KR102259476B1 - Process for producing component mounting substrate - Google Patents

Abstract

[Problem] A method for manufacturing a component mounting board that is unlikely to cause warpage of the board even after a high temperature of component mounting by a reflow process, which can respond to new thinning of the component mounting board, and formation of an insulating layer for a thin component mounting board To provide a thermosetting resin composition suitable for
[Solutions] Includes a thermosetting step of heating and curing the thermosetting resin composition layer formed on the inner layer substrate to form a cured product layer, and a reflow step of mounting the component on the substrate having the cured material layer by reflow. and the shrinkage ratio (S1) in the xy direction after the thermosetting step of the thermosetting resin composition layer is 0.35% or less, and the shrinkage ratio (S2) in the xy direction after the reflow step of the cured product layer is 0.4% or less, and A method for manufacturing a component mounting board, wherein S1 and S2 satisfy the relationship S2-S1≤0.08, and a thermosetting resin composition for forming an insulating layer, wherein the shrinkage rate (S1) in the xy direction after thermosetting is 0.35 % or less, the shrinkage rate (S2) in the xy direction after heating the cured product of the thermosetting resin composition thermoset to a reflow temperature profile conforming to IPC/JEDEC J-STD-020C is 0.4% or less, and A thermosetting resin composition, characterized in that S1 and S2 satisfy the relationship of S2-S1≤0.08.

Description

Manufacturing method of component mounting board {PROCESS FOR PRODUCING COMPONENT MOUNTING SUBSTRATE}

This invention relates to the manufacturing method of a component mounting board|substrate, and the thermosetting resin composition useful for formation of the insulating layer of a component mounting board|substrate.

As a manufacturing technique of a multilayer printed circuit board, the manufacturing method by the buildup system which laminates|stacks an insulating layer and a conductor layer alternately on a core board|substrate is known. In the manufacturing method by the build-up method, in general, an insulating layer is formed by hardening|curing a resin composition. As such a resin composition, it is known to use an epoxy resin composition (patent document 1).

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

Japanese Patent Laid-Open No. 2007-254709 Japanese Patent Laid-Open No. 2010-202865

While further thinning of a multilayer printed circuit board is desired, the thickness of a core board|substrate or an insulating layer tends to become thin gradually. However, due to the reduction in thickness of the core substrate or the insulating layer, the insulating layer is easily affected by heat shrinkage. The present inventors have found that when a component is mounted on a substrate by a reflow process to manufacture a component mounting substrate, in particular, in a thin substrate, the bending of the substrate is realized due to the shrinkage of the insulating layer under high temperature. found the problem that it becomes easy to exist.

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

MEANS TO SOLVE THE PROBLEM As a result of earnest examination in view of the said subject, the present inventors WHEREIN: In the thermosetting resin composition used for formation of the insulating layer of a component mounting board|substrate, the shrinkage rate after the thermosetting process of the thermosetting resin composition layer formed on the inner-layer board|substrate, and thermosetting Paying attention to the shrinkage rate and their difference after the reflow process of the cured material layer (insulating layer) formed by It was discovered that the curvature of the subsequent board|substrate was suppressed, and came to complete this invention. That is, the present invention includes the following contents.

[1] including a thermosetting step of heating and curing the thermosetting resin composition layer formed on the inner layer substrate to form a cured product layer, and a reflow step of mounting the component on the substrate having the cured material layer by reflow; , the shrinkage ratio (S1) in the xy direction after the thermosetting step of the thermosetting resin composition layer is 0.35% or less, the shrinkage ratio (S2) in the xy direction after the reflow step of the cured product layer 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 contains silica as an inorganic filler.

[4] The method according to [2], which contains titanium-doped silica 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 content of the inorganic filler in the thermosetting resin composition 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 120°C to 240°C.

[7] The method according to any one of [1] to [6], wherein the peak temperature in the reflow step is 210°C to 330°C.

[8] The method according to any one of [1] to [7], wherein the thermosetting resin composition layer is formed of a prepreg in which the thermosetting resin composition is impregnated into a fiber base material.

[9] The method according to any one of [1] to [8], wherein the thermosetting resin composition layer is formed by laminating an adhesive film in which a thermosetting resin crude composition layer is formed on a carrier film to an inner layer substrate.

[10] The thermosetting resin composition layer according to any one of [1] to [8], wherein the prepreg formed by impregnating a fiber base with a thermosetting resin composition on a carrier film is formed by laminating a prepreg with a carrier to an inner layer substrate. , Way.

[11] The method according to any one of [1] to [10], wherein the cured product layer has a thickness of 3 to 200 µm.

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

[13] The method according to [12], wherein the component is a semiconductor chip.

[14] A thermosetting resin composition for forming an insulating layer, comprising:

The cured product of the thermosetting resin composition thermosetting under the condition that the shrinkage rate (S1) in the xy direction after thermosetting is 0.35% or less is heated to a reflow temperature profile based on IPC/JEDEC J-STD-020C in the xy direction A thermosetting resin composition, characterized in that the shrinkage ratio (S2) of is 0.4% or less, and S1 and S2 satisfy the relationship of S2-S1≤0.08.

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

[16] The thermosetting resin composition according to [15], wherein the thermosetting resin composition contains an epoxy resin, a curing agent, and an inorganic filler.

[17] The thermosetting resin composition according to [16], which contains silica as an inorganic filler.

[18] The thermosetting resin composition according to [16], comprising silica doped with titanium as an inorganic filler.

[19] The thermosetting resin composition according to any one of [16] to [18], wherein when the nonvolatile component in the thermosetting resin composition is 100% by mass, the content of the inorganic filler in the thermosetting resin composition is 40% by mass or more.

[20] A prepreg obtained by impregnating a fiber base with the thermosetting resin composition according to any one of [15] to [19].

[21] A multilayer printed wiring board in which an insulating layer is formed of the cured product of the thermosetting resin composition according to any one of [15] to [19].

[22] A component mounting substrate in which an insulating layer is formed of the cured product of the thermosetting resin composition according to any one of [15] to [19].

[23] The component mounting board according to [22], wherein the component is a semiconductor chip, an interposer, or a passive element.

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

ADVANTAGE OF THE INVENTION According to this invention, even after going through the high temperature of component mounting by a reflow process, the manufacturing method of the component mounting board|substrate which the board|substrate is hard to produce is provided. Moreover, according to this invention, the thermosetting resin composition suitable for formation of the insulating layer of a thin component mounting board|substrate is provided. INDUSTRIAL APPLICATION This invention can be used suitably especially for manufacture of the thin component mounting board|substrate which the board|substrate warp easily produces.

1 is a diagram showing the names of points A, B, C, and D when calculating S1 and S2.
Fig. 2 is a view for explaining a reflow temperature profile described in IPC/JEDEC J-STD-020C.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on the suitable embodiment.

An embodiment of the present invention provides a thermosetting step of heat-curing a thermosetting resin composition layer formed on an inner-layer substrate to form a cured product layer, and a reflow step of mounting components on a substrate having the cured product layer by reflow. Including, the shrinkage ratio (S1) in the xy direction after the thermosetting process of the thermosetting resin composition layer is 0.35% or less, and the shrinkage ratio (S2) in the xy direction after the reflow process of the cured material layer is 0.4% or less, and , and S1 and S2 satisfy the relationship of S2-S1 ≤ 0.08, it is a method for manufacturing a component mounting board.

<Thermal curing process>

The manufacturing method of this invention includes a thermosetting process, In the thermosetting process, the thermosetting resin composition layer formed on the inner-layer substrate is heat-hardened, and the hardened|cured material layer is formed.

Although the temperature of thermosetting may differ depending on the composition of the thermosetting resin composition used specifically, from a viewpoint of the balance between shortening of curing time and the heat resistance of a board|substrate, it is generally 120 degreeC - 240 degreeC, and 140 degreeC - 210 degreeC is preferable, and 150 to 200°C is more preferable.

The "inner-layer substrate" in the present invention is a substrate used as an intermediate product when manufacturing a printed circuit board such as a component-embedded substrate, and an insulating layer and/or a conductor layer are further formed on the inner-layer substrate to constitute the inner layer of the printed circuit board. It refers to the board to be made. One or both surfaces of the inner layer substrate may have circuit wirings subjected to pattern processing. Examples of the substrate used for the inner layer substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and a coreless substrate. .

When the circuit wiring is provided on one side or both sides of the substrate, the thickness of the circuit wiring is not particularly limited, but from the viewpoint of reducing the thickness of the layer, it is preferably 70 µm or less, more preferably 30 µm or less, and still more preferably It is preferably 20 μm or less. Although the lower limit in particular of the thickness of a circuit wiring is not restrict|limited, Preferably it is 1 micrometer or more, More preferably, it is 3 micrometers or more, More preferably, it is 5 micrometers or more.

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

The thermosetting resin composition used for the thermosetting resin composition layer of this invention is not specifically limited, The hardened|cured material may just have sufficient hardness and insulation as an insulating layer. For example, it is preferable to use a thermosetting resin composition comprising an epoxy resin, a curing agent and an inorganic filler.

(epoxy resin)

Although it does not specifically limit as an epoxy resin used for this invention, Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolak type epoxy resin, tert-butylcatechol type Epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidyl amine type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin Epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, dicyclopentadiene type epoxy resin and the like. You may use these 1 type or in combination of 2 or more types.

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

Although an epoxy resin may use 2 or more types together, it is preferable to contain the epoxy resin which has two or more epoxy groups in 1 molecule. Among them, an aromatic epoxy resin having two or more epoxy groups in one molecule and liquid at a temperature of 20°C (hereinafter referred to as “liquid epoxy resin”.) and three or more epoxy groups in one molecule, having a temperature of 20°C A form containing a solid aromatic epoxy resin (hereinafter referred to as "solid epoxy resin".) is more preferable. In addition, the aromatic epoxy resin as used in this invention means the epoxy resin which has an aromatic ring structure in the molecule|numerator. As an epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used together, when the resin composition is used in the form of an adhesive film, it has moderate flexibility and the cured product of the resin composition has an appropriate breaking strength. (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 further in the range of 1:0.6 to 1:1.5 by mass ratio. desirable.

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

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

In the resin composition suitable for the manufacturing method of this invention, when the nonvolatile component in a resin composition is 100 mass % from a viewpoint of improving the mechanical strength and water resistance of the hardened|cured material of a resin composition, content of an epoxy resin is 3-35 mass It is preferable that it is %, It is more preferable that it is 5-40 mass %, It is more preferable that it is 10-45 mass %.

(hardener)

Although it does not specifically limit as a hardening|curing agent used in this invention, A phenol-type hardening|curing agent, a naphthol-type hardening|curing agent, an active ester-type hardening|curing agent, a benzoxazine-type hardening|curing agent, a cyanate ester-type hardening|curing agent, an acid anhydride-type hardening|curing agent, etc. are mentioned, Among them, a phenol-type hardening|curing agent A curing agent, a naphthol-based curing agent, and an active ester-based curing agent are preferred. You may use these 1 type or in combination of 2 or more types.

Although there is no restriction|limiting in particular as a phenol-type hardening|curing agent and a naphthol-type hardening|curing agent, For example, a phenol-type hardening|curing agent which has a novolak structure, and a naphthol-type hardening|curing agent which has a novolak structure are mentioned, A phenol novolak resin, triazine skeleton containing phenol furnace A bolac resin, a naphthol novolak resin, a naphthol aralkyl type resin, a triazine skeleton containing naphthol resin, and a biphenyl aralkyl type phenol resin are preferable. As a commercial item, it is a biphenyl aralkyl type phenol resin, "MEH-7700", "MEH-7810", "MEH-7851", "MEH7851-4H" (made by Meiwa Kasei Co., Ltd.), "GPH" (Nippon Kaya) Co., Ltd.), as a naphthol novolac resin, "NHN", "CBN" (manufactured by Nippon Kayaku Co., Ltd.), as a naphthol aralkyl resin, "SN170", "SN180", "SN190", "SN475" , "SN485", "SN495", "SN395", "SN375" (manufactured by Toto Kasei Corporation), "TD2090" (manufactured by DIC Corporation) as a phenol novolac resin, phenol novolac resin containing a triazine skeleton "LA3018", "LA7052", "LA7054", "LA1356" (made by DIC Corporation), etc. are mentioned. These may use 1 type or 2 or more types together.

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

As an active ester-type hardening|curing agent containing a dicyclopentadiene type diphenol condensed structure, the compound of the following formula is mentioned more specifically.

In Formula 1,

R is a phenyl group, a naphthyl group,

k is 0 or 1,

n is 0.05 to 2.5 as the average of repeat units.

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

Although there is no restriction|limiting in particular as a benzoxazine type hardening|curing agent, F-a, P-d (made by Shikoku Kasei Co., Ltd.), HFB2006M (made by Showa Kobunshi Co., Ltd.) etc. are mentioned as a specific example.

Although there is no restriction|limiting in particular as a cyanate ester type hardening|curing agent, For example, a novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardener, a dicyclopentadiene type cyanate ester type hardener, a bisphenol type. (Bisphenol A type, bisphenol F type, bisphenol S type, etc.) A cyanate ester type hardening|curing agent and the prepolymer etc. by which these were partially triazined are mentioned. Although the weight average molecular weight of a cyanate ester type hardening|curing agent is not specifically limited, 500-4500 are preferable and 600-3000 are more preferable. Specific examples of the cyanate ester curing agent include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2) ,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenyl propane, 1,1-bis (4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis( Polyfunctional cyanates derived from bifunctional cyanate resins such as 4-cyanatephenyl)thioether and bis(4-cyanatephenyl)ether, phenol novolac, cresol novolac, dicyclopentadiene structure-containing phenol resin, etc. and resins and prepolymers in which these cyanate resins are partially triazined. You may use these 1 type or in combination of 2 or more types.

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

[In the formula (2), n represents an arbitrary number (preferably 0 to 20) as an average value]

A prepolymer in which some or all of the bisphenol A dicyanate represented by the following formula has been triazined to form a trimer (Ronza Japan Co., Ltd., BA230, cyanate equivalent 232)

Cyanate ester resin containing dicyclopentadiene structure represented by the following formula (manufactured by Ronza Japan Co., Ltd., DT-4000, DT-7000)

[In Formula 4, n represents a number of 0 to 5 as an average value]

and the like.

Although it does not specifically limit as an acid anhydride type hardening|curing agent, For example, For example, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride , trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride , trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4, 4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[ and polymeric acid anhydrides such as 1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and styrene/maleic acid resin copolymerized with styrene and maleic acid.

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

In the above resin composition, from the viewpoint of improving the mechanical strength and water resistance of the cured product of the resin composition, when the nonvolatile component in the resin composition is 100% by mass, the content of the curing agent is preferably 3 to 30% by mass, 5 It is more preferable that it is -25 mass %, and it is still more preferable that it is 10-20 mass %.

(Inorganic filling material)

It is preferable that the thermosetting resin composition of this invention contains an inorganic filler from a viewpoint of a thermal expansion coefficient fall. Although it does not specifically limit as an inorganic filler to be used, For example, Silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, titanic acid. Barium, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, etc. are mentioned. Among them, silica is preferable. Further, preferred are silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, spherical silica, and titanium doped silica. Moreover, as a silica, a spherical thing is preferable. As an example of a spherical silica, "SOC1" and "SOC2" by Adomatex Corporation are mentioned. You may use an inorganic filler 1 type or in combination of 2 or more type. In the present invention, adjustment of the coefficient of thermal expansion can be performed by adjusting the type and amount of components contained in the thermosetting resin composition. In particular, since the inorganic filler greatly contributes to the low thermal expansion of the thermosetting resin composition, the type of the inorganic filler By adjusting the amount of , it is possible to suitably adjust the coefficient of thermal expansion. Moreover, since titanium-doped silica becomes especially low thermal expansion tendency among an inorganic filler, in order to adjust the value of thermal expansion coefficient in this invention, it can be used especially suitably.

The term "titanium-doped silica" means, for example, _{TiCl 4} and SiCl ₄ , which are raw materials for forming glass of _{TiO 2} -SiO ₂ glass, respectively, after gasifying, mixing, and thermal hydrolysis (flame hydrolysis) in an oxyhydrogen flame. TiO ₂ -SiO ₂ glass microparticles obtained. The silica doped with titanium is well-known, As an example of a commercial item, the "AZ filler" by Asahi Glass Co., Ltd. is mentioned. When titanium-doped silica is blended with the inorganic filler, the amount of the inorganic filler contained in the resin composition is 100% by mass, and the compounding amount of the titanium-doped silica in the inorganic filler is preferably 10% by mass or more, 20 mass % or more is more preferable, 30 mass % or more is more preferable, 40 mass % or more is more preferable, 50 mass % or more is more preferable, 60 mass % or more is more preferable, 70 mass % or more is more preferable. More preferably, 80 mass % or more is more preferable, 90 mass % or more is more preferable, and 100 mass % is especially preferable.

Moreover, as an inorganic filler, in order to improve moisture resistance and dispersibility, a silane coupling agent (epoxy silane type coupling agent, aminosilane type coupling agent, mercapto silane type coupling agent, etc.), a titanate type coupling agent, a silazane compound What surface-treated with surface treating agents, such as these is preferable. You may use these 1 type or in combination of 2 or more types.

Examples of the epoxy silane coupling agent include glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3, 4-epoxycyclohexyl) ethyl trimethoxysilane etc. are mentioned, As an aminosilane type coupling agent, aminopropyl methoxysilane, aminopropyl triethoxysilane, N-phenyl-3- aminopropyl tri, for example. Methoxysilane, N-2 (aminoethyl) aminopropyl trimethoxysilane, etc. are mentioned, As a mercapto silane type coupling agent, For example, mercaptopropyl trimethoxysilane, mercaptopropyl triethoxysilane. and the like. You may use these 1 type or in combination of 2 or more types. As a commercially available coupling agent, for example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyl trimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercapto) propyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltri methoxysilane) and the like.

Although the average particle diameter of the inorganic filler is not particularly limited, the upper limit of the average particle diameter of the inorganic filler is preferably 5 µm or less, more preferably 3 µm or less, from the viewpoint of forming fine wiring on the insulating layer, 1 micrometer or less is more preferable, 0.7 micrometer or less is still more preferable, 0.5 micrometer or less is especially preferable, 0.4 micrometer or less is especially preferable, and 0.3 micrometer or less is especially more preferable. On the other hand, the lower limit of the average particle diameter of the inorganic filler is preferably 0.01 µm or more, and 0.03 from the viewpoint of preventing an increase in the viscosity of the varnish and a decrease in handleability when the epoxy resin composition is used as a resin composition varnish. Micrometer or more is more preferable, 0.05 micrometer or more is still more preferable, 0.07 micrometer or more is especially preferable, 0.1 micrometer or more is especially preferable. The average particle diameter of the said inorganic filler can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, it can measure by creating the particle size distribution of an inorganic filler on a volume basis with a laser diffraction type particle size distribution measuring apparatus, and making the median diameter into an average particle diameter. As a measurement sample, what disperse|distributed the inorganic filler in water by ultrasonic wave can be used preferably. As a laser diffraction type particle size distribution measuring apparatus, Horiba Corporation LA-500, 750, 950, etc. can be used.

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

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

-Thermoplastic resin-

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

The range of 8,000-70,000 is preferable, as for the weight average molecular weight of polystyrene conversion of a thermoplastic resin, the range of 10,000-60,000 is more preferable, The range of 20,000-60,00 is still more preferable. The weight average molecular weight in terms of polystyrene 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 was measured as a measuring device (LC-9A/RID-6A manufactured by Shimadzu Corporation, Shodex K-800P/K manufactured by Showa Denko Corporation as a column) -804L/K-804L can be calculated using a standard polystyrene calibration curve using chloroform or the like as a mobile phase and measuring at a column temperature of 40°C.

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

Specific examples of the polyvinyl acetal resin include Denki Butyral 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Denki Chemical Co., Ltd., S-Rec BH series manufactured by Sekisui Chemical Co., Ltd. , BX series, KS series, BL series, BM series, and the like.

As a specific example of polyimide resin, "Ricacoat SN20" and "Ricacoat PN20" by Shin-Nippon Rica Co., Ltd. are mentioned. As a specific example of the polyimide resin, furthermore, a linear polyimide obtained by reacting a difunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (the one described in Japanese Patent Application Laid-Open No. 2006-37083); Modified polyimides, such as polysiloxane skeleton containing polyimide (the thing described in Unexamined-Japanese-Patent No. 2002-12667, Unexamined-Japanese-Patent No. 2000-319386, etc.) are mentioned.

Specific examples of the polyamideimide resin include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyo Boseki Co., Ltd. Specific examples of the polyamideimide resin include modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Corporation.

As a specific example of polyether sulfone resin, the Tsumitomo Chemical Co., Ltd. product "PES5003P" etc. are mentioned.

As a specific example of polysulfone resin, the polysulfone "P1700", "P3500" of Solvay Advansto Formaz Co., Ltd. product, etc. are mentioned.

When content of the non-volatile component in a resin composition is 100 %, it is preferable that content of the thermoplastic resin in a resin composition is 0.1 mass % - 20 mass %. By making content of a thermoplastic resin into such a range, the viscosity of a resin composition becomes moderate, and the uniform resin composition of thickness and bulk property can be formed. When content of the thermoplastic resin in a resin composition makes the nonvolatile component in a resin composition 100 mass %, it is more preferable that they are 1 mass % - 10 mass %.

-curing accelerator-

Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators, and amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators. Accelerators are preferred.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphoniumdecanoate, (4-methylphenyl)triphenyl Phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc. are mentioned, Triphenyl phosphine and tetrabutyl phosphonium decanoate are preferable.

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimeritate, 1-cyanoethyl-2-phenylimidazolium Trimeritate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl Imidazolyl-(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-triazineisocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a ]Imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins sieves, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, and diphenylguanidine. , trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc. are mentioned, dicyandiamide, 1,5,7-triazabicyclo[4.4.0]deca-5-ene is preferred.

Although it does not specifically limit as a metal type hardening accelerator, For example, organometallic complexes or organometallic salts of metals, such as cobalt, copper, zinc, iron, nickel, manganese, and tin, are mentioned. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organic copper complexes such as copper(II) acetylacetonate, and organic copper complexes such as zinc(II) acetylacetonate. and organic iron complexes such as zinc complex and iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like. You may use these 1 type or in combination of 2 or more types.

In the resin composition of the present invention, an organic cobalt complex is preferably used as the metal-based curing accelerator, and in particular, cobalt (III) acetylacetonate is preferably used. When the content of the metal-based curing accelerator is 100% by mass of the nonvolatile component in the resin composition, the content of the metal 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. .

A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type. When content of the hardening accelerator in a resin composition makes the nonvolatile component in a resin composition 100 mass %, 0.01 mass % - 1 mass % are preferable, 0.02 mass % - 0.5 mass % are more preferable, 0.03 mass % - 0.1 % by mass is even more preferred.

-Flame retardant-

Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide, and 10-(2,5-dihydroxyphenyl)-10-hydro-9- Oxa-10-phosphaphenanthrene-10-oxide (for example, Sanko Corporation "HCA-HQ") is preferable. A flame retardant may be used individually by 1 type, or may use 2 or more types together. The content of the flame retardant in the resin composition layer is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 5% by mass, , 1.5 mass % - 3 mass % are more preferable.

<Reflow process>

The manufacturing method of this invention includes a reflow process, In a reflow process, a component is mounted by reflow on the board|substrate which has the hardened|cured material layer manufactured by the said thermosetting process.

It does not specifically limit as a component to mount, For example, although a semiconductor, an interposer, a passive element etc. are mentioned, The manufacturing method of this invention can be used especially suitably for semiconductor mounting.

The heating temperature in the reflow step may vary depending on conditions such as the type of solder used or the type of components to be mounted, but is generally 210°C to 330°C, preferably 220°C to 300°C, and 230°C to 230°C. 280 degreeC is more preferable. The manufacturing method of the present invention is more suitable when a lead-free solder is used as the solder.

The manufacturing method of this invention contains the said thermosetting process and the said reflow process.

In the method for manufacturing a component mounting board of the present invention, the shrinkage rate (S1) in the xy direction after the thermosetting step of the thermosetting resin composition layer is 0.35% or less, preferably 0.3% compared to the thermosetting resin composition layer before the thermosetting step Hereinafter, it is more preferably 0.2% or less, and the shrinkage ratio (S2) in the xy direction of the cured material layer after the reflow step is 0.4% or less, preferably 0.3% or less, compared to the thermosetting resin composition layer before the thermosetting step. , 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 measurements of S1 and S2 are performed as follows.

<Measurement of S1>

(1-1) Measurement of initial length

Four through holes are formed by punching in a portion about 20 mm from the square of the 200 mm square resin of the thermosetting resin composition layer (thickness 40 μm) (the holes A, B, C, D) and the length L(L _AB , L _BC , L _CD , L _DA , L _AC , L _BD ) between the centers of each formed hole (see FIG. 1 ) are measured with a non-contact image measuring device.

(1-2) Thermosetting of thermosetting resin composition layer

The thermosetting resin composition layer whose length measurement has been completed is heated and thermosetted.

(1-3) Measurement of thermal curing shrinkage

After thermosetting, in the cured thermoplastic resin composition layer, the length L'(L' _AB , L' _BC , L' _CD , L' _DA , L after curing between the centers of the holes formed in (1-1)) ' _AC , L' _BD ), like L, is measured with a non-contact image measuring instrument.

_S 1 _AB =(L _AB -L' _AB )/L _AB

to calculate Similarly, s1 _BC , s1 _CD , s1 _DA , s1 _AC , s1 _DA , L _BC and L' _BC , L _CD and L' _CD , L _DA and L' _DA , L _AC and L' _AC , L _BD and L' _BD .

The thermosetting shrinkage rate is computed by the following formula|equation.

Thermosetting shrinkage [Shrinkage in x-y direction: S1] (%)

={(s1 _AB + s1 _BC + s1 _CD + s1 _DA + s1 _AC +s1 _DA )/6}×100

<Measurement of S2>

(1-4) Reflow process

The substrate after the step (1-3) has been completed is reflowed.

(1-5) Measurement of reflow shrinkage

After the reflow step, in the exact same manner as in (1-3), the length L"(L" _AB , L" _BC , L" _CD , L" after reflow between the centers of the holes formed in (1-1)) _DA , L" _AC , L" _BD ) are measured with a non-contact imager, like L.

s2 _AB =(L _AB -L" _AB )/L _AB

to calculate Similarly, s2 _BC , s2 _CD , s2 _DA , s2 _AC , s2 _DA , L _BC and L" _BC , L _CD and L" _CD , L _DA and L" _DA , L _AC and L" _AC , L _BD and L" _BD .

A reflow shrinkage rate is computed with the following formula.

Reflow shrinkage [shrinkage in x-y direction: S2] (%)

={(s2 _AB + s2 _BC + s2 _CD + s2 _DA + s2 _AC +s2 _DA )/6}×100

The above parameters can preferably be satisfied by using a thermosetting resin composition containing the previously described epoxy resin, curing agent and inorganic filler. According to such a thermosetting resin composition, the hardened|cured material suitable for the insulating layer in which the shrinkage|contraction of an insulating layer was suppressed and warpage was suppressed and the deformation|transformation of a board|substrate hardly produced can be obtained. The hardened|cured material of this thermosetting resin composition is suitable for manufacture of a component mounting board|substrate (especially semiconductor mounting board|substrate), and it is also suitable especially for forming the insulating layer of a board|substrate. The thickness of one hardened|cured material layer (1 insulating layer) is about 3-200 micrometers normally, but in the case of multilayering, the thickness of the whole insulating layer becomes thicker than this, and it becomes about 10-300 micrometers normally.

<Thermosetting resin composition>

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

The said thermosetting resin composition is a reflow temperature profile based on IPC/JEDEC J-STD-020C of the hardened|cured material of the said thermosetting resin composition thermosetting under the condition that the shrinkage rate (S1) in the xy direction after thermosetting becomes 0.35% or less. The shrinkage ratio (S2) in the xy direction after heating with a furnace 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 thermosetting under the condition that the shrinkage ratio (S1) in the xy direction after thermosetting is 0.35% or less is heated to a reflow temperature profile in accordance with IPC/JEDEC J-STD-020C in the xy direction As long as the shrinkage ratio (S2) of is 0.4% or less and S1 and S2 satisfy the relationship of S2-S1 ≤ 0.08, the thermoplastic resin composition will warp of the substrate even after high temperature of component mounting by the reflow process. This is difficult to occur and is suitable for forming an insulating layer on a thin component mounting substrate.

Suitable examples of the raw material that can be used for the thermoplastic resin composition are as described above.

The method of measuring S1 and S2 is as described above.

The reflow temperature profile described in IPC/JEDEC J-STD-020C is cited in FIG. 2 and Tables 1-3. The time may be any condition within the range described in the table. For example, for Sn-Pb eutectic solder, t _S = 90 sec, t _L = 105 sec, t _P = 20 sec, and for Pb-free solder, t _{Conditions such that S} = 120 seconds, t _L =105 seconds, and t _P =30 seconds are exemplified. In addition, in this invention, the package mentioned here corresponds to the board|substrate before component mounting by reflow. The package thickness is preferably less than 2.5 mm if it is a Sn-Pb eutectic solder, preferably less than 2.5 mm if it is a Pb-free solder, more preferably less than 2.5 mm to 1.6 mm, and still more preferably less than 1.6 mm.

The said thermosetting resin composition can be used suitably as a resin composition (resin composition for insulating layers on an inner-layer board|substrate) for forming the insulating layer of a multilayer printed wiring board. By using the above thermosetting resin composition to form the insulating layer of the multilayer printed wiring board, the shrinkage of the insulating layer is suppressed, an insulating layer that is less prone to deformation of the substrate can be realized, and the problem of warpage of the substrate can be significantly improved. . Among them, in the production of a multilayer printed wiring board by a build-up method, it can be suitably used as a resin composition for forming an insulating layer (resin composition for a build-up insulating layer of a multilayer printed wiring board), and a conductor is plated thereon. It can be used further suitably as a resin composition (resin composition for buildup insulating layers of a multilayer printed wiring board which forms a conductor layer by plating) for forming the insulating layer in which a layer is formed. Moreover, the said thermosetting resin composition can be used suitably also when a multilayer printed wiring board is a circuit board with built-in components. That is, the resin composition of this invention can be used suitably as a resin composition (resin composition for component embedding) for embedding a component built-in circuit board component. Regarding the core board used for manufacturing the circuit board with built-in components, it has a cavity for embedding components, and the density of the cavity tends to increase due to the request for miniaturization of the circuit board itself with built-in components, and due to the lack of rigidity of the core board. Although the problem of warpage tends to become more serious, by using the thermosetting resin composition as a resin composition for embedding components, the problem of warpage can be significantly alleviated even when a core substrate having a high cavity density and a thin core is used.

<Prepreg>

The said thermosetting resin composition is good also as a prepreg by impregnating a sheet-like fiber base material. A prepreg is formed by impregnating the said thermosetting resin composition in a sheet-like fiber base material.

The sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as the base material for prepregs, such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric, can be used. When used for the formation of the insulating layer of a multilayer printed wiring board, a thin sheet-like fibrous substrate having a thickness of 50 µm or less is preferably used, and in particular, a sheet-like fibrous substrate having a thickness of 10 µm to 40 µm is preferable, and 10 µm to A 30-micrometer sheet-like fiber base material is more preferable, and a 10-20 micrometers sheet-like fiber base material is still more preferable. As a specific example of the glass cloth base material used as a sheet-like fiber base material, "Style 1027MS" (warp) density of 75 pieces/25 mm by Asahi Shueberu Co., Ltd. and a weft density of 75 pieces/25 mm , fabric weight 20 g/m2, thickness 19 µm), "Style 1037MS" manufactured by Asahi Shueberu Co., Ltd. (warp density 70/25mm, weft density 73/25mm, fabric weight 24g/m2, thickness 28 μm), “1078” manufactured by Arisawa Sesakusho Co., Ltd. (warp density 54/25 mm, weft density 54/25 mm, fabric weight 48 g/m2, thickness 43 μm), Arisawa Sesaku Co., Ltd. "1037NS" manufactured by Shaw (warp density of 72 pieces/25mm, weft density of 69 pieces/25mm, fabric weight 23g/m2, thickness 21㎛), "1027NS" manufactured by Arisa and Sesakusho Co., Ltd. (warp density 75 pieces) /25mm, weft density 75/25mm, fabric weight 19.5g/m2, thickness 16㎛), Arisa and Sesakusho Co., Ltd. "1015NS" (warp density 95/25mm, weft density 95/25mm, Fabric weight 17.5 g/m2, thickness 15 µm), "1000NS" manufactured by Arisa and Sesakusho Co., Ltd. (warp density 85/25 mm, weft density 85/25 mm, fabric weight 11 g/m2, thickness 10 µm) and the like. In addition, as a specific example of the liquid crystal polymer nonwoven fabric, "Vekurus" (amount of wood 6 to 15 g/m2) by a melt blow method of an aromatic polyester nonwoven fabric manufactured by Kuraray Co., Ltd., "Bekutoran", etc. can be heard

You may manufacture a prepreg by well-known methods, such as a hot melt method and a solvent method.

In one embodiment of the present invention, the thermosetting resin composition layer is a component mounting substrate formed by laminating a prepreg with a carrier on a carrier film, a prepreg formed by impregnating a fiber base with the thermosetting resin composition to an inner layer substrate.

<Multilayer printed wiring board using prepreg>

Next, an example of the method of manufacturing a multilayer printed wiring board using the prepreg manufactured as mentioned above is demonstrated. One sheet or several sheets of the prepreg of this invention are laminated|stacked on a circuit board as needed, it pinches|interposed with a metal plate through a release film, and vacuum press lamination|stacking under pressure and heating conditions. The pressure/heating conditions are preferably 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. Moreover, after laminating a prepreg on a circuit board by the vacuum lamination method similarly to an adhesive film, it is also possible to heat-harden. Then, after carrying out similarly to the method described above, after roughening the hardened|cured prepreg surface, a conductor layer is formed by plating, and a multilayer printed wiring board can be manufactured.

<Adhesive film>

An adhesive film may be formed using the thermosetting resin composition.

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

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

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, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Acetic acid esters, such as cellosolve, carbitols, such as butylcarbitol, aromatic hydrocarbons, such as toluene and xylene, amide solvents, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are mentioned. can An organic solvent may be used individually by 1 type, or may use 2 or more types together.

The resin varnish may be dried by a known drying method such as heating or hot air spraying. Although it also varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30 mass % to 60 mass % of an organic solvent, by drying at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes, the adhesive film can form.

As a support body used for formation of an adhesive film, the film which consists of a plastic material, metal foil (copper foil, aluminum foil, etc.), and a release paper are mentioned, The film which consists of a plastic material is used suitably. Examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”), and polycarbonate (hereinafter, abbreviated as “PEN”). "PC" may be abbreviated), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. can Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable. In one suitable embodiment, the support is a polyethyleneterephthalate film.

A support body may give a mad process and corona treatment to the surface to join with the resin composition layer.

Moreover, as a support body, you may use the support body with a mold release layer which has a mold release layer on the surface to join with the resin composition layer. As a mold release agent used for the mold release layer of a support body with a mold release layer, 1 or more types of mold release agents are mentioned from the group which consists of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin, for example.

In this invention, you may use a commercial item as a support body with a mold release layer. As a commercial item, "SK-1", "AL-5", "AL-7" etc. which are PET film which is a PET film which has a release layer which has an alkyd resin type release agent as a main component, for example, manufactured by Lintec Corporation are mentioned, for example. .

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

In the adhesive film produced by using the thermosetting resin composition as described above, the thickness of the resin composition layer is not particularly limited, but from the viewpoint of reducing the thickness of the multilayer printed wiring board, preferably 100 µm or less, more preferably 80 µm or less ㎛ or less, more preferably 60 ㎛ or less, even more preferably 50 ㎛ or less. The minimum of the thickness of a resin composition layer is 15 micrometers or more normally.

As described above, in the adhesive film produced using the thermosetting resin composition, a protective film conforming to the support is additionally laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). can Although the thickness of a protective film is not specifically limited, For example, it is 1 micrometer - 40 micrometers. By laminating|stacking a protective film, adhesion of dust, etc. to the surface of a resin composition layer, and a flaw can be prevented. An adhesive film can be wound up in roll shape and can be stored, and when forming an insulating layer in manufacture of a multilayer printed wiring board, it becomes usable by peeling off a protective film.

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

<Multilayer printed wiring board using adhesive film>

An example of the method of manufacturing a multilayer printed wiring board using the adhesive film manufactured as mentioned above is demonstrated.

First, an adhesive film is laminated on one or both sides of a circuit board using a vacuum laminator. As a board|substrate used for a circuit board, a glass epoxy board|substrate, a metal board|substrate, a polyester board|substrate, a polyimide board|substrate, a BT resin board|substrate, a thermosetting polyphenylene ether board|substrate etc. are mentioned, for example. In addition, the circuit board here means that the conductor layer (circuit) by which the pattern process was formed is formed on one side or both surfaces of the board|substrate as mentioned above. Further, in a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, one or both surfaces of the outermost layer of the multilayer printed wiring board are pattern-processed conductor layers (circuits). Included. Moreover, the roughening process may be previously given to the conductor layer surface by blackening process, copper etching, etc.

In the above laminate, when the adhesive film has a protective film, after the protective film is removed, the adhesive film and the circuit board are preheated if necessary, and the adhesive film is pressed against the circuit board while pressing and heating. In the adhesive film of this invention, the method of laminating on a circuit board under reduced pressure by the vacuum lamination method is used suitably. The conditions of the lamination are not particularly limited, but, for example, the compression temperature (laminate temperature) is preferably 70 to 140°C, and the compression pressure is preferably 1 to 11 kgf/cm 2 (9.8 × 10 ⁴ to 107.9 × 10 ^{4 )} N/m 2 ) and lamination is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less. In addition, the method of lamination may be a batch type, or the continuous type with a roll may be sufficient as it. Vacuum lamination can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, For example, Nichigo Morton Co., Ltd. vacuum applicator, Meiki Sesakusho's vacuum pressurization type laminator, Hitachi Industries, Ltd. roll type dry coater, Hitachi AICI Co., Ltd. A Geisha vacuum laminator etc. are mentioned.

In addition, the lamination|stacking process of heating and pressurizing under reduced pressure can also be performed using a general vacuum hot press machine. For example, it can carry out by pressing metal plates, such as a heated SUS plate, from the support body layer side. Press conditions make the degree of reduced pressure under a reduced pressure of usually 1×10 ^-2 MPa or less, preferably 1×10 ^-3 MPa or less. Although heating and pressurization may be performed in one step, it is preferable to carry out by dividing conditions into two or more steps from a viewpoint of controlling the leaching of resin. For example, the press of the first step, the temperature is 70 to 150 ℃, the pressure is in the range of 1 to 15 kgf / ㎠, the second stage press, the temperature is 150 to 200 ℃, the pressure is 1 to 40 kgf / ㎠ It is preferable to do it within the range. The time for each step is preferably 30 to 120 minutes. As a commercially available vacuum hot press machine, MNPC-V-750-5-200 (made by Meiki Sesakusho Co., Ltd.), VH1-1603 (made by Kitagawa Seiki Co., Ltd.) etc. are mentioned, for example. .

The thermosetting resin composition layer is preferably formed by laminating an adhesive film in which a thermosetting resin crude composition layer is formed on a carrier film on an inner layer substrate. After laminating an adhesive film on a circuit board, after cooling to room temperature vicinity, when peeling a support body, it peels and can form an insulating layer in a circuit board by thermosetting. The thermosetting conditions may be appropriately selected depending on the type, content, etc. of the resin component in the resin composition, preferably at 150° C. to 220° C. for 20 minutes to 180 minutes, more preferably at 160° C. to 210° C. for 30 to 120 minutes. selected from the range of minutes.

After forming an insulating layer, when a support body is not peeled before hardening, it peels here. Next, if necessary, the insulating layer formed on the circuit board is drilled to form a via hole and a through hole. Although the drilling can be performed, for example, by a known method such as a drill, a laser, a plasma, or a combination of these methods if necessary, the drilling by a laser such as a carbon dioxide laser or a YAG laser is the most common method. to be.

Then, a conductor layer is formed on the insulating layer by dry plating or wet plating. As dry plating, well-known methods, such as vapor deposition, sputtering, and ion plating, can be used. In the case of wet plating, an uneven anchor is formed by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid on the surface of the insulating layer in this order. The swelling treatment by the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 to 80°C for 5 to 20 minutes. Examples of the swelling solution include an alkali solution and a surfactant solution, preferably an alkali solution, and examples of the alkali solution include a sodium hydroxide solution and a potassium hydroxide solution. As a commercially available swelling liquid, Swelling Dip Securiganth P (Swelling Dip Securiganth P) by Atotech Japan Co., Ltd., Swelling Dip Securiganth SBU, etc. are mentioned, for example. The roughening process by an oxidizing agent is performed by immersing an insulating layer in the oxidizing agent solution at 60 degreeC - 80 degreeC for 10 minutes - 30 minutes. As an oxidizing agent, the alkaline permanganic acid solution which melt|dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid etc. are mentioned, for example. In addition, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by weight. As a commercially available oxidizing agent, alkaline permanganic acid solutions, such as Atotech Japan Co., Ltd.|KK Concentrate Compact CP, and dosing solution Securiganth P, are mentioned, for example. The neutralization treatment with a neutralizing liquid is performed by immersing in the neutralizing liquid at 30-50 degreeC for 3 to 10 minutes. As a neutralizing liquid, an acidic aqueous solution is preferable, As a commercial item, Atotech Japan Co., Ltd. product reduction solution security P is mentioned.

Next, a conductor layer is formed by combining electroless plating and electrolytic plating. In addition, a plating resist having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. As a method of pattern formation thereafter,

For example, the subtractive method, the semi-additive method, etc. which are well-known to those skilled in the art can be used.

By using the multilayer printed wiring board manufactured using the thermosetting resin composition, it is possible to manufacture a substrate on which components such as a semiconductor chip, an interposer, and a passive element are mounted.

An example of the manufacturing method of a semiconductor mounting board|substrate is described.

<Semiconductor mounting board>

A semiconductor mounting board can be manufactured by mounting a semiconductor chip in the conduction|electrical_connection location of the multilayer printed wiring board manufactured using the said thermosetting resin composition. A "conduction location" is "a location through which an electric signal is transmitted in a multilayer printed wiring board", and the location may be a surface or a buried location, either. In addition, a semiconductor chip will not be specifically limited if it is an electric circuit element which uses a semiconductor as a material.

The semiconductor chip mounting method when manufacturing the semiconductor mounting substrate is not particularly limited as long as the semiconductor chip functions effectively, and specifically, a wire bonding mounting method, a flip chip mounting method, and a bumpless build-up layer The mounting method by (BBUL), the mounting method by an anisotropic conductive film (ACF), the mounting method by a nonelectroconductive film (NCF), etc. are mentioned.

[Example]

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, "part" in the following description means a "mass part."

First, the measuring method and evaluation method in the physical property evaluation in this specification are demonstrated.

[Measurement of shrinkage]

(1-1) Preparation of polyimide film with resin

For the resin sheet (200 mm square) produced in the following production example, a batch type vacuum pressurization laminator (2-stage build-up laminator CVP700 manufactured by Nichigo Morton, Ltd.) was used, and the resin composition layer was a polyimide film (Ube). It was laminated on one side so that it might contact with the center of the smooth surface of Kosan Corporation Upirex 25S, 25 micrometers thickness, 240 mm square). After lamination was pressure-reduced for 30 second and the atmospheric pressure was 13 hPa or less, it performed by crimping|bonding for 30 second at 100 degreeC and pressure 0.74 MPa.

(1-2) Measurement of initial length

Four through holes (diameter of about 6 mm) were formed by punching the obtained polyimide film with resin from the top of the resin sheet support, in a portion about 20 mm from the square of a 200 mm square resin, (the holes were clockwise A , B, C, and D.), the length L between the centers of the holes formed after peeling off the support of the resin sheet (L _AB , L _BC , L _CD , L _DA , L _AC , L _BD ) (FIG. 1) was measured with a non-contact image measuring device (manufactured by Mitsutoyo Co., Ltd., Quick Vision format: QVH1X606-PRO Ⅲ_BHU2G).

(1-3) Thermosetting of the resin composition layer

The polyimide film side of the polyimide film with resin after length measurement is mounted on a glass cloth-based epoxy resin double-sided copper-clad laminate (0.7 mm thick, "R5715ES" manufactured by Matsushita Denko Co., Ltd.) of 255 mm × 255 mm size, 4 The sides were fixed with polyimide adhesive tape (width 10 mm), and the resin composition layer was thermosetted by heating at 150° C. for 90 minutes to obtain a cured product layer. Similarly, it heated at 190 degreeC for 90 minutes and 200 degreeC for 90 minutes, respectively, and obtained hardened|cured material layer.

(1-4) Measurement of heat curing shrinkage

After thermosetting, the polyimide adhesive tape is peeled off, the polyimide film with a cured material layer is peeled off from the laminate, and the cured material layer is further peeled from the polyimide film, between the centers of the holes formed in (1-2). The length L'(L' _AB , L' _BC , L' _CD , L' _DA , L' _AC , L' _BD ) after curing was measured with a non-contact imager like L.

s1 _AB =(L _AB -L' _AB )/L _AB

was calculated. Similarly, s1 _BC , s1 _CD , s1 _DA , s1 _AC , s1 _DA , L _BC and L' _BC , L _CD and L' _CD , L _DA and L' _DA , L _AC and L' _AC , L _BD and L' _BD were calculated.

The thermosetting shrinkage rate was computed with the following formula.

Thermal curing shrinkage [shrinkage in x-y direction: S1] (%)

={(sl _AB +s1 _BC +s1 _CD +s1 _DA +s1 _AC +s1 _DA )/6}×100

(1-5) Reflow process

The substrate having completed the step (1-3) was transferred to a reflow device with a peak temperature of 260° C. (“HAS-6116” manufactured by Nippon Antomu Co., Ltd., the temperature profile conformed to IPC/JEDEC J-STD-020C) passed once.

(1-6) Measurement of reflow shrinkage

_{After the reflow step, the length L"(L" AB} , L" _BC , L" _CD , L" after reflow between the centers of the holes formed in (1-2) in the exact same manner as in (1-4). _DA , L" _AC , L" _BD ) were measured with a non-contact imager as L.

s2 _AB =(L _AB -L" _AB )/L _AB

was calculated. Similarly, s2 _BC , s2 _CD , s2 _DA , s2 _AC , s2 _DA , L _BC and L" _BC , L _CD and L" _CD , L _DA and L" _DA , L _AC and L" _AC , L _BD and L" _BD .

The reflow shrinkage rate was computed with the following formula.

Reflow shrinkage [shrinkage in x-y direction: S2] (%)

={(s2 _AB + s2 _BC + s2 _CD + s2 _DA + s2 _AC +s2 _DA )/6}×100

[Preparation of substrate for reflow behavior evaluation]

(2-1) Preparation of inner layer substrate

As the inner-layer substrate, a glass cloth-based epoxy resin laminate (unclad plate with copper foil etching-out completed, 0.06 mm thick, “LaXY-4785TH-B” manufactured by Tsumitomo Bakelite Co., Ltd.) was prepared.

(2-2) Lamination of resin sheets

The resin sheet produced in the following Production Example was laminated on both sides of the inner layer substrate so that the resin composition layer was in contact with the inner layer substrate using a batch vacuum pressurized laminator (2-stage build-up laminator CVP700 manufactured by Nichigo Morton Co., Ltd.). . After lamination was pressure-reduced for 30 second and the atmospheric pressure was 13 hPa or less, it performed by crimping|bonding for 30 second at 100 degreeC and pressure 0.74 MPa. Then, it hot-pressed for 60 second at 100 degreeC and the pressure of 0.5 MPa.

(2-3) Thermosetting of the resin composition layer

After peeling the support body of the resin sheet from the board|substrate on which the resin sheet was laminated, it heated at 150 degreeC for 90 minutes, the resin composition layer was thermosetted, and the hardened|cured material layer was obtained. Similarly, it heated at 190 degreeC for 90 minutes and 200 degreeC for 90 minutes, respectively, and hardened|cured material layers were obtained.

(2-4) Reflow behavior evaluation

After cutting into 45 mm square pieces (n = 5), it was passed once through a reflow device ("HAS-6116" manufactured by Nippon Antomu Co., Ltd.) having a peak temperature of 260°C (this condition is also IPC /According to JEDEC J-STD-020C). Next, using a Shadow Moire apparatus (TherMoire AXP manufactured by Akrometrix), heating was performed from the bottom of the substrate in a temperature profile conforming to IPC/JEDEC J-STD-020C (peak temperature 260° C.), and the center of the substrate was 10 mm square. The bending behavior of the part was measured.

The difference between the maximum height and the minimum height of the obtained displacement data was 40 μm or more for even one sample in the entire temperature range, and ×, and less than 40 μm for all samples was designated as ○.

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

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

12 parts of bisphenol A epoxy resin (“828EL” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 185), 3 parts of naphthalene-type epoxy resin (“HP4032SS” manufactured by DIC Corporation, about 144 epoxy equivalent), biphenyl type 6 parts of epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 185), 25 parts of biphenyl type epoxy resin (“NC3000H” manufactured by Nippon Kayaku Co., Ltd., about 288 epoxy equivalent), phenoxy resin (Mitsubishi Chemical Co., Ltd. "YX6954BH30", MEK/cyclohexanone = 1/1 solution of 30 mass % of solid content) 20 parts were heat-dissolved, stirring 15 parts of solvent naphtha. After cooling to room temperature, thereto, 20 parts of a triazine skeleton-containing phenol novolac curing agent (“LA-7054” manufactured by DIC Corporation, a MEK solution having a hydroxyl equivalent of 125 and a solid content of 60%), a naphthol-based curing agent (thinnit) Tetsu Chemical Co., Ltd. "SN485", hydroxyl equivalent 215, MEK solution having a solid content of 60%) 10 parts, a curing accelerator (4-dimethylaminopyridine (DMAP), a MEK solution having a solid content of 5% by mass) 0.4 parts, a flame retardant ( "HCA-HQ" manufactured by Sanko Corporation, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 2 µm) 3 Spherical silica (average particle diameter 0.25 μm, “SOC1” manufactured by Adomatex Co., Ltd., carbon amount per unit surface area of 0.36) surface-treated with an amino silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) mg/m) 40 parts, a spherical glass filler (average particle diameter 0.2 μm, “AZ filler” manufactured by Asahi Glass Co., Ltd.) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) , 0.38 mg/m 2) 10 parts of carbon per unit surface area were mixed and uniformly dispersed with a high-speed rotary mixer to prepare resin varnish 1.

Next, on the release layer side of the alkyd resin-based PET film with a release layer ("AL5" manufactured by Lintec Corporation, 38 µm in thickness), the resin varnish 1 is uniformly applied so that the thickness of the resin composition layer after drying is 40 µm, 80 The resin sheet 1 was produced by drying at ∼120°C (average 100°C) for 5 minutes.

<Production Example 2 (Production of Resin Sheet 2)>

5 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Shin-Nippon Chemical Co., Ltd., 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent of about 169) 5 parts, biphenyl type epoxy resin (Mitsubishi Chemical Co., Ltd.) Co., Ltd. "YX4000HK", epoxy equivalent about 185) 12 parts, dicyclopentadiene type epoxy resin (DIC Corporation "HP-7200H", epoxy equivalent about 275) 9 parts, phenoxy resin (Mitsubishi Chemical Co., Ltd.) "YL7553BH30" manufactured by Corporation, and 16 parts of MEK/cyclohexanone = 1/1 solution of 30 mass % of solid content) were heat-dissolved, stirring 30 parts of solvent naphtha. After cooling to room temperature, 40 parts of an active ester curing agent ("HPC8000-65T" manufactured by DIC Corporation, about 223 active group equivalents, 65% by mass of nonvolatile matter in toluene solution), a curing accelerator (4-dimethylamino) 3 parts of pyridine, MEK solution having a solid content of 5% by mass), spherical silica (average particle diameter of 0.5 µm, Adomatex Corporation) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) Manufactured "SOC2", carbon content per unit surface area of 0.38 mg/m2) 100 parts, spherical glass filler surface-treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle diameter 0.2 µm, 40 parts of "AZ filler" manufactured by Asahi Glass Co., Ltd., carbon amount per unit surface area of 0.38 mg/m 2 ) were mixed, and uniformly dispersed with a high-speed rotary mixer to prepare resin varnish 2.

Next, using the resin varnish 2, a resin sheet 2 was produced in the same procedure as in Production Example 1.

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

6 parts of naphthalene type epoxy resin ("HP4032SS" manufactured by DIC Corporation, epoxy equivalent about 144) 6 parts, biphenyl type resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent about 185) 6 parts, biphenyl type epoxy 20 parts of resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent about 288), 8 parts of phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., MEK solution having a solid content of 30% by mass), solvent naphtha 15 It was heat-dissolved while stirring in the part. After cooling to room temperature, 20 parts of prepolymer of bisphenol A dicyanate ("BA230S75" manufactured by Lonza Japan Co., Ltd., about 232 cyanate equivalent, MEK solution having a nonvolatile content of 75% by mass) 20 parts, phenol novolac 8 parts of polyfunctional cyanate ester resin ("PT30S" manufactured by Ronza Japan Co., Ltd., MEK solution having a cyanate equivalent weight of about 133 and 85% by mass of nonvolatile content), an active ester curing agent (“HPC8000-65T” manufactured by DIC Corporation) , 8 parts of a toluene solution with an active group equivalent of about 223 and a nonvolatile content of 65% by mass), a curing accelerator (4-dimethylaminopyridine, a MEK solution having a solid content of 5% by mass) 0.4 parts, a curing accelerator (manufactured by Tokyo Kasei Co., Ltd., cobalt) (III) Acetylacetonate, MEK solution having a solid content of 1% by mass) 3 parts, a flame retardant (“HCA-HQ” manufactured by Sanko Corporation, 10-(2,5-dihydroxyphenyl)-10-hydro-9- 3 parts of oxa-10-phosphaphenanthrene-10-oxide, average particle diameter of 2 µm), spherical silica (average particle diameter) surface-treated with an amino silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 µm, manufactured by Adomatex Corporation "SOC2", carbon content per unit surface area of 0.39 mg/m2) 50 parts, spheres surface-treated with an amino silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 50 parts of glass filler (average particle diameter 0.2 µm, "AZ filler" manufactured by Asahi Glass Co., Ltd., carbon amount per unit surface area of 0.38 mg/m 2 ) was mixed and uniformly dispersed with a high-speed rotary mixer to prepare resin varnish 3 .

Next, using the resin varnish 3, a resin sheet 3 was produced in the same procedure as in Production Example 1.

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

12 parts of bisphenol A epoxy resin (“828EL” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 185), 3 parts of naphthalene-type epoxy resin (“HP4032SS” manufactured by DIC Corporation, about 144 epoxy equivalent), biphenyl type 6 parts of epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 185), 25 parts of biphenyl type epoxy resin (“NC3000H” manufactured by Nippon Kayaku Co., Ltd., about 288 epoxy equivalent), phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Corporation, MEK/cyclohexanone = 1/1 solution having a solid content of 30 mass%) 20 parts were heated and dissolved while stirring in 10 parts of solvent naphtha. After cooling to room temperature, thereto, 20 parts of a triazine skeleton-containing phenol novolac curing agent (“LA-7054” manufactured by DIC Corporation, a MEK solution having a hydroxyl equivalent of 125 and a solid content of 60%), a naphthol-based curing agent (thinnit) Tetsu Chemical Co., Ltd. "SN485", hydroxyl equivalent 215, MEK solution having a solid content of 60%) 10 parts, a curing accelerator (4-dimethylaminopyridine (DMAP), a MEK solution having a solid content of 5% by mass) 0.4 parts, a flame retardant ( "HCA-HQ" manufactured by Sanko Corporation, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 2 µm) 3 Spherical silica (average particle diameter 0.25 μm, “SOC1” manufactured by Adomatex Co., Ltd., carbon amount per unit surface area of 0.36) surface-treated with an amino silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) mg/m 2 ) 40 parts were mixed and uniformly dispersed with a high-speed rotary mixer to prepare resin varnish 4.

Next, using the resin varnish 4, a resin sheet 4 was produced in the same procedure as in Production Example 1.

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

6 parts of naphthalene type epoxy resin ("HP4032SS" manufactured by DIC Corporation, epoxy equivalent about 144) 6 parts, biphenyl type resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent about 185) 6 parts, biphenyl type epoxy 20 parts of resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 288), 16 parts of phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., MEK solution with a solid content of 30% by mass), solvent naphtha 5 It was heat-dissolved while stirring in the part. After cooling to room temperature, 20 parts of prepolymer of bisphenol A dicyanate ("BA230S75" manufactured by Lonza Japan Co., Ltd., about 232 cyanate equivalent, MEK solution having a nonvolatile content of 75% by mass) 20 parts, phenol novolac 8 parts of polyfunctional cyanate ester resin ("PT30S" manufactured by Lonza Japan Co., Ltd., MEK solution having a cyanate equivalent weight of about 133, and nonvolatile content of 85% by mass), an active ester curing agent ("HPC8000-65T" manufactured by DIC Corporation) , 8 parts of a toluene solution with an active group equivalent weight of about 223 and a nonvolatile content of 65% by mass), a curing accelerator (4-dimethylaminopyridine, a MEK solution with a solid content of 5% by mass) 0.4 parts, a curing accelerator (manufactured by Tokyo Kasei Corporation, cobalt) (III) Acetylacetonate, MEK solution having a solid content of 1% by mass) 3 parts, a flame retardant (“HCA-HQ” manufactured by Sanko Corporation, 10-(2,5-dihydroxyphenyl)-10-hydro-9- 3 parts of oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 2 µm), spherical silica (average particle diameter) surface-treated with an amino silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 0.25 μm, “SOC1” manufactured by Adomatex Co., Ltd., carbon amount per unit surface area of 0.36 mg/m 2) 40 parts were mixed and uniformly dispersed with a high-speed rotary mixer to prepare resin varnish 5.

Next, using the resin varnish 5, a resin sheet 5 was produced in the same procedure as in Production Example 1.

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

Table 5 shows the results of the evaluation.

As is clear from the results in Table 2, even when the same resin sheet 1 is used, when the temperature of the thermosetting step is 190°C (Test Example 1) × 90 minutes, a composition satisfying the provisions of the present invention is obtained, In the case of 150 degreeC (Test Example 5) x 90 minutes, the composition which satisfies the prescription|regulation of this invention was not obtained. In addition, similarly, even if the same resin sheet 2 is used, when the temperature of the thermosetting step is 200°C (Test Example 2)×90 minutes, the composition satisfying the regulations of the present invention is obtained at 150°C (Test Example 6). ) x 90 minutes, a composition satisfying the provisions of the present invention was not obtained.

Although the resin sheet 1 and the resin sheet 4 have similar compositions, although the thermosetting process is the same condition, Test Example 1 is an AZ filler composition satisfying the provisions of the present invention is obtained. In the case of Test Example 4, No composition was obtained which satisfies the provisions of the present invention.

Although the resin sheet 3 and the resin sheet 5 had similar compositions, although the thermosetting process was under the same conditions, the resin sheet 3 (Test Example 3) had a composition satisfying the provisions of the present invention, whereas the resin sheet 5 ( In the case of Test Example 7), a composition satisfying the provisions of the present invention was not obtained. Moreover, in the case of the resin sheet 5, even if the temperature of the thermosetting process was changed, the composition which satisfy|fills the prescription|regulation of this invention was not obtained (Test Example 8).

Claims (24)

A thermosetting process of forming a cured material layer by heating and curing the thermosetting resin composition layer formed on the inner layer substrate (except for the prepreg in which the thermosetting resin composition is impregnated into the fiber base material), and a substrate having the cured material layer Including a reflow step of mounting the parts by reflow on top, the 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 product layer A method of manufacturing a component mounting board, characterized in that the shrinkage ratio (S2) in the xy direction of 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 curing agent and an inorganic filler. The method according to claim 2, comprising silica as an inorganic filler. The method according to claim 2, comprising silica doped with titanium as an inorganic filler. The method of Claim 2 whose content of the inorganic filler in a thermosetting resin composition is 40 mass % or more when the nonvolatile component in a thermosetting resin composition is 100 mass %. The method according to claim 1, wherein the heating temperature in the thermosetting process is 120°C to 240°C. The method of claim 1 , wherein the peak temperature in the reflow process is between 210°C and 330°C. The method according to claim 1, wherein the thermosetting resin composition layer is formed by laminating an adhesive film in which a thermosetting resin crude composition layer is formed on a carrier film to an inner layer substrate. The method according to claim 1, wherein the thickness of the cured product layer is 3 to 200 μm. The method of claim 1 , wherein the component is a semiconductor chip, an interposer, or a passive device. The method of claim 10 , wherein the component is a semiconductor chip. A thermosetting resin composition for forming an insulating layer (except for a prepreg formed by impregnating a thermosetting resin composition in a fiber base material by heating),
The cured product of the thermosetting resin composition thermosetting under the condition that the shrinkage rate (S1) in the xy direction after thermosetting is 0.35% or less is heated to a reflow temperature profile based on IPC/JEDEC J-STD-020C in the xy direction A thermosetting resin composition, characterized in that the shrinkage ratio (S2) of is 0.4% or less, and S1 and S2 satisfy the relationship of S2-S1≤0.08. The thermosetting resin composition according to claim 12, wherein the peak temperature of reflow is 260°C. The thermosetting resin composition according to claim 12, wherein the thermosetting resin composition contains an epoxy resin, a curing agent and an inorganic filler. The thermosetting resin composition according to claim 14, comprising silica as the inorganic filler. The thermosetting resin composition according to claim 14, comprising titanium-doped silica as an inorganic filler. The thermosetting resin composition of Claim 14 whose content of the inorganic filler in a thermosetting resin composition is 40 mass % or more when the nonvolatile component in a thermosetting resin composition is 100 mass %. The multilayer printed wiring board in which the insulating layer is formed of the hardened|cured material of the thermosetting resin composition in any one of Claims 12-17. The component mounting board|substrate in which the insulating layer is formed of the hardened|cured material of the thermosetting resin composition in any one of Claims 12-17. The component mounting board according to claim 19, wherein the component is a semiconductor chip, an interposer, or a passive element. The component mounting board according to claim 20, wherein the component is a semiconductor chip. delete delete delete

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