ceria as an inorganic filler. In the method of claim 2, when the non-volatile 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. The method of claim 1, wherein the heating temperature in the heat hardening step is from 120 ° C to 240 ° C. The method of claim 1, wherein the peak temperature in the reflow step is 210 ° C to 330 ° C. The method of claim 1, wherein the thermosetting resin composition layer is formed by impregnating the thermosetting resin composition into the fibrous substrate Formed by dipping. The method of claim 1, wherein the thermosetting resin composition layer is formed by laminating the film on the inner layer substrate, and the film is formed on the carrier film by forming a layer of the thermosetting resin coarse composition layer. The method of claim 1, wherein the thermosetting resin composition layer is formed by laminating a prepreg to the carrier on the inner substrate, and the prepreg system of the carrier is formed with a thermosetting resin on the carrier film. A prepreg formed by impregnating a fibrous substrate with a composition. The method of claim 1, wherein the hardened layer has a thickness of from 3 to 200 μm. The method of claim 1, wherein the part is a semiconductor wafer, an interposer or a passive component. The method of claim 12, wherein the part is a semiconductor wafer. A thermosetting resin composition which is a thermosetting resin composition for forming an insulating layer, which is characterized in that it is thermally hardened under the condition that the shrinkage ratio (S1) in the xy direction after thermosetting is 0.35% or less. The cured product of the thermosetting resin composition has a shrinkage ratio (S2) of 0.4% or less in the xy direction after heating according to the reflow temperature distribution of IPC/JEDEC J-STD-020C, and S1 and S2 satisfy S2-S1≦ The relationship of 0.08. The thermosetting resin composition of claim 14, wherein the peak temperature of the reflow is 260 °C. The thermosetting resin composition according to claim 15, wherein the thermosetting resin composition contains an epoxy resin, a curing agent, and an inorganic filler. The thermosetting resin composition of claim 16, which comprises cerium oxide as an inorganic filler. The thermosetting resin composition of claim 16, which comprises titanium doped ceria as an inorganic filler. The thermosetting resin composition of claim 16, wherein the non-volatile component in the thermosetting resin composition is 100% by mass, and the content of the inorganic filler in the thermosetting resin composition is 40% by mass. the above. A prepreg obtained by impregnating a thermosetting resin composition according to any one of claims 15 to 19 into a fibrous base material. A multilayer printed wiring board obtained by forming an insulating layer from a cured product of the thermosetting resin composition according to any one of claims 15 to 19. A component mounting substrate obtained by forming an insulating layer from a cured product of the thermosetting resin composition according to any one of claims 15 to 19. The component mounting substrate of claim 22, wherein the component is a semiconductor wafer, an interposer or a passive component. The component mounting substrate of claim 23, wherein the component is a semiconductor wafer.