JP6828242B2 - Thermosetting resin composition, prepreg, film with resin, laminated board and multilayer printed wiring board - Google Patents

Description

The present invention relates to thermosetting resin compositions, prepregs, resin-coated films, laminated boards and multilayer printed wiring boards.

In recent years, along with the trend toward miniaturization and higher performance of electronic devices, the wiring density and high integration of printed wiring boards have been increasing, and along with this, laminated boards for printed wiring boards have been introduced. There is an increasing demand for improved reliability by improving heat resistance. In general, it is known that the dimensions of a wiring board material change before and after mounting a chip on a substrate (shrink after mounting), which causes cracks in the solder and poor connection. What happens is a problem. Further, in the substrate for a semiconductor package, the occurrence of warpage due to the difference in the coefficient of thermal expansion from the chip during component mounting and package assembly has become a major problem as the size and thickness of the substrate are reduced.

Epoxy resins are known to be excellent in dimensional stability, chemical resistance, hygroscopicity and electrical insulation, and are widely used in wiring board materials, encapsulants, adhesives, paints and the like. Since the epoxy resin has a large coefficient of thermal expansion, the coefficient of thermal expansion is reduced by selecting an epoxy resin containing an aromatic ring or by highly filling an inorganic filler such as silica (see, for example, Patent Document 1). ..
However, it is known that increasing the filling amount of the inorganic filler causes a decrease in insulation reliability due to moisture absorption, insufficient adhesion between the resin composition layer and the wiring layer, poor press molding, and the like. There was a limit to reducing the coefficient of thermal expansion only by increasing the filling of the resin.

Compared with other polymer resin materials, polyimide resin has extremely excellent strength, heat resistance and low thermal expansion property, and is also excellent in electrical insulation, but has a problem of low adhesiveness. If the adhesiveness is low, when used as a wiring board material, there is a possibility that the wiring may be peeled off due to the warp generated at the time of mounting, causing problems such as disconnection. Therefore, studies have been conducted to improve the adhesiveness by modifying the end of the polyimide resin with an amine compound having an acidic substituent and reacting it with an epoxy resin or the like (see, for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 5-148343 Japanese Unexamined Patent Publication No. 2014-024927

However, due to the stricter demand for reliability in recent years, further low warpage, low shrinkage and low thermal expansion are desired.
In view of these circumstances, the present invention provides a thermosetting resin composition having excellent low shrinkage and low thermal expansion property and capable of suppressing warpage during mounting, and a prepreg, a film with resin, a laminated board and a multilayer printed wiring using the same. The purpose is to provide a board.

As a result of intensive studies to achieve the above object, the present inventors have made a thermosetting resin composition containing a plate-like filler, an amino-modified siloxane, and a thermosetting resin into low shrinkage and low thermal expansion. We have found that it is excellent and can suppress warpage during mounting, and arrived at the present invention.
That is, the present invention provides the following [1] to [17].
[1] A thermosetting resin composition containing (A) a filler, (B) an amino-modified siloxane, and (C) a thermosetting resin, wherein the (A) filler is a (A1) plate. A thermosetting resin composition containing a filler.
[2] The thermosetting resin composition according to the above [1], wherein the filler (A) further contains (A2) a spherical filler.
[3] The thermosetting resin composition according to the above [1], wherein the content of the (A1) plate-like filler in the (A) filler is 20 to 100% by mass.
[4] The thermosetting resin composition according to any one of the above [1] to [3], wherein the plate-shaped filler has an average particle size of 0.05 to 300 μm.
[5] The thermosetting according to any one of [1] to [4] above, wherein the (A1) plate-shaped filler contains one or more selected from the group consisting of talc, mica, clay, montmorillonite, silica and glass. Sex resin composition.
[6] The heat according to any one of [1] to [5] above, wherein the (C) thermosetting resin contains (C1) a maleimide resin having at least two N-substituted maleimide groups in one molecule. Curable resin composition.
[7] The thermosetting resin composition according to any one of [1] to [6] above, wherein the (B) amino-modified siloxane contains (B1) an amino-modified siloxane containing an aromatic azomethine skeleton.
[8] The component (B1) is a structural unit derived from an aromatic azomethine compound having at least one aldehyde group in one molecule of (b-1), and at least two primary components at the end of the molecule (b-2). The thermosetting resin composition according to the above [7], which comprises a structural unit derived from a siloxane compound having an amino group.
[9] The thermosetting resin composition according to any one of [1] to [8] above, further comprising (D) an amine compound having an acidic substituent.
[10] As the component (B), (B1) an aromatic azomethine skeleton-containing amino-modified siloxane, and as the component (C), a maleimide resin having at least two N-substituted maleimide groups in one molecule (C1). Aromatic azomethine containing (D) an amine compound having an acidic substituent, the structural unit derived from the component (B1), the structural unit derived from the component (C1), and the structural unit derived from the component (D). The thermocurable resin composition according to any one of the above [1] to [9], which is contained as a skeleton-containing siloxane-modified imide resin.
[11] The thermosetting resin composition according to any one of the above [1] to [10], further comprising (E) a thermoplastic elastomer.
[12] The thermosetting resin composition according to any one of the above [1] to [11], which further contains (F) a curing accelerator.
[13] A prepreg containing the thermosetting resin composition according to any one of the above [1] to [12].
[14] A resin-containing film containing the thermosetting resin composition according to any one of the above [1] to [12].
[15] A laminated board containing a cured product of the prepreg according to the above [13].
[16] A laminated board containing a cured product of the resin-containing film according to the above [14].
[17] A multilayer printed wiring board including the laminate according to the above [15] or [16].

According to the present invention, there is provided a thermosetting resin composition which is excellent in low shrinkage and low thermal expansion property and can suppress warpage during mounting, and a prepreg, a film with resin, a laminated board and a multilayer printed wiring board using the same. can do.

Hereinafter, embodiments of the present invention will be described in detail. In this specification, a numerical range (X and Y are real numbers) that are greater than or equal to X and less than or equal to Y may be expressed as "X to Y". For example, the description "0.1 to 2" indicates a numerical range of 0.1 or more and 2 or less, and the numerical range includes 0.1, 0.34, 1.03, 2, and the like.

Further, in the present specification, the "resin composition" refers to a mixture of each component described later, a semi-cured (so-called B-stage) mixture, and a cured (so-called C-stage) mixture. Including all of.

[Thermosetting resin composition]
The thermosetting resin composition of the present invention is a thermosetting resin composition containing (A) a filler, (B) an amino-modified siloxane, and (C) a thermosetting resin, and is (A). The filler contains (A1) plate-like filler.
By having the above-mentioned structure, the thermosetting resin composition of the present invention is excellent in low shrinkage and low thermal expansion engagement, and can suppress warpage during mounting. The reason why such an effect can be obtained is not clear, but the inventors of the present application think as follows.
Since the conventional wiring board material is cured in a stretched state during laminating molding by a press or the like, internal stress is generated in the material. When exposed to a heating environment such as chip mounting in the presence of the internal stress, it is considered that the internal stress is relaxed and shrinks to the original size.
On the other hand, the thermosetting resin composition of the present invention contains a plate-like filler as a filler. For example, when a prepreg to which the thermosetting resin composition of the present invention is applied is pressed and laminated, a plate is formed. The filler shows good orientation in the thermosetting resin composition. As a result, the elongation of the resin due to the stress during pressing can be suppressed, so that the internal stress existing in the obtained laminated plate can be reduced, and the amount of dimensional change that occurs during heating such as chip mounting, that is, the shrinkage rate is reduced. It is thought that.
Further, since the warpage caused by the shrinkage of the package at the time of chip mounting or laminating can be reduced by reducing the shrinkage rate, it is considered that the thermosetting resin composition of the present invention is excellent in low warpage property.

<(A) Filler>
The thermosetting resin composition of the present invention contains (A) a filler, and the (A) filler contains (A1) a plate-like filler.
In the present invention, "plate-like" is used to mean, for example, flat, flat, flaky, scaly, etc., and the aspect ratio (average) defined by the average maximum major axis and the average thickness of the particles. Maximum major axis / average thickness) is 3 or more.
(A1) The average maximum major axis and average thickness of the plate-shaped filler can be measured by electron microscope observation, and the maximum major axis and thickness of each of 50 or more arbitrarily selected particles are measured, and these are measured. The average can be obtained as the average maximum major axis and the average thickness.

The material of the plate-shaped filler (A1) is not particularly limited, and either an inorganic material or an organic material can be used, but a prepreg, a film with a resin, and a laminate obtained by using the thermosetting resin composition of the present invention can be used. Inorganic materials are preferable from the viewpoint of improving heat resistance (thermal characteristics), low shrinkage, and mechanical properties of boards, multilayer printed wiring boards, and the like.
Examples of the inorganic material include talc, mica, clay, montmorillonite, silica, glass (E glass, S glass, C glass, D glass, NE glass) and the like. These can be used alone or in admixture of two or more. Among these, glass and mica are preferably used because they can suppress the decomposition of the resin. When glass is used as the inorganic material, glass flakes can be used as the (A1) plate-like filler, and it is preferable to use non-alkali glass flakes.
Examples of the organic material include wood flour, pulp, crushed cloth, thermosetting resin cured product powder and the like.

The average particle size of the plate-shaped filler (A1) is not particularly limited, but is preferably 0.05 to 300 μm, more preferably 0.1 to 200 μm. When the average particle size is equal to or larger than the lower limit, (A1) aggregation of the plate-shaped fillers can be suppressed. Further, when the thermosetting resin composition of the present invention is used as a varnish or the thermosetting resin composition of the present invention is applied to a glass cloth, a film or the like because the average particle size is not more than the above upper limit value. At that time, the sedimentation of the (A1) plate-like filler can be suppressed. As a result, a prepreg containing a thermosetting resin composition having a high dispersibility of the (A1) plate-like filler, a film with a resin, and the like can be produced.
Here, the average particle size is the particle size of a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle size is obtained with the total volume of the particles as 100%, and the laser diffraction scattering method is used. It can be measured with the particle size distribution measuring device or the like.

The shape of the plate-shaped filler (A1) is not particularly limited as long as it is plate-shaped, but the aspect ratio (average maximum major axis / average thickness) is preferably 5 to 2000, and more preferably 10 to 1000. preferable. When the aspect ratio is at least the above lower limit value, the flat surface of the filler becomes sufficiently wide, and more excellent low shrinkage and elastic modulus are exhibited. Further, when the aspect ratio is not more than the above upper limit value, the dispersibility of the (A1) plate-shaped filler in the thermosetting resin composition is improved, and the dispersibility of the (A1) plate-shaped filler is higher. A prepreg containing a resin composition, a film with a resin, and the like can be produced.

When (A1) the plate-shaped filler is an inorganic material, (C) a coupling agent such as a silane coupling agent or a titanate-based coupling agent for the purpose of improving the adhesion of the interface with the thermosetting resin. It is preferable to treat with. By treating with a coupling agent, the dispersibility of the (A1) plate-like filler in the thermosetting resin composition can be improved, and the storage stability when the thermosetting resin composition is used as a varnish can be improved. it can. Further, when the varnish is applied to a glass cloth, a film, etc., or when a prepreg or the like containing the thermosetting resin composition of the present invention is press-molded, the resin component and the (A1) plate-like filler are separated. Can be suppressed.

Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropyltriditrimethoxy. Amino group-containing silane coupling agent such as methylsilane; glycidyl group-containing silane such as γ-glycidoxypropylmethoxysilane, γ-glycidoxypropylethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Coupling agents: Titanium-based coupling agents such as isopropyltristearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, and tetraisopropylbis (dioctylphosphite) titanate can be mentioned. These can be used alone or in admixture of two or more. Among these, γ-aminopropyltrimethoxysilane and γ-glycidoxypropylmethoxysilane are preferable.
The coupling agent may be added at the time of blending the thermosetting resin composition or the varnish described later, or the plate-shaped filler (A1) before blending may be used in a pretreatment manner.

The content of the (A1) plate-like filler in the thermosetting resin composition of the present invention is 30 to 500 parts by mass per 100 parts by mass of the total amount of solid content-equivalent resin components in the thermosetting resin composition. Is preferable, and it is more preferably 150 to 300 parts by mass. By setting the content as described above, the orientation of the (A1) plate-like filler can be kept good, and excellent low shrinkage, low thermal expansion and low warpage can be obtained.
The total amount of the resin component in terms of solid content is the total amount of (B) amino-modified siloxane, (C) thermosetting resin, and optionally used resin component in the thermosetting resin composition converted into solid content. The amount.

The content of the (A1) plate-like filler in the (A) filler is preferably 20 to 100% by mass, more preferably 40 to 100% by mass, and further preferably 60 to 100% by mass. preferable. By setting the content as described above, the orientation of the (A1) plate-like filler can be kept good, and excellent low shrinkage, low thermal expansion and low warpage can be obtained.

The thermosetting resin composition of the present invention may contain a filler other than the (A1) plate-like filler as the (A) filler.
(A1) The material of the filler other than the plate-shaped filler is not particularly limited, and either an inorganic material or an organic material can be used, but a laminated plate or the like obtained by using the thermosetting resin composition of the present invention can be used. Inorganic materials are preferable from the viewpoint of improving heat resistance (thermal properties), low shrinkage and mechanical properties.
Further, the shape of the filler other than (A1) plate-shaped filler is not particularly limited as long as it is not plate-shaped, but it may be (A2) spherical filler from the viewpoint of being able to be packed densely and having excellent low thermal expansion. preferable.
In the present invention, "spherical" is a concept including shapes such as true spherical shape, granular shape, and elliptical shape, and more specifically, the aspect ratio (major axis / minor axis) between the major axis and the minor axis is 1. Means ~ 2.
The major axis of the spherical filler is the maximum length that can be taken in the projected image of the particles, and the minor axis means the maximum length in the direction orthogonal to the maximum length.
(A2) The aspect ratio of the spherical filler is determined by arbitrarily selecting 50 or more particles from the image taken with an electron microscope, obtaining the ratio of the major axis and the minor axis of each, and calculating the average value. Can be done.

(A1) Examples of the inorganic filler other than the plate-shaped filler include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, and tinic acid having a shape other than the plate-shaped filler. Examples thereof include zinc, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, aluminum borate, potassium titanate, glass powder such as E glass, S glass, D glass and C glass, and hollow glass beads. These can be used alone or in admixture of two or more. Among these, silica is preferable from the viewpoint of dielectric properties, heat resistance and low thermal expansion. By using silica having a shape other than the plate shape in combination with the (A1) plate-shaped filler, the orientation of the (A1) plate-shaped filler can be controlled, and a low coefficient of thermal expansion of silica can be imparted to the resin.
Examples of silica include precipitated silica manufactured by a wet method and having a high water content, dry silica manufactured by a dry method and containing almost no bound water, and the like, and dry silica further depends on the manufacturing method. , Fused silica, crushed silica, fumed silica, spherical silica and the like. Among these, spherical silica is preferable from the viewpoint of low thermal expansion and high fluidity when filled in a resin. That is, it is preferable to use spherical silica as the (A2) spherical filler.

(A2) When spherical silica is used as the spherical filler, the average particle size thereof is preferably 0.1 to 10 μm, more preferably 0.3 to 8 μm. When the average particle size of the spherical silica is 0.1 μm or more, good fluidity can be maintained when the resin is highly filled, and when it is 10 μm or less, the probability of mixing coarse particles is reduced. , It is possible to suppress the occurrence of defects caused by coarse particles. The average particle size can be measured in the same manner as in the case of the (A1) plate-shaped filler.

When the thermosetting resin composition of the present invention contains (A2) spherical filler, the content of (A2) spherical filler is 10 per 100 parts by mass of the total amount of solid content-equivalent resin components in the thermosetting resin composition. It is preferably ~ 200 parts by mass, and more preferably 30 to 100 parts by mass. By setting the content as described above, excellent low thermal expansion property and high fluidity when filled in the resin can be obtained.

When the thermosetting resin composition of the present invention contains (A2) spherical filler, the content of (A2) spherical filler in the (A) filler is preferably 5 to 80% by mass, preferably 10 to 60% by mass. It is more preferably%, and further preferably 15 to 40% by mass. By setting the content as described above, excellent low thermal expansion property and high fluidity when filled in the resin can be obtained.

(A1) Examples of the organic filler other than the plate-shaped filler include a resin filler having a shape other than the plate-shaped filler and having a uniform structure made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, siloxane resin, tetrafluoroethylene resin and the like. A rubber-like core layer made of an acrylic acid ester resin, a methacrylate ester resin, a conjugated diene resin, etc., an acrylic acid ester resin, a methacrylate ester resin, an aromatic vinyl resin, a vinyl cyanide resin, etc. Examples thereof include a resin filler having a core-shell structure having a shell layer in a glass state.

The content of the filler (A) in the thermosetting resin composition of the present invention may be 30 to 600 parts by mass per 100 parts by mass of the total amount of solid content-equivalent resin components in the thermosetting resin composition. It is preferably 150 to 400 parts by mass, more preferably 150 to 400 parts by mass. By setting the content of the filler (A) within the above range, the moldability and low thermal expansion of the prepreg can be kept good.

<(B) Amino-modified siloxane>
The thermosetting resin composition of the present invention contains (B) an amino-modified siloxane. The amino-modified siloxane (hereinafter, also referred to as “component (B)”) is not particularly limited, and for example, a compound represented by the following general formula (1) can be used.

In the general formula (1), a plurality of R ₁ each independently represent an alkyl group, a phenyl group or substituted phenyl group, may be the same or different from each other, a plurality of R ₂ each independently represent an alkyl group, a phenyl It represents a group or a substituted phenyl group and may be the same or different from each other. R ₃ and R ₄ independently represent an alkyl group, a phenyl group or a substituted phenyl group, and R ₅ and R ₆ each independently represent a divalent organic group. n represents an integer of 2 to 50.

In the general formula (1), as the alkyl group represented by R ₁ , R ₂ , R ₃ or R ₄ , an alkyl group having 1 to 5 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable. Alkyl groups having 1 or 2 carbon atoms are more preferable.
Specific examples of the alkyl group represented by R ₁ , R ₂ , R ₃ or R ₄ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like, and among these, a methyl group is preferable. ..
Examples of the substituent in the substituted phenyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include an alkyl group, an alkenyl group, an alkynyl group and the like, and among these, an alkyl group is preferable. As the alkyl group, the same group as described above is preferably mentioned.
Among the groups represented by R ₁ , R ₂ , R ₃ or R ₄ , a phenyl group or a methyl group is preferable, and a methyl group is more preferable, from the viewpoint of solubility with other resins.
Examples of the organic group represented by R ₅ or R ₆ include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O— or a divalent linking group in which these are combined. Among these, an alkylene group and an arylene group are preferable. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group and the like. Examples of the arylene group include a phenylene group and a naphthylene group.

As the amino-modified siloxane (B), a commercially available product can be used. Examples of the commercially available (B) amino-modified siloxane include "KF-8010" (amino group equivalent 430 g / mol) and "X-22-161A" (amino group equivalent 800 g / mol) having amino groups at both ends. , "X-22-161B" (amino group equivalent 1500 g / mol), "KF-8012" (amino group equivalent 2200 g / mol), "KF-8008" (amino group equivalent 5700 g / mol), "X-22-" 9409 "(amino group equivalent 700 g / mol)," X-22-1660B-3 "(amino group equivalent 2200 g / mol) (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.)," BY-16-853U "(amino group equivalent) 460 g / mol), "BY-16-853" (amino group equivalent 650 g / mol), "BY-16-853B" (amino group equivalent 2200 g / mol) (all manufactured by Toray Dow Corning Co., Ltd.), on the side chain "KF-868" having an amino group (amino group equivalent 8800 g / mol), "KF-865" (amino group equivalent 5000 g / mol), "KF-864" (amino group equivalent 3800 g / mol), "KF-880" "(Amino group equivalent 1800 g / mol)," KF-8004 "(Amino group equivalent 1500 g / mol) (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like. These can be used alone or in admixture of two or more. Among these, from the viewpoint of low water absorption, "X-22-161A", "X-22-161B", "KF-8012", "KF-8008", "X-22-1660B-3" and " "BY-16-853B" is preferable, and "X-22-161A", "X-22-161B" and "KF-8012" are more preferable from the viewpoint of low thermal expansion.

Further, it is preferable that the (B) amino-modified siloxane contains (B1) aromatic azomethine skeleton-containing amino-modified siloxane (hereinafter, also referred to as “(B1) component”). (B1) By containing the aromatic azomethine skeleton-containing amino-modified siloxane, the orientation of the resin can be enhanced, and the cured product of the thermosetting resin composition of the present invention can be further reduced in thermal expansion and high elastic modulus. Can be done.

((B1) Amino-modified siloxane containing aromatic azomethine skeleton)
The component (B1) includes, for example, an aromatic azomethine compound having at least one aldehyde group in one molecule of (b-1) (hereinafter, also referred to as “component (b-1)”) and (b-2). It can be obtained by reacting with a siloxane compound having at least two primary amino groups at the end of the molecule (hereinafter, also referred to as “component (b-2)”). That is, the component (B1) can be composed of a structural unit derived from the component (b-1) and a structural unit derived from the component (b-2).

[(B-1) Aromatic azomethine compound having at least one aldehyde group in one molecule]
The component (b-1) is, for example, an aromatic aldehyde compound having at least two aldehyde groups in the molecular structure (hereinafter, also referred to as “polyfunctional aldehyde compound”) and at least two primary aminos in the molecular structure. It can be obtained by reacting with an amine compound having a group (hereinafter, also referred to as “polyfunctional amine compound”).

Examples of the polyfunctional aldehyde compound include terephthalaldehyde, isophthalaldehyde, o-phthalaldehyde, 2,2'-bipyridine-4,4'-dicarboxyaldehyde and the like. These can be used by mixing two or more kinds. Among these, terephthalaldehyde is preferable because it can be expanded by a lower temperature, has high reactivity, has excellent solvent solubility, and is easily commercially available.

Examples of the polyfunctional amine compound include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1,4-diaminobenzene, 2,5-dimethyl-1,4-diaminobenzene, and 4 , 4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-diaminodiphenyl ether, 4,4 ′ -Diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylketone, benzene, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4, 4'-diaminobiphenyl, 3,3'-dihydroxybenzene, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3'-dimethyl-5,5'-diethyl-4,4'- Diphenylmethanediamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3 -Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone , Bis (4- (3-aminophenoxy) phenyl) sulfone, 9,9-bis (4-aminophenyl) fluorene and the like. These can be used by mixing two or more kinds.
Among these, for example, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino- because of its high reactivity and higher heat resistance. 3,3'-Dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-bis (4-aminophenoxy) biphenyl and bis (4- (4-aminophenoxy) phenyl ) Propane is preferred, inexpensive and soluble in solvents, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-3. , 3'-diethyl-diphenylmethane and bis (4- (4-aminophenoxy) phenyl) propane are more preferred, and 4,4'-diamino-3,3'-diethyl-diphenylmethane from the viewpoint of low thermal expansion and dielectric properties. , Bis (4- (4-aminophenoxy) phenyl) propane is more preferred. Further, p-phenylenediamine, m-phenylenediamine, 3-methyl-1,4-diaminobenzene and 2,5-dimethyl-1,4-diaminobenzene are also preferable from the viewpoint of increasing the elastic modulus.

Here, the amount of the polyfunctional aldehyde compound and the polyfunctional amine compound used is, for example, the number of primary amino groups of the polyfunctional amine compound [amount of the polyfunctional amine compound used / the primary amino group equivalent of the polyfunctional amine compound]. It is preferable to use the aldehyde compound in a range of 0.1 to 5.0 times the number of aldehyde groups [amount of polyfunctional aldehyde compound used / aldehyde group equivalent of polyfunctional aldehyde compound]. When the value is 0.1 times or more, the molecular weight of the aromatic azomethine compound obtained by this reaction can be kept good, and when the value is 5.0 times or less, good solubility in a solvent can be obtained. Be done.

The polyfunctional aldehyde compound and the polyfunctional amine compound are preferably reacted in an organic solvent.
The amount of the organic solvent used is, for example, preferably 25 to 2000 parts by mass, more preferably 40 to 1000 parts by mass, based on 100 parts by mass of the total of the polyfunctional aldehyde compound and the polyfunctional amine compound. It is more preferably 40 to 500 parts by mass. When the amount of the organic solvent used is 25 parts by mass or more, good solubility can be obtained, and when it is 2000 parts by mass or less, a sufficient reaction rate can be obtained.

A polyfunctional aldehyde compound, a polyfunctional amine compound, an organic solvent, and a reaction catalyst, if necessary, are charged into a reaction vessel, and if necessary, the mixture is stirred while being heated and kept warm, and undergoes a dehydration condensation reaction to form (b-1) one molecule. An aromatic azomethine compound having at least one aldehyde group is obtained.
The reaction conditions are not particularly limited and may be appropriately determined according to the type of raw material and the like. The reaction time can be, for example, in the range of 0.1 to 10 hours. The reaction temperature is, for example, preferably 70 to 150 ° C., and more preferably 100 to 130 ° C. because it is desirable to react while removing water as a by-product. A sufficient reaction rate can be obtained by setting the reaction temperature to 70 ° C. or higher. Further, by setting the reaction temperature to 150 ° C. or lower, a solvent having a high boiling point is not required as the reaction solvent, so that the solvent is less likely to remain in the cured product, and the heat resistance of the obtained prepreg, laminated board, etc. becomes excellent. ..

[(B-2) A siloxane compound having at least two primary amino groups at the end of the molecule]
The component (b-2) is not particularly limited as long as it is a siloxane compound having at least two primary amino groups at the molecular terminal, and examples thereof include a compound represented by the general formula (1).
Further, as the component (b-2), a commercially available product can be used, and as the component (b-2) of the commercially available product, for example, a siloxane having amino groups at both ends listed as the component (B). Can be mentioned. These can be used alone or in admixture of two or more. Among these, from the viewpoint of low water absorption, "X-22-161A", "X-22-161B", "KF-8012", "KF-8008", "X-22-1660B-3", "BY-16-853B" is preferable, and "X-22-161A", "X-22-161B", and "KF-8012" are preferable from the viewpoint of low thermal expansion.

The amount of the component (b-1) and the component (b-2) used is, for example, the number of primary amino groups of the component (b-2) [the amount of the component (b-2) used / the primary amino of the component (b-2)). The base equivalent] should be in the range of 1.0 to 10.0 times the number of aldehyde groups of the (b-1) component [the amount of the (b-1) component used / the aldehyde group equivalent of the (b-1) component]. It is preferable to use it for. When it is 1.0 times or more, good solubility in a solvent can be obtained, and when it is 10.0 times or less, the elastic modulus of the thermosetting resin composition becomes excellent.

The existence of the (B1) aromatic azomethine skeleton-containing amino-modified siloxane obtained by the above reaction can be confirmed by performing IR measurement. Specifically, by IR measurement, to confirm that the peak of 1620 cm ^-1 attributable to the azomethine group (-N = CH-) appears, also, around at 3,440 cm ^-1 and 3370cm ^-1 due to primary amino groups By confirming the presence of the peak of, it can be confirmed that the reaction proceeds well and the desired compound is obtained.

The weight average molecular weight (Mw) of the amino-modified siloxane (B) is not particularly limited, but is preferably, for example, 1,000 to 300,000, and more preferably 6,000 to 150,000. When the weight average molecular weight (Mw) is at least the above lower limit value, low shrinkage and low thermal expansion tend to be further improved, and when it is at least the above upper limit value, compatibility and elastic modulus tend to be further improved. ..
The weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) and converted by a calibration curve prepared using standard polystyrene. For example, it can be measured under the following conditions.
Examples of the measuring device include an auto sampler (AS-8020 manufactured by Tosoh Corporation), a column oven (860-C0 manufactured by JASCO Corporation), an RI detector (830-RI manufactured by JASCO Corporation), and UV / A VIS detector (870-UV manufactured by JASCO Corporation) and an HPLC pump (880-PU manufactured by JASCO Corporation) can be used. Further, as the column to be used, for example, TSKGEL SuperHZ2000, 2300 manufactured by Tosoh Corporation can be used, and as the measurement conditions, for example, the measurement temperature is 40 ° C., the flow rate is 0.5 ml / min, and tetrahydrofuran is used as the solvent. it can.

The content of the (B) amino-modified siloxane in the thermosetting resin composition of the present invention is 2 to 50 parts by mass per 100 parts by mass of the total amount of solid content-equivalent resin components in the thermosetting resin composition. Is more preferable, 5 to 40 parts by mass is more preferable, and 10 to 30 parts by mass is further preferable. Within this range, excellent elastic modulus and low thermal expansion can be obtained.

<(C) Thermosetting resin>
The thermosetting resin composition of the present invention further contains (C) a thermosetting resin (hereinafter, also referred to as “component (C)”).
The thermosetting resin (C) is not particularly limited, and for example, maleimide resin, epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, and unsaturated polyester. Examples thereof include resins, allyl resins, dicyclopentadiene resins, siloxane resins, triazine resins, and melamine resins. These can be used alone or in admixture of two or more. Among these, epoxy resin and cyanate resin are preferable from the viewpoint of moldability and electrical insulation, and maleimide resin is preferable from the viewpoint of heat resistance, moisture absorption resistance and low decomposability by moisture in the resin (C1). ) A maleimide resin having at least two N-substituted maleimide groups in one molecule is more preferable.

Examples of the maleimide resin include N, N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N'-(1,3-phenylene) bismaleimide, N, N'-[1,3. -(2-Methylphenylene)] bismaleimide, N, N'-[1,3- (4-methylphenylene)] bismaleimide, N, N'-(1,4-phenylene) bismaleimide, bis (4-) Maleimidephenyl) methane, bis (3-methyl-4-maleimidephenyl) methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, bis (4-maleimidephenyl) ether, Bis (4-maleimidephenyl) sulfone, bis (4-maleimidephenyl) sulfide, bis (4-maleimidephenyl) ketone, bis (4-maleimidecyclohexyl) methane, 1,4-bis (4-maleimidephenyl) cyclohexane, 1 , 4-bis (maleimide methyl) cyclohexane, 1,4-bis (maleimide methyl) benzene, 1,3-bis (4-maleimide phenoxy) benzene, 1,3-bis (3-maleimide phenoxy) benzene, bis [4 -(3-Maleimide phenoxy) phenyl] methane, bis [4- (4-maleimide phenoxy) phenyl] methane, 1,1-bis [4- (3-maleimide phenoxy) phenyl] ethane, 1,1-bis [4 -(4-Maleimide phenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimide phenoxy) phenyl] ethane, 1,2-bis [4- (4-maleimide phenoxy) phenyl] ethane, 2,2 -Bis [4- (3-maleimide phenoxy) phenyl] propane, 2,2-bis [4- (4-maleimide phenoxy) phenyl] propane, 2,2-bis [4- (3-maleimide phenoxy) phenyl] butane , 2,2-bis [4- (4-maleimide phenoxy) phenyl] butane, 2,2-bis [4- (3-maleimide phenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Propane, 2,2-bis [4- (4-maleimide phenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-maleimide phenoxy) biphenyl, 4, 4-Bis (4-maleimide phenoxy) biphenyl, bis [4- (3-maleimide phenoxy) phenyl] ketone, bis [4- (4-maleimide phenoxy) phenyl] ketone, 2,2-Bis (4-maleimidephenyl) disulfide, bis (4-maleimidephenyl) disulfide, bis [4- (3-maleimidephenoxy) phenyl] sulfide, bis [4- (4-maleimidephenoxy) phenyl] sulfide, Bis [4- (3-maleimide phenoxy) phenyl] sulfoxide, bis [4- (4-maleimide phenoxy) phenyl] sulfoxide, bis [4- (3-maleimide phenoxy) phenyl] sulfone, bis [4- (4-maleimide) phenyl] Phenoxy) phenyl] sulfone, bis [4- (3-maleimide phenoxy) phenyl] ether, bis [4- (4-maleimide phenoxy) phenyl] ether, 1,4-bis [4- (4-maleimide phenoxy) -α , Α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimide phenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimide phenoxy) -α, α -Dimethylbenzyl] Benzene, 1,3-bis [4- (3-maleimidephenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-maleimidephenoxy) -3,5-dimethyl -Α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidephenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3) -Maleimide phenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimide phenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, Examples thereof include polyphenylmethane maleimide (for example, manufactured by Daiwa Kasei Kogyo Co., Ltd., product name: BMI-2300, etc.). These can be used alone or in admixture of two or more. Among these, bis (4-maleimidephenyl) methane, bis (4-maleimidephenyl) sulfone, N, N'-(1,3-phenylene) bismaleimide because of its high reaction rate and higher heat resistance. , 2,2-Bis (4- (4-maleimidephenoxy) phenyl) propane and polyphenylmethane Maleimide are preferred, and bis (4-maleimidephenyl) methane and 2,2-bis [from the viewpoint of solubility in a solvent. 4- (4-Maleimidephenoxy) phenyl] propane is more preferred.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, and bisphenol F novolac type epoxy resin. , Stilben type epoxy resin, triazine skeleton containing epoxy resin, fluorene skeleton containing epoxy resin, triphenolphenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene Examples thereof include type epoxy resins, alicyclic epoxy resins, polycyclic aromatic diglycidyl ether compounds such as polyfunctional phenols and anthracene, and phosphorus-containing epoxy resins in which a phosphorus compound is introduced therein. These can be used alone or in admixture of two or more. Among these, a biphenyl aralkyl type epoxy resin and a naphthalene type epoxy resin are preferable from the viewpoint of heat resistance and flame retardancy.

Examples of the cyanate resin include bisphenol type cyanate resins such as novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, tetramethylbisphenol F type cyanate resin, and prepolymers in which these are partially triazined. Be done. These can be used alone or in admixture of two or more. Among these, novolak type cyanate resin is preferable from the viewpoint of heat resistance and flame retardancy.

The content of the (C) thermosetting resin in the thermosetting resin composition of the present invention is 40 to 95 parts by mass per 100 parts by mass of the total amount of solid content-equivalent resin components in the thermosetting resin composition. It is preferably 50 to 90 parts by mass, more preferably 60 to 90 parts by mass. Within this range, excellent elastic modulus and low thermal expansion can be obtained.

<(D) Amine compound having an acidic substituent>
The thermosetting resin composition of the present invention preferably further contains (D) an amine compound having an acidic substituent (hereinafter, also referred to as “component (D)”).
As the component (D), for example, a compound represented by the following general formula (2) (hereinafter, also referred to as "a compound represented by (D1) general formula (2)" or "component (D1)") is preferable. Can be mentioned.

In the general formula (2), R ₇ represents a hydroxyl group, a carboxy group or a sulfonic acid group which are acidic substituents, and R ₈ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. , X is an integer of 1 to 5, y is an integer of 0 to 4, and x + y = 5. If R ₇ and _{R 8} there are a plurality, a plurality of _{R 7} and _{R 8} are either the same or may be different from one another.

(D1) Examples of the compound represented by the general formula (2) include o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, and p-aminobenzoic acid. , O-Aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like. Among these, o-aminophenol, m-aminophenol, p-aminophenol, m-aminobenzoic acid, p-aminobenzoic acid and 3,5-dihydroxyaniline are preferable from the viewpoint of solubility and synthetic yield. From the viewpoint of heat resistance, m-aminophenol and p-aminophenol are more preferable.

The content of the amine compound having the (D) acidic substituent in the thermosetting resin composition of the present invention is 0.1 to 100 parts by mass per 100 parts by mass of the total amount of solid content-equivalent resin components in the thermosetting resin composition. It is preferably 20 parts by mass, and more preferably 1 to 10 parts by mass. When the content of the component (D) is 0.1 parts by mass or more, excellent heat resistance and copper foil adhesion can be obtained, and when it is 20 parts by mass or less, excellent heat resistance can be ensured.

The thermosetting resin composition of the present invention preferably contains (D) an amine compound having an acidic substituent in addition to the components (A) to (C), but (B) an amino-modified siloxane and (C). ) The thermosetting resin and (D) the amine compound having an acidic substituent can also be used by prereacting.
Various combinations can be applied to each component used in the pre-reaction. For example, (B) as an amino-modified siloxane, (B1) an aromatic azomethine skeleton-containing amino-modified siloxane, and (C) as a thermosetting resin (C1). ) A maleimide resin having at least two N-substituted maleimide groups in one molecule is preferably used. By pre-reacting these, (B1) a structural unit derived from an amino-modified siloxane containing an aromatic azomethine skeleton and (C1) a structural unit derived from a maleimide resin having at least two N-substituted maleimide groups in one molecule can be obtained. , (D) Can be used as an aromatic azomethine skeleton-containing siloxane-modified imide resin containing a structural unit derived from an amine compound having an acidic substituent. Further, as the amine compound having (D) an acidic substituent, (D1) the compound represented by the general formula (2) is preferably used.

The pre-reaction is preferably carried out while being heated and kept warm in an organic solvent.
In this pre-reaction, the amount of the component (B1), the component (C1) and the component (D1) used is, for example, the number of maleimide groups of the component (C1) [the amount of the component (C1) used / the equivalent of the maleimide group of the component (C1). ] Is the total number of primary amino groups of (B1) component and (D1) component [Amount of (B1) component used / primary amino group equivalent of (B1) component + amount of (D1) component used / (D1) component It is preferably in the range of 2.0 to 10.0 times the primary amino group equivalent. By setting it to 2.0 times or more, gelation is suppressed and excellent heat resistance can be obtained, and by setting it to 10.0 times or less, good solubility in an organic solvent and excellent heat resistance can be obtained. Is obtained.

The amount of the component (C1) used in the pre-reaction is preferably 50 to 3000 parts by mass and 100 to 1500 parts by mass with respect to 100 parts by mass of the component (B1) while maintaining the above relationship. Is more preferable. When the content of the component (C1) is 50 parts by mass or more, good heat resistance can be obtained, and when it is 3000 parts by mass or less, low thermal expansion can be kept good.
The amount of the component (D1) used in the pre-reaction is preferably 1 to 1000 parts by mass, preferably 10 to 500 parts by mass, based on 100 parts by mass of the component (B1) while maintaining the above relationship. It is more preferably by mass. When the content of the component (D1) is 1 part by mass or more, excellent heat resistance can be obtained, and when it is 1000 parts by mass or less, low thermal expansion can be kept good.

Examples of the organic solvent used in the pre-reaction include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Ester solvents such as ethyl acetate and γ-butyrolactone; Ether solvents such as tetrahydrofuran; Aromatic solvents such as toluene, xylene and mesitylen; Nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; dimethyl Examples thereof include a sulfur atom-containing solvent such as sulfoxide. These can be used alone or in admixture of two or more. Among these organic solvents, for example, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve and γ-butyrolactone are preferable from the viewpoint of solubility, and cyclohexanone is low in toxicity and is highly volatile and does not easily remain as a residual solvent. , Propylene glycol monomethyl ether and dimethylacetamide are preferred.
The amount of the organic solvent used is, for example, preferably 25 to 2000 parts by mass, preferably 40 to 1000 parts by mass, based on 100 parts by mass of the total of the components (B1), (C1) and (D1). More preferably, it is more preferably 40 to 500 parts by mass. When the amount of the organic solvent used is 25 parts by mass or more, good solubility can be obtained, and when it is 2000 parts by mass or less, a sufficient reaction rate can be obtained.

A reaction catalyst can be optionally used for the pre-reaction. Examples of the reaction catalyst include amines such as triethylamine, pyridine and tributylamine; imidazoles such as methylimidazole and phenylimidazole; phosphorus catalysts such as triphenylphosphine; alkali metal amides such as lithium amide, sodium amide and potassium amide. And so on. These can be used alone or in admixture of two or more.

The reaction temperature of the pre-reaction is, for example, preferably 70 to 150 ° C, more preferably 100 to 130 ° C. The reaction time is, for example, preferably 0.1 to 10 hours, more preferably 1 to 6 hours.

When the thermosetting resin composition of the present invention contains an aromatic azomethine skeleton-containing siloxane-modified imide resin obtained by the pre-reaction, the content thereof is the total amount of solid content-equivalent resin components in the thermosetting resin composition. It is preferably 50 to 100 parts by mass, and more preferably 60 to 80 parts by mass per 100 parts by mass. By setting the content of the aromatic azomethine skeleton-containing siloxane-modified imide resin to 50 parts by mass or more, a thermosetting resin composition having a low coefficient of thermal expansion and a high elastic modulus can be obtained.

The thermosetting resin composition of the present invention has good thermosetting reactivity, but if necessary, it contains a curing agent and / or a polymerization initiator to further improve heat resistance, adhesiveness and mechanical strength. Can be done.

Examples of the curing agent include dicyandiamide, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-diaminodiphenylsulfone, phenylenediamine, xylenediamine and the like. Aromatic amines; aliphatic amines such as hexamethylenediamine and 2,5-dimethylhexamethylenediamine; guanamine compounds such as melamine and benzoguanamine can be mentioned. These can be used alone or in admixture of two or more. Among these, for example, aromatic amines are preferable from the viewpoint of good reactivity and heat resistance.
Examples of the polymerization initiator include organic peroxides such as acyl peroxides, hydroperoxides, ketone peroxides, organic peroxides having a t-butyl group, and peroxides having a cumyl group. .. These can be used alone or in admixture of two or more.
When the thermosetting resin composition of the present invention contains a curing agent, the content of the curing agent is, for example, the functional group equivalent of the curing agent is the number of maleimide groups of the maleimide compound [the amount of the maleimide compound used / the maleimide group equivalent of the maleimide compound. ] Is preferably in the range of 2.0 to 10 times. When it is 2.0 times or more, excellent adhesiveness and heat resistance can be obtained, and when it is 10 times or less, good solubility in an organic solvent and mechanical strength can be obtained.

<(E) Thermoplastic Elastomer>
The thermosetting resin composition of the present invention may further contain (E) a thermoplastic elastomer.
Examples of the (E) thermoplastic elastomer include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, siloxane-based elastomers, and derivatives thereof. These consist of a hard segment component and a soft segment component, and the former generally contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. These can be used alone or in admixture of two or more. Among these, for example, styrene-based elastomers, olefin-based elastomers, polyamide-based elastomers and siloxane-based elastomers are preferable from the viewpoint of heat resistance and insulation reliability, and styrene-based elastomers and olefin-based elastomers are more preferable from the viewpoint of dielectric properties. ..

As the thermoplastic elastomer (E), one having a reactive functional group at the molecular end or in the molecular chain can be used. Examples of the reactive functional group include an epoxy group, a hydroxyl group, a carboxy group, an amino group, an amide group, an isocyanato group, an acrylic group, a methacryl group and a vinyl group. By having these reactive functional groups at the molecular ends or in the molecular chain, the compatibility with the resin is improved, and the internal stress generated during curing of the thermosetting resin composition of the present invention is more effectively reduced. be able to. As a result, the warpage of the substrate can be significantly reduced.
Among these reactive functional groups, for example, an epoxy group, a hydroxyl group, a carboxy group, an amino group and an amide group are preferable from the viewpoint of adhesion to a metal foil, and an epoxy group is preferable from the viewpoint of heat resistance and insulation reliability. A hydroxyl group and an amino group are more preferable.

When the thermosetting resin composition of the present invention contains (E) a thermoplastic elastomer, the content of the (E) thermoplastic elastomer is per 100 parts by mass of the total amount of solid content-equivalent resin components in the thermosetting resin composition. , 0.1 to 50 parts by mass, more preferably 2 to 30 parts by mass. By setting the content of the thermosetting elastomer resin within the above range, it is possible to effectively exhibit excellent compatibility of the resin, low shrinkage of the cured product, low thermal expansion, and excellent dielectric properties. it can.

<(F) Curing accelerator>
The thermosetting resin composition of the present invention may further contain (F) a curing accelerator. By using (F) a curing accelerator in combination, the shrinkage rate and the amount of warpage can be further reduced.
Examples of the (F) curing accelerator include imidazoles and derivatives thereof, organophosphorus compounds, secondary or tertiary amines, quaternary ammonium salts and the like. These can be used alone or in admixture of two or more. Among these, imidazoles are preferable from the viewpoint of reactivity, and an adduct of hexamethylene diisocyanate represented by the following general formula (3) and 2-ethyl-4-methylimidazole is more preferable. The compound represented by the following general formula (3) is available as, for example, "G-8009L" (trade name) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.

When the thermosetting resin composition of the present invention contains (F) a curing accelerator, the content of the (F) curing accelerator is, for example, 100 mass by mass of the total amount of solid content-equivalent resin components in the thermosetting resin composition. It is preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 2 parts by mass. By setting the content of the curing accelerator (F) within the above range, the cured product can more effectively exhibit low shrinkage, low thermal expansion, and excellent dielectric properties.

<Other ingredients>
The thermosetting resin composition of the present invention comprises (E) a thermoplastic resin other than the thermoplastic elastomer, a flame retardant, an ultraviolet absorber, an antioxidant, an antioxidant, a photopolymerization initiator, and fluorescence, as long as the effects of the present invention are not impaired. It may contain a whitening agent, an adhesiveness improving agent and the like. These can be used alone or in admixture of two or more.

(Thermoplastic resin)
Examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, and poly. Examples thereof include ether ether ketone resin, polyetherimide resin, siloxane resin, tetrafluoroethylene resin and the like.

(Flame retardants)
Examples of the flame retardant include halogen-containing flame retardants containing bromine, chlorine and the like; phosphorus-based flame retardants such as triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphazene, phosphate ester compounds and red phosphorus; sulfamine. Nitrogen-based flame retardants such as guanidine acid, melamine sulfate, melamine polyphosphate, and melamine cyanurate; phosphazene-based flame retardants such as cyclophosphazene and polyphosphazene; and inorganic flame retardants such as antimony trioxide.

(UV absorber, etc.)
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers. Examples of the antioxidant include hindered phenol-based and hindered amine-based antioxidants. Examples of the photopolymerization initiator include benzophenones, benzyl ketals, thioxanthone-based photopolymerization initiators and the like. Examples of the fluorescent whitening agent include a fluorescent whitening agent of a stilbene derivative. Examples of the adhesiveness improving agent include urea compounds such as ureasilane, and coupling agents such as silane-based, titanate-based, and aluminate-based coupling agents.

(Organic solvent)
In the thermosetting resin composition of the present invention, each component is dissolved or uniformly dispersed in an organic solvent from the viewpoint of facilitating handling by diluting and facilitating the production of a prepreg and a film with a resin, which will be described later. It is preferably in the state of a varnish.
The organic solvent used for producing the varnish is not particularly limited, and for example, a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; an alcohol solvent such as methyl cellosolve; an ether solvent such as tetrahydrofuran; toluene, Examples thereof include aromatic solvents such as xylene and mesitylen. These can be used alone or in admixture of two or more.
The content of the thermosetting resin composition in the varnish is preferably 40 to 90% by mass, more preferably 50 to 80% by mass of the entire varnish. By keeping the content of the thermosetting resin composition within the above range, it is possible to obtain a prepreg and a film with a resin to which an appropriate amount of the thermosetting resin composition is attached while maintaining good coatability.

[Prepreg]
The prepreg of the present invention contains the thermosetting resin composition of the present invention.
The prepreg of the present invention can be produced, for example, by impregnating or applying the thermosetting resin composition of the present invention to a base material and then semi-curing (B-stage). More specifically, the thermosetting resin composition of the present invention is applied to a base material by a method such as impregnation, spraying, or extrusion, and then semi-cured (B-staged) by, for example, heating. The prepreg of the present invention containing a base material and a semi-cured (B-staged) thermosetting resin composition can be produced. Hereinafter, the prepreg of the present invention will be described in detail.

As the base material used for the prepreg of the present invention, for example, well-known materials used for various laminated plates for electrical insulating materials can be used. Examples of the material include inorganic fibers such as E glass, D glass, S glass and Q glass; organic fibers such as polyimide, polyester and tetrafluoroethylene, and a mixture thereof.
These substrates have shapes such as woven fabrics, non-woven fabrics, robinks, chopped strand mats, and surfaced mats. The material and shape of the base material may be selected according to the intended use and performance of the molded product, and may be used alone or in combination of two or more types, if necessary.
Further, as the base material, those surface-treated with a silane coupling agent or the like or those subjected to mechanical opening treatment are suitable from the viewpoint of heat resistance, moisture resistance and processability.
The thickness of the base material is not particularly limited and can be, for example, in the range of 0.03 to 0.5 mm.

The content (adhesion amount) of the thermosetting resin composition in the prepreg of the present invention is preferably 20 to 90% by mass in terms of the content of the thermosetting resin composition of the prepreg after drying.
The prepreg of the present invention is, for example, 100 to 200 ° C. after impregnating or coating a base material with a thermosetting resin composition so that the content of the thermosetting resin composition in the prepreg is within the above range. It can be produced by heating and drying at the same temperature for 1 to 30 minutes and semi-curing (B-stage).

[Film with resin]
The resin-containing film of the present invention contains the thermosetting resin composition of the present invention.
The resin-coated film of the present invention can be obtained, for example, by applying the thermosetting resin composition of the present invention to a support. Specifically, a varnish containing the thermosetting resin composition of the present invention is applied to a support and dried to volatilize the organic solvent in the varnish, and the thermosetting resin composition is semi-cured (B stage). It can be produced by forming a resin composition layer made of the thermosetting resin composition of the present invention on the support.
The resin-coated film of the present invention thus obtained has a support and a semi-cured resin composition layer formed from the thermosetting resin composition of the present invention on one surface of the support. It is a thing. However, this semi-cured state is a state in which the adhesive force between the thermosetting resin composition and the circuit pattern substrate is ensured when the thermosetting resin composition is cured, and the circuit pattern substrate can be embedded. It is desirable that (fluidity) is ensured.

As a method (coating machine) for applying the thermosetting resin composition to the support, a die coater, a comma coater, a bar coater, a kiss coater, a roll coater, or the like can be used. These coating machines can be appropriately selected depending on the desired thickness of the resin composition layer.

As a drying method after applying the thermosetting resin composition to the support, a method such as heating or hot air blowing can be applied.
The drying conditions can be, for example, a condition in which the content of the organic solvent in the resin composition layer after formation is 10% by mass or less, preferably 5% by mass or less. The drying conditions vary depending on the amount of the organic solvent in the varnish, the boiling point of the organic solvent, etc., but for example, by drying the varnish containing 30 to 60% by mass of the organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. A resin composition layer can be formed. Further, it is preferable that the drying conditions are appropriately set in advance by a simple experiment.

The thickness of the resin composition layer in the resin-containing film is usually preferably equal to or larger than the thickness of the conductor layer of the circuit board. The thickness of the conductor layer is, for example, 5 to 70 μm, and is preferably 5 to 50 μm, more preferably 5 to 30 μm, from the viewpoint of lightness, thinness, shortness, and miniaturization of the multilayer printed wiring board. Therefore, the thickness of the resin composition layer can be, for example, 5 μm or more, and for example, 80 μm or less, preferably 60 μm or less, more preferably 40 μm or less, and more than the thickness of the conductor layer. You can choose the thickness.

The support in the resin-coated film of the present invention is, for example, a film made of a polyolefin such as polyethylene, polypropylene or polyvinyl chloride, polyethylene terephthalate (hereinafter also referred to as "PET"), polyester such as polyethylene naphthalate, polycarbonate or polyimide; Release paper: Metal foil such as copper foil and aluminum foil can be mentioned. These supports and the protective film described later may be subjected to a matte treatment, a corona treatment, a mold release treatment, or the like.
The thickness of the support is, for example, preferably 10 to 150 μm, more preferably 25 to 50 μm.
A protective film similar to the support can be further laminated on the surface of the resin composition layer where the support is not in close contact. By laminating a protective film, it is possible to prevent foreign matter from entering. The thickness of the protective film is, for example, 1 to 40 μm. The resin-coated film can also be rolled up and stored.

[Laminated board]
The laminated board of the present invention contains a cured product of the prepreg of the present invention and / or a cured product of the resin-containing film of the present invention.
Hereinafter, the method for producing the laminated board of the present invention will be described in detail. In the laminated board of the present invention, the layer made of the cured product of the prepreg or the film with resin of the present invention may be referred to as an "insulating resin layer".

Examples of the method for forming a laminated plate using the resin-coated film of the present invention include a method of laminating the resin-coated film of the present invention on one side or both sides of a circuit board using a vacuum laminator.
Examples of the substrate used for the circuit board include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a heat-curable polyphenylene ether substrate, and the like. The circuit board means a circuit board having a patterned conductor layer (circuit) formed on one side or both sides of the board as described above. Further, in a laminated board formed by alternately laminating conductor layers and insulating layers and a multilayer printed wiring board manufactured from the laminated board, a conductor layer in which one or both sides of the outermost layer of the multilayer printed wiring board is patterned. What is (circuit) is also included in the circuit board referred to here. The surface of the conductor layer may be roughened in advance by a blackening treatment or the like.

In the above lamination, when the resin-attached film has a protective film, after removing the protective film, the resin-attached film and the circuit board are preheated as necessary, and the resin-attached film is pressurized and heated. Crimped to the circuit board.
In the resin-coated film of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used. The laminating conditions are, for example, a crimping temperature (lamination temperature) preferably 70 to 140 ° C., a crimping pressure preferably 0.1 to 1.1 MPa, and laminating under a reduced pressure of 20 mmHg (26.7 hPa) or less. preferable. Further, the laminating method may be a batch method or a continuous method using a roll.

An insulating resin layer can be formed on the circuit board by laminating the resin-containing film on the circuit board, cooling it to around room temperature, peeling the support, and then heat-curing the support. The conditions for thermosetting may be appropriately selected according to the type and content of the resin component in the resin composition layer of the resin-coated film, and are, for example, in the range of 20 to 180 minutes at 150 ° C to 220 ° C. It is selected, preferably at 160 ° C. to 200 ° C. for 30 to 120 minutes.

If the support is not peeled off before the resin composition layer is cured, the support is peeled off after the insulating resin layer is formed, and then, if necessary, the insulating resin layer formed on the circuit board is perforated. Via holes, through holes and the like may be formed.
Drilling can be performed by, for example, a drill, a laser, a plasma, or a combination method thereof. Among these, drilling with a laser such as a carbon dioxide gas laser or a YAG laser is a general method.

Then, the conductor layer may be formed on the insulating resin layer by dry plating or wet plating. As the dry plating, known methods such as thin film deposition, sputtering, and ion plating can be used. In the case of wet plating, first, the surface of the cured insulating resin layer is coated with permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, etc. It is roughened with an oxidizing agent to form an uneven anchor. As the oxidizing agent, an aqueous solution of sodium hydroxide (aqueous solution of alkaline permanganate) such as potassium permanganate and sodium permanganate is particularly preferably used. Next, the conductor layer is formed by a method that combines electroless plating and electrolytic plating. It is also possible to form a plating resist having a pattern opposite to that of the conductor layer, and to form the conductor layer only by electroless plating. As a method for subsequent pattern formation, for example, a known subtractive method, semi-additive method, or the like can be used.

Next, a method for manufacturing the laminated board of the present invention using the prepreg of the present invention will be described.
The laminated board of the present invention can be produced by laminating and molding the prepreg of the present invention. In this case, the laminated board of the present invention includes an insulating resin layer obtained by curing the prepreg of the present invention.
Specifically, a laminated board can be manufactured by laminating 1 to 20 sheets of the prepreg of the present invention and laminating and molding a metal foil such as copper or aluminum on one side or both sides thereof. .. The metal foil is not particularly limited as long as it is used in a laminated board for an electrically insulating material.
As the molding conditions, for example, the method of a laminated plate for an electrically insulating material and a multilayer plate can be applied. For example, using a multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine, etc., the temperature is 100 to 250 ° C. It can be molded under the conditions of 2 to 10 MPa and a heating time of 0.1 to 5 hours. Further, the laminated board of the present invention can also be manufactured by combining the prepreg of the present invention and the wiring board for the inner layer and laminating and molding.

[Multilayer printed wiring board]
The multilayer printed wiring board of the present invention includes the laminated board of the present invention.
The multilayer printed wiring board of the present invention can be manufactured by circuit-processing a conductor layer (metal leaf) arranged on one side or both sides of the insulating resin layer in the laminated board of the present invention.
Specifically, first, the conductor layer of the laminated plate of the present invention is wired by an ordinary etching method, and then a plurality of laminated plates wired via the prepreg of the present invention are laminated and heat-pressed. Multi-layered collectively by. After that, the multilayer printed wiring board of the present invention can be manufactured through the formation of through holes or blind via holes by drilling or laser processing and the formation of interlayer wiring by plating or conductive paste.

Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.
The characteristics of the resin plate and the copper-clad laminate obtained in the following examples were measured and evaluated by using the following methods.

[Evaluation methods]
(1) Shrinkage rate of resin plate A resin plate having a length of 5 mm (X direction), a width of 5 mm (Y direction), and a thickness of 1.5 mm ± 0.5 mm (Z direction) was prepared, and a TMA test device (TA instrument) was prepared. Thermomechanical analysis was performed by the compression method using Q400) manufactured by the company. After mounting the resin plate on the device in the X direction, the load is 5 G, the heating rate is 45 ° C./min, and the temperature profile is 20 ° C. (holding for 5 minutes) to 260 ° C. (holding for 2 minutes) to 20 ° C. (holding for 5 minutes). Measured at. From the dimensions of 20 ° C. before the start of temperature rise and the dimensions of 20 ° C. after temperature rise, the amount of dimensional change in the X direction before and after the temperature rise was obtained, and the shrinkage rate of the resin plate was calculated using the following formula. ..
Curing shrinkage rate (%) = {(Dimension at 20 ° C before the start of temperature rise (mm) Dimension at 20 ° C after the start of temperature rise (mm)) / Dimension at 20 ° C before the start of temperature rise (mm)} × 100

(2) Thermal expansion coefficient of resin plate A resin plate with a length of 5 mm (X direction), a width of 5 mm (Y direction), and a thickness of 1.5 mm ± 0.5 mm (Z direction) was prepared, and a TMA test device (TA instrument) was prepared. Thermomechanical analysis was performed by the compression method using Q400) manufactured by Ment. After mounting the resin plate on the device in the X direction, the load is 5 G, the heating rate is 45 ° C./min, and the temperature profile is 20 ° C. (holding for 5 minutes) to 260 ° C. (holding for 2 minutes) to 20 ° C. (holding for 5 minutes). Measured at. The average coefficient of thermal expansion at 50 to 120 ° C. during cooling was calculated, and this was used as the coefficient of thermal expansion of the resin plate.

(3) Mounted Warpage Amount of warpage of the copper-clad laminate was evaluated using Thermoray PS200 Shadow Moire analysis manufactured by AKROMETRIX. The size of the copper-clad laminate was 40 mm × 40 mm, and the measurement area was 36 mm × 36 mm. The amount of warpage when the copper-clad laminate was heated to room temperature (25 ° C.) to 260 ° C. and then cooled to 50 ° C. was measured.

[(B) Production of amino-modified siloxane]
Production Example 1: (B1) Production of Amino-Modified Siloxane Compound Containing Aromatic Azomethine Skeleton A terephthalaldehyde (terephthalaldehyde) (terephthalaldehyde) (terephthalaldehyde) Toray Fine Chemicals Co., Ltd. 22.75 g, 4,4'-diamino-3,3'-diethyldiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., KAYAHARD A-A) 17.25 g, propylene glycol monomethyl ether (hereinafter, "" 60.0 g (also referred to as "PGM") was added and refluxed for 2 hours to obtain a dialdehyde compound (hereinafter, also referred to as "LCA") containing an aromatic azomethine structural unit represented by the following formula (4).
Next, in a reaction vessel with a volume of 500 ml that can be heated and cooled equipped with a thermometer, a stirrer, and a moisture meter with a reflux cooling tube, 22.15 g of LCA prepared above and a diamine-modified siloxane at both ends (Shinetsu Chemical Industry Co., Ltd.) Manufactured by Co., Ltd., trade name: X-22-161B) 96.14 g and PGM 144.21 g were added, refluxed for 2 hours, then heated to 130 ° C. and concentrated under atmospheric pressure, using the following formula (4). A solution containing a represented aromatic azomethine structural unit and a siloxane structural unit represented by the following formula (5) and containing a siloxane compound having an amino group at both ends (hereinafter, also referred to as "AZS") is obtained. (Content of resin component: 70% by mass).

Production Example 2: Aromatic azomethine skeleton-containing siloxane-modified imide resin In a reaction vessel with a volume of 5 liters that can be heated and cooled equipped with a thermometer, a stirrer, and a moisture meter with a reflux cooling tube, 2,2-bis (4- (4-Maleimidephenoxy) Phenyl) Propane [manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000] 791.82 g, AZS 101.22 g obtained in Production Example 1, p-aminophenol 18.93 g, 4, Add 63.4 g of 4'-diamino-3,3'-diethyldiphenylmethane (KAYAHARD A-A manufactured by Nippon Kayaku Co., Ltd.) and 1387.13 g of PGM, react at 115 ° C. for 4 hours, and then reach 130 ° C. The temperature was raised and concentrated at atmospheric pressure to obtain a solution containing an aromatic azomethine skeleton-containing siloxane-modified imide resin (hereinafter, also referred to as “AZS-modified imide resin”) (resin component content: 63% by mass).

Examples 1 to 13, Comparative Examples 1 to 5
Various components shown below were mixed at the ratios shown in Tables 1 and 2 and diluted with methyl ethyl ketone as necessary to obtain a varnish having a thermosetting resin composition content of 65% by mass.
Next, the above varnish was applied onto a PET film having a thickness of 30 μm using a film applicator (manufactured by Yoshimitsu Seiki Co., Ltd., trade name: YBA type baker applicator) so as to have a thickness of 30 μm after drying. It was dried at 130 ° C. for 5 minutes. The semi-cured resin plate obtained by drying was crushed to collect resin powder, and the resin powder was placed between two copper foils at a pressure of 2.5 MPa and a temperature of 240 ° C. at 60 ° C. Press molded for minutes. Then, the electrolytic copper foils on both sides were removed by peeling to obtain a resin plate. At the time of press molding, the copper foil was arranged so that the surface on the resin powder side became a glossy surface.

Further, the varnish was impregnated and coated on an S glass cloth having a thickness of 0.1 mm and dried by heating at 110 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 50% by mass.
Four of these prepregs were stacked, 18 μm electrolytic copper foils were arranged one above the other, and press molding was performed at a pressure of 2.5 MPa and a temperature of 230 ° C. for 90 minutes to obtain a copper-clad laminate.
The evaluation results of the obtained resin plate and copper-clad laminate are shown in Tables 1 and 2.

The names of raw materials and the like and product names used in Examples and Comparative Examples are described below.
(1) (A1) Plate-shaped filler-MEG160FY-M01 [manufactured by Nippon Sheet Glass Co., Ltd .; sample name]
Glass composition: E glass Average thickness: 0.7 μm
Ignition loss (LOI): 0.7%
Average particle size: 160 μm
・ Sunburari [manufactured by AGC Si-Tech Co., Ltd .; product name]
Glass composition: SiO ₂
Average particle size (tertiary agglomerated particles): 4.0-6.0 μm

(2) (A2) Spherical filler ・ SC-2050KNK: Spherical silica [manufactured by Admatex Co., Ltd .; trade name, average particle size: 0.5 μm]

(2) (B) Amino-modified siloxane-X-22-161B: Both-terminal amine-modified siloxane [manufactured by Shin-Etsu Chemical Co., Ltd .; product name]
AZS: Amino-modified siloxane containing azomethine skeleton prepared in Production Example 1 [in-house synthesized product]

(4) (C) Thermosetting resin-BMI-4000: 2,2-bis [4- (4-maleimide phenoxy) phenyl] propane [manufactured by Daiwa Kasei Kogyo Co., Ltd .; product name]
-AZS-modified imide resin: Aromatic azomethine skeleton-containing siloxane-modified imide resin prepared in Production Example 2-NC-7000L: α-naphthol / cresol novolac type epoxy resin [manufactured by Nippon Kayaku Co., Ltd .; product name]

(5) (D) Amine compound having an acidic substituent ・ p-aminophenol [manufactured by Kanto Chemical Co., Inc .; trade name]

(6) (F) Curing Accelerator G-8009L: Adduct of hexamethylene diisocyanate represented by the general formula (3) and 2-ethyl-4-methylimidazole (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .; trade name)

(7) Hardener-KAYAHARD A-A: 3,3'-diethyl-4,4'-diaminodiphenylmethane [manufactured by Nippon Kayaku Co., Ltd .; trade name]

From Tables 1 and 2, the resin plates and copper-clad laminates of Examples 1 to 13 obtained from the thermosetting resin composition of the present invention have small shrinkage rate, coefficient of thermal expansion and warpage amount, and have low shrinkage and shrinkage. It can be seen that it has excellent low thermal expansion and can suppress warpage during mounting.
On the other hand, the resin plates of Comparative Examples 1 to 5 and the copper-clad laminates obtained from the thermosetting resin (A1) which does not contain the plate-like filler as the filler (A) are compared with those of Examples 1 to 13. It can be seen that the shrinkage rate, the coefficient of thermal expansion, and the amount of warpage are all inferior.

Claims (14)

A prepreg containing a thermosetting resin composition containing (A) a filler, (B) an amino-modified siloxane, and (C) a thermosetting resin, wherein the (A) filler is a (A1) plate. the Jo filler seen including,
The content of the plate-shaped filler (A1) is 30 to 300 parts by mass per 100 parts by mass of the total amount of the solid content-equivalent resin component in the thermosetting resin composition.
(B) A prepreg having an amino-modified siloxane content of 10 to 30 parts by mass per 100 parts by mass of the total amount of solid content-equivalent resin components in the thermosetting resin composition . The prepreg according to claim 1, wherein the filler (A) further comprises (A2) a spherical filler. The prepreg according to claim 1, wherein the content of the (A1) plate-like filler in the (A) filler is 20 to 100% by mass. (A1) The prepreg according to any one of claims 1 to 3, wherein the plate-shaped filler has an average particle size of 0.05 to 300 μm. (A1) The prepreg according to any one of claims 1 to 4, wherein the plate-shaped filler contains one or more selected from the group consisting of talc, mica, clay, montmorillonite, silica and glass. Any one of claims 1 to 5, wherein the thermosetting resin composition contains (C1) a maleimide resin having at least two N-substituted maleimide groups in one molecule as the (C) thermosetting resin. The prepreg described in the section. The prepreg according to any one of claims 1 to 6, wherein the thermosetting resin composition contains (B1) an aromatic azomethine skeleton-containing amino-modified siloxane as (B) amino-modified siloxane. The component (B1) has a structural unit derived from an aromatic azomethine compound having at least one aldehyde group in one molecule (b-1) and at least two primary amino groups at the terminal of the molecule (b-2). The prepreg according to claim 7, which comprises a structural unit derived from a siloxane compound having. The prepreg according to any one of claims 1 to 8, wherein the thermosetting resin composition further contains (D) an amine compound having an acidic substituent. The thermosetting resin composition
As the component (B), (B1) an aromatic azomethine skeleton-containing amino-modified siloxane, and as the component (C), a maleimide resin having at least two N-substituted maleimide groups in one molecule (C1), and (D). An aromatic azomethine skeleton-containing siloxane containing an amine compound having an acidic substituent, a structural unit derived from the component (B1), a structural unit derived from the component (C1), and a structural unit derived from the component (D). The prepreg according to any one of claims 1 to 9, which is included as a modified imide resin. The prepreg according to any one of claims 1 to 10, wherein the thermosetting resin composition further contains (E) a thermoplastic elastomer. The prepreg according to any one of claims 1 to 11, wherein the thermosetting resin composition further contains (F) a curing accelerator. A laminated board containing a cured product of the prepreg according to any one of claims 1 to 12. A multilayer printed wiring board including the laminated board according to claim 13.