JP2017132858A - Thermosetting resin composition, prepreg, film with resin, laminate and multilayer printed board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition that has low contractility and low thermal expansion and can prevent warpage at the time of implementation, and a prepreg, a film with resin, a laminate and a multilayer printed board prepared therewith.SOLUTION: A thermosetting resin composition comprises (A) filler, (B) amino modified siloxane, and (C) thermosetting resin, where (A) filler comprises (A1) tabular filler. There are also provided a prepreg, a film with resin, a laminate and a multilayer printed board prepared therewith.SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting resin composition, a prepreg, a film with a resin, a laminated board, and a multilayer printed wiring board.

  In recent years, along with the trend toward miniaturization and high performance of electronic devices, advancement of wiring density and high integration have progressed in printed wiring boards, and with this, laminated boards for printed wiring boards include: There is an increasing demand for improved reliability by improving heat resistance. In general, it is known that the wiring board material changes its dimensions before and after mounting (shrinks after mounting) when a chip is mounted on a substrate, which causes cracks in solder and poor connection. What happens is a problem. Further, in the semiconductor package substrate, with the downsizing and thinning, the occurrence of warpage due to the difference in thermal expansion coefficient from the chip during component mounting and package assembly has become a major issue.

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

  A polyimide resin has very excellent strength, heat resistance and low thermal expansion as compared with other polymer resin materials, and is excellent in electrical insulation, but has a problem of low adhesion. 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 warpage generated during mounting, causing a problem such as disconnection. Therefore, studies have been made to improve the adhesion by modifying the terminal of the polyimide resin with an amine compound having an acidic substituent and reacting with an epoxy resin or the like (see, for example, Patent Document 2).

Japanese Patent Laid-Open No. 5-148343 Japanese Patent Laid-Open No. 2014-024927

However, due to recent demands for more stringent reliability, further low warpage, low shrinkage and low thermal expansion are desired.
In view of the current situation, the present invention is a thermosetting resin composition that is excellent in low shrinkage and low thermal expansion and can suppress warping during mounting, and a prepreg, a film with a resin, a laminate, 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 found that a thermosetting resin composition containing a plate-like filler, an amino-modified siloxane and a thermosetting resin has low shrinkage and low thermal expansion. The present inventors have found that it is excellent and can suppress warping during mounting, and have reached the present invention.
That is, the present invention provides the following [1] to [17].
[1] A thermosetting resin composition comprising (A) a filler, (B) an amino-modified siloxane, and (C) a thermosetting resin, wherein (A) the filler is (A1) plate A thermosetting resin composition containing a filler.
[2] The thermosetting resin composition according to [1], wherein the (A) filler further includes (A2) a spherical filler.
[3] The thermosetting resin composition according to the above [1], wherein the content of the (A1) plate filler in the (A) filler is 20 to 100% by mass.
[4] The thermosetting resin composition according to any one of [1] to [3], wherein the average particle diameter of the (A1) plate-like filler is 0.05 to 300 μm.
[5] (A1) The thermosetting according to any one of [1] to [4], wherein the plate-like filler includes one or more selected from the group consisting of talc, mica, clay, montmorillonite, silica, and glass. Resin composition.
[6] The heat according to any one of [1] to [5], wherein (C) includes a maleimide resin having (C1) at least two N-substituted maleimide groups in one molecule as the thermosetting resin. Curable resin composition.
[7] The thermosetting resin composition according to any one of the above [1] to [6], which comprises (B1) an amino-modified siloxane containing an aromatic azomethine skeleton as the amino-modified siloxane.
[8] The component (B1) comprises (b-1) a structural unit derived from an aromatic azomethine compound having at least one aldehyde group in one molecule, and (b-2) at least two primary units at the molecular end. The thermosetting resin composition according to the above [7], comprising 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], further including (D) an amine compound having an acidic substituent.
[10] (B1) aromatic azomethine skeleton-containing amino-modified siloxane as the component (B), and (C1) a maleimide resin having at least two N-substituted maleimide groups in one molecule as the component (C); (D) Aromatic azomethine comprising 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 thermosetting resin composition according to any one of [1] to [9], which is included as a skeleton-containing siloxane-modified imide resin.
[11] The thermosetting resin composition according to any one of [1] to [10], further including (E) a thermoplastic elastomer.
[12] The thermosetting resin composition according to any one of [1] to [11], further including (F) a curing accelerator.
[13] A prepreg comprising the thermosetting resin composition according to any one of [1] to [12].
[14] A film with a resin comprising the thermosetting resin composition according to any one of [1] to [12].
[15] A laminate comprising a cured product of the prepreg according to [13].
[16] A laminate including a cured product of the film with resin according to [14].
[17] A multilayer printed wiring board including the laminated board according to [15] or [16].

  According to the present invention, there are provided a thermosetting resin composition excellent in low shrinkage and low thermal expansion and capable of suppressing warpage during mounting, and a prepreg, a resin-coated film, a laminate 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 that is greater than or equal to X and less than or equal to Y (X and Y are real numbers) may be expressed as “X to Y”. For example, the description “0.1-2” indicates a numerical range that is 0.1 or more and 2 or less, and the numerical range includes 0.1, 0.34, 1.03, 2, and the like.

  In the present specification, the “resin composition” refers to a mixture of components described later, a product obtained by semi-curing the mixture (so-called B-stage shape), and a product obtained by curing (so-called C-stage shape). Including all of.

[Thermosetting resin composition]
The thermosetting resin composition of the present invention is a thermosetting resin composition comprising (A) a filler, (B) an amino-modified siloxane, and (C) a thermosetting resin. The filler contains (A1) a plate-like filler.
When the thermosetting resin composition of the present invention has the above-described configuration, the thermosetting resin composition is excellent in low shrinkage and low thermal expansion, and can suppress warping during mounting. The reason why such an effect is obtained is not clear, but the inventors consider as follows.
Since conventional wiring board materials are cured in a stretched state during lamination 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 contracts to its 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, -Like filler exhibits good orientation in the thermosetting resin composition. As a result, it is possible to suppress the elongation of the resin due to the stress at the time of pressing, so it is possible to reduce the internal stress existing in the obtained laminate, and the amount of dimensional change that occurs during heating such as chip mounting, that is, the shrinkage rate is reduced. It is thought.
Further, since the warpage caused by the shrinkage of the package during chip mounting or lamination 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.

<(A) Filler>
The thermosetting resin composition of the present invention contains (A) a filler, and (A) the filler contains (A1) a plate-like filler.
In the present invention, the term “plate shape” is used to mean, for example, a flat shape, a flat plate shape, a flake shape, a scale shape, etc., and an aspect ratio (average) defined by the average maximum long diameter and average thickness of particles. (Maximum major axis / average thickness) means 3 or more.
(A1) The average maximum major axis and the average thickness of the plate-like filler can be measured by observation with an electron microscope, and for each of 50 or more arbitrarily selected particles, the respective maximum major axis and thickness are measured. The average can be obtained as the average maximum major axis and the average thickness.

(A1) The material of the plate filler is not particularly limited, and any of inorganic materials and organic materials can be used. However, a prepreg, a film with a resin, and a laminate obtained by using the thermosetting resin composition of the present invention. An inorganic material is preferable from the viewpoint of improving heat resistance (thermal characteristics), low shrinkage, and mechanical characteristics of a board, a multilayer printed wiring board, 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, it is preferable to use glass and mica from the viewpoint that decomposition of the resin can be suppressed. Moreover, when using glass as an inorganic material, glass flakes can be used as (A1) plate-like filler, and it is preferable to use an alkali free glass flake.
Examples of the organic material include wood powder, pulp, pulverized cloth, thermosetting resin cured product powder, and the like.

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

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

  (A1) When the plate-like filler is an inorganic material, (C) a coupling agent such as a silane coupling agent or a titanate coupling agent for the purpose of improving the adhesion at 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 is improved, and the storage stability when the thermosetting resin composition is used as a varnish is improved. it can. Further, when the varnish is applied to a glass cloth, a film or the like, and when a prepreg 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, N-β- (aminoethyl) -γ-aminopropyltriditrimethoxy. Amino group-containing silane coupling agents such as methylsilane; glycidyl group-containing silanes such as γ-glycidoxypropylmethoxysilane, γ-glycidoxypropylethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Coupling agents: Titanium coupling agents such as isopropyltristearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, tetraisopropylbis (dioctyl phosphite) titanate, and the like. 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 below, or (A1) the plate-like filler before blending may be used in a form of pretreatment.

The content of the (A1) plate 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 resin components in terms of solid content in the thermosetting resin composition. Is preferable, and it is more preferable that it is 150-300 mass parts. By setting it as the said content, the orientation of (A1) plate-shaped filler can be kept favorable, and the outstanding low shrinkage rate, low thermal expansibility, and low curvature property are obtained.
The total amount of 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 in terms of solid content. Amount.

  (A) The content of the (A1) plate filler in the 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 it as the said content, the orientation of (A1) plate-shaped filler can be kept favorable, and the outstanding low shrinkage rate, low thermal expansibility, and low curvature property are obtained.

The thermosetting resin composition of the present invention may contain a filler other than (A1) a plate-like filler as (A) a filler.
(A1) The material of the filler other than the plate-like filler is not particularly limited, and both inorganic materials and organic materials can be used. Laminated plates obtained using the thermosetting resin composition of the present invention, etc. From the viewpoint of improving the heat resistance (thermal characteristics), low shrinkage and mechanical properties of the inorganic materials, inorganic materials are preferable.
Further, the shape of the filler other than (A1) plate-like filler is not particularly limited as long as it is other than plate-like, but (A2) is a spherical filler from the viewpoint that it can be closely packed and is excellent in low thermal expansion. preferable.
In the present invention, the term “spherical” is a concept including shapes such as a true sphere, a circular particle, and an ellipse. More specifically, the aspect ratio (major axis / minor axis) between the major axis and the minor axis is 1. Means ~ 2.
The major axis in the spherical filler is the maximum length that can be taken in the projected image of the particle, 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 an image taken with an electron microscope, determining the ratio of the major axis to the minor axis, and calculating the average value. Can do.

(A1) Examples of inorganic fillers other than plate-like fillers include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, and stannic acid, which have shapes other than plate-like fillers. Examples 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 viewpoints of dielectric properties, heat resistance, and low thermal expansion. By using silica having a shape other than a plate shape together with the (A1) plate filler, the orientation of the (A1) plate filler can be controlled, and a low thermal expansion coefficient of silica can be imparted to the resin.
Examples of the silica include precipitated silica produced by a wet method and having a high water content, dry method silica produced by a dry method and containing almost no bound water, and the like. , 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 is preferably 0.1 to 10 μm, and more preferably 0.3 to 8 μm. When the average particle diameter of the spherical silica is 0.1 μm or more, the fluidity when the resin is highly filled can be kept good, and when it is 10 μm or less, the mixing probability of coarse particles is reduced. Moreover, generation | occurrence | production of the defect resulting from a coarse particle can be suppressed. The average particle diameter can be measured in the same manner as in the case of (A1) plate 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 resin components in terms of solid content in the thermosetting resin composition. It is preferable that it is -200 mass parts, and it is more preferable that it is 30-100 mass parts. By setting it as the said content, the outstanding low thermal expansibility and the high fluidity | liquidity at the time of filling with resin are obtained.

  When the thermosetting resin composition of the present invention contains (A2) spherical filler, the content of (A2) spherical filler in (A) filler is preferably 5 to 80% by mass, and 10 to 60% by mass. % Is more preferable, and 15 to 40% by mass is even more preferable. By setting it as the said content, the outstanding low thermal expansibility and the high fluidity | liquidity at the time of filling with resin are obtained.

  (A1) As an organic filler other than the plate-like filler, for example, a resin filler having a uniform structure made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, siloxane resin, tetrafluoroethylene resin, etc. having a shape other than plate-like, Rubber core layer made of acrylic ester resin, methacrylic ester resin, conjugated diene resin, etc., acrylic ester resin, methacrylic ester resin, aromatic vinyl resin, 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 is 30 to 600 parts by mass per 100 parts by mass of the total solid resin component in the thermosetting resin composition. Preferably, it is 150-400 mass parts. (A) By making content of a filler into the said range, the moldability and low thermal expansibility of a prepreg can be kept favorable.

<(B) Amino-modified siloxane>
The thermosetting resin composition of the present invention contains (B) an amino-modified siloxane. (B) The amino-modified siloxane (hereinafter also referred to as “component (B)”) is not particularly limited. 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 Group or substituted phenyl group, which may be the same or different. R ₃ and R ₄ each independently represents 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 general formula (1), the alkyl group represented by R ₁ , R ₂ , R ₃ or R ₄ is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, More preferred are alkyl groups having 1 or 2 carbon atoms.
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, and a pentyl group. 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 among these, an alkyl group is preferable. The alkyl group is preferably the same as described above.
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, and a propylene group. Examples of the arylene group include a phenylene group and a naphthylene group.

  (B) A commercial item can be used for amino modified siloxane. Examples of the commercially available (B) amino-modified siloxane include “KF-8010” having an amino group at both ends (amino group equivalent: 430 g / mol) and “X-22-161A” (amino group equivalent: 800 g / mol). , “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) (above, manufactured by Shin-Etsu Chemical 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) ol) (manufactured by Toray Dow Corning Co., Ltd.), “KF-868” having an amino group in the side chain (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) (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Is mentioned. These can be used alone or in admixture of two or more. Among these, from the point of low water absorption, "X-22-161A", "X-22-161B", "KF-8012", "KF-8008", "X-22-1660B-3" and " "BY-16-853B" is preferred, and "X-22-161A", "X-22-161B" and "KF-8012" are more preferred from the viewpoint of low thermal expansion.

  The (B) amino-modified siloxane preferably contains (B1) an aromatic azomethine skeleton-containing amino-modified siloxane (hereinafter also referred to as “component (B1)”). (B1) By including an amino-modified siloxane containing an aromatic azomethine skeleton, the orientation of the resin can be increased, and the cured product of the thermosetting resin composition of the present invention can have a lower thermal expansion and a higher elastic modulus. Can do.

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

[(B-1) an aromatic azomethine compound having at least one aldehyde group in one molecule]
The component (b-1) includes, 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 amino acids in the molecular structure. It can be obtained by reacting 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'-dicarboxaldehyde, and the like. These can be used in combination of two or more. Among these, terephthalaldehyde is preferable from the viewpoints of lower thermal expansion, high reactivity, excellent solvent solubility, and easy commercial availability.

Examples of the polyfunctional amine compound include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1,4-diaminobenzene, 2,5-dimethyl-1,4-diaminobenzene, 4 , 4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-diaminodiphenyl ether, 4,4 '-Diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, benzidine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4, 4′-diaminobiphenyl, 3,3′-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) Nyl) 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 Etc. These can be used in combination of two or more.
Among these, for example, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino-, because of 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, is inexpensive, and is 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′-diene is preferred from the viewpoint of low thermal expansion and dielectric properties. Amino-3,3'-diethyl - diphenylmethane, bis (4- (4-aminophenoxy) phenyl) propane is more preferred. Moreover, 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 usage amount of the polyfunctional aldehyde compound and the polyfunctional amine compound is, for example, the number of primary amino groups of the polyfunctional amine compound [the amount of polyfunctional amine compound used / the primary amino group equivalent of the polyfunctional amine compound] It is preferable to use the aldehyde compound so as to be in the range of 0.1 to 5.0 times the number of aldehyde groups of the aldehyde compound [amount of use of polyfunctional aldehyde compound / aldehyde group equivalent of polyfunctional aldehyde compound]. By making it 0.1 times or more, the molecular weight of the aromatic azomethine compound obtained by this reaction can be kept good, and by making it 5.0 times or less, good solubility in a solvent can be obtained. It is 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 with respect to 100 parts by mass of the total of the polyfunctional aldehyde compound and the polyfunctional amine compound. More preferably, it is 40-500 mass parts. When the amount of the organic solvent used is 25 parts by mass or more, good solubility is obtained, and when it is 2000 parts by mass or less, a sufficient reaction rate is obtained.

(B-1) In one molecule, a polyfunctional aldehyde compound, a polyfunctional amine compound, an organic solvent, and, if necessary, a reaction catalyst are charged in a reaction kettle and stirred while being heated and kept warm as necessary to cause a dehydration condensation reaction. 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. The reaction time can be, for example, in the range of 0.1 to 10 hours. The reaction temperature is preferably, for example, 70 to 150 ° C, and more preferably 100 to 130 ° C because it is desirable to perform the reaction while removing water as a by-product. By setting the reaction temperature to 70 ° C. or higher, a sufficient reaction rate can be obtained. 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 hardly remains in the cured product, and the heat resistance of the obtained prepreg, laminate, etc. becomes excellent. .

[(B-2) Siloxane compound having at least two primary amino groups at the molecular terminals]
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 terminals, and examples thereof include compounds represented by the general formula (1).
Moreover, as a (b-2) component, a commercial item can be used, and as a (b-2) component of a commercial item, the siloxane which has an amino group in the both terminal mentioned as said (B) component, for example Is mentioned. These can be used alone or in admixture of two or more. Among these, from the point 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 in the component (b-2) [the amount of component used in the component (b-2) / the primary amino group of the component (b-2). Group equivalent] is in the range of 1.0 to 10.0 times the number of aldehyde groups of component (b-1) [amount of component (b-1) / aldehyde group equivalent of component (b-1)]. It is preferable to use for. By making it 1.0 times or more, good solubility in a solvent is obtained, and by making it 10.0 times or less, the elastic modulus of the thermosetting resin composition becomes excellent.

The presence 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 It can be confirmed that the reaction proceeds satisfactorily and the desired compound is obtained by confirming the presence of the peak.

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

  The content of (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 resin component total amount in the thermosetting resin composition. Is preferable, it is more preferable that it is 5-40 mass parts, and it is further more preferable that it is 10-30 mass parts. If it is this range, the outstanding elasticity modulus and low thermal expansibility will 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)”).
(C) The thermosetting resin is not particularly limited. For example, maleimide resin, epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, 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, an epoxy resin and a cyanate resin are preferable from the viewpoint of moldability and electrical insulation, and a maleimide resin is preferable from the viewpoint of heat resistance, moisture absorption resistance, and low decomposability due to moisture in the resin, and (C1 ) Maleimide resins having at least two N-substituted maleimide groups in one molecule are more preferred.

  Examples of maleimide resins 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- Maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, bis (4-maleimidophenyl) ether, Bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, bis (4- Reimidocyclohexyl) methane, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis (maleimidomethyl) cyclohexane, 1,4-bis (maleimidomethyl) benzene, 1,3-bis (4-maleimide) Phenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, bis [4- (4-maleimidophenoxy) phenyl] methane, 1,1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1 , 2-bis [4- (4-maleimidophenoxy) phenyl] ethane, 2,2-bis [4- ( -Maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [ 4- (4-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-Maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-maleimidophenoxy) biphenyl, 4,4-bis (4-maleimide) Phenoxy) biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (4-maleimidophenoxy) phenyl] ketone, 2,2-bis (4-maleimidophenyl) disulfide, bis (4-maleimidophenyl) disulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfide, bis [4- (4-maleimidophenoxy) phenyl] sulfide, Bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (4-maleimide) Phenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] ether, 1,4-bis [4- (4-maleimidophenoxy) -α , Α-dimethylbenzyl] benzene, 1,3-bis [4- (4-Maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4 -(3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3 -Bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, polyphenylmethanemaleimide (For example, product name: BMI-2300 manufactured by Daiwa Kasei Kogyo Co., Ltd.). These can be used alone or in admixture of two or more. Among these, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, N, N ′-(1,3-phenylene) bismaleimide has a high reaction rate and can be made more heat resistant. 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane and polyphenylmethanemaleimide are preferable. From the viewpoint of solubility in a solvent, bis (4-maleimidophenyl) methane and 2,2-bis [ 4- (4-Maleimidophenoxy) 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 novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin. , Stilbene 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 -Type epoxy resin, alicyclic epoxy resin, polyfunctional phenols and diglycidyl ether compounds of polycyclic aromatics such as anthracene And phosphoric-containing epoxy resin obtained by introducing a phosphorus compounds thereto. These can be used alone or in admixture of two or more. Among these, biphenyl aralkyl type epoxy resins and naphthalene type epoxy resins are preferable from the viewpoint of heat resistance and flame retardancy.

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

  Content of (C) thermosetting resin in the thermosetting resin composition of this invention is 40-95 mass parts per 100 mass parts of solid content conversion resin component total amount in a thermosetting resin composition. It is preferable that it is 50-90 mass parts, It is more preferable that it is 60-90 mass parts. If it is this range, the outstanding elasticity modulus and low thermal expansibility will be obtained.

<(D) Amine compound having an acidic substituent>
The thermosetting resin composition of the present invention preferably further comprises (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 “(D1) a compound represented by the general formula (2)” or “(D1) component”) is preferable. Can be mentioned.

In general formula (2), R ₇ represents an acidic substituent, ie, a hydroxyl group, a carboxy group, or a sulfonic acid group, 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 synthesis yield. From the viewpoint of heat resistance, m-aminophenol and p-aminophenol are more preferable.

  Content of the amine compound which has (D) acidic substituent in the thermosetting resin composition of this invention is 0.1-per 100 mass parts of solid content conversion resin component total amount in a thermosetting resin composition. The amount is preferably 20 parts by mass, and more preferably 1 to 10 parts by mass. By making content of (D) component 0.1 mass part or more, the outstanding heat resistance and copper foil adhesiveness are obtained, and the outstanding heat resistance is securable by setting it as 20 mass parts or less.

In addition to the components (A) to (C), the thermosetting resin composition of the present invention preferably contains (D) an amine compound having an acidic substituent, but (B) an amino-modified siloxane, (C The thermosetting resin and (D) the amine compound having an acidic substituent can be used after being pre-reacted.
Various combinations of the components used in the pre-reaction can be applied. For example, (B1) amino-modified siloxane (B1) aromatic azomethine skeleton-containing amino-modified siloxane, (C) thermosetting resin (C1 ) Maleimide resins having at least two N-substituted maleimide groups in one molecule are preferably used. By pre-reacting these, (B1) a structural unit derived from an aromatic azomethine skeleton-containing amino-modified siloxane, and (C1) a structural unit derived from a maleimide resin having at least two N-substituted maleimide groups in one molecule; And (D) an aromatic azomethine skeleton-containing siloxane-modified imide resin containing a structural unit derived from an amine compound having an acidic substituent. Moreover, as (D) amine compound which has an acidic substituent, it is preferable to use the compound represented by (D1) said general formula (2).

The pre-reaction is preferably carried out in an organic solvent while being heated and kept warm.
In this pre-reaction, the amount of component (B1), component (C1) and component (D1) used is, for example, the number of maleimide groups in component (C1) [the amount of component (C1) used / maleimide group equivalent in component (C1) ] Is the total number of primary amino groups of component (B1) and component (D1) [(B1) component usage / (B1) component primary amino group equivalent + (D1) component usage / (D1) component] It is preferably in the range of 2.0 to 10.0 times the primary amino group equivalent]. By making it 2.0 times or more, excellent heat resistance can be obtained while suppressing gelation, and by making it 10.0 times or less, good solubility in organic solvents 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. It is more preferable that By setting the content of the component (C1) to 50 parts by mass or more, good heat resistance can be obtained, and by setting it to 3000 parts by mass or less, low thermal expansion can be favorably maintained.
The amount of the component (D1) used in the pre-reaction is preferably 1 to 1000 parts by mass, for example, with respect to 100 parts by mass of the component (B1) while maintaining the above relationship. More preferably, it is part by mass. By setting the content of the component (D1) to 1 part by mass or more, excellent heat resistance can be obtained, and by setting it to 1000 parts by mass or less, low thermal expansion can be favorably maintained.

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; 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 mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; dimethyl And sulfur atom-containing solvents 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 has low toxicity and is highly volatile and hardly remains 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, and 40 to 1000 parts by mass with respect to 100 parts by mass of the sum of the components (B1), (C1) and (D1). It is more preferable, and it is still more preferable that it is 40-500 mass parts. When the amount of the organic solvent used is 25 parts by mass or more, good solubility is obtained, and when it is 2000 parts by mass or less, a sufficient reaction rate is 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-based catalysts such as triphenylphosphine; alkali metal amides such as lithium amide, sodium amide, and potassium amide Etc. 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, and more preferably 100 to 130 ° C. For example, the reaction time is preferably 0.1 to 10 hours, and 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 is the total amount of resin components in terms of solid content in the thermosetting resin composition The amount 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 thermal expansion coefficient and a high elastic modulus can be obtained.

  Although the thermosetting resin composition of the present invention has good thermosetting reactivity, it can further improve heat resistance, adhesiveness and mechanical strength by containing a curing agent and / or a polymerization initiator, if necessary. Can do.

Examples of the curing agent include dicyandiamide, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-diethyl-diphenylmethane, 4,4′-diaminodiphenylsulfone, phenylenediamine, and xylenediamine. Aromatic amines; aliphatic amines such as hexamethylene diamine and 2,5-dimethylhexamethylene diamine; guanamine compounds such as melamine and benzoguanamine. 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 maleimide compound used / the maleimide group equivalent of the maleimide compound] ] Is preferably in a range that is 2.0 to 10 times as large as. By making it 2.0 times or more, excellent adhesiveness and heat resistance can be obtained, and by making it 10 times or less, good solubility in organic solvents 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 thermoplastic elastomer (E) include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, siloxane elastomers, and derivatives thereof. These are composed of a hard segment component and a soft segment component. In general, the former 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 elastomers, olefin elastomers, polyamide elastomers and siloxane elastomers are preferable from the viewpoint of heat resistance and insulation reliability, and styrene elastomers and olefin elastomers are more preferable from the viewpoint of dielectric characteristics. .

(E) What has a reactive functional group in a molecular terminal or a molecular chain can be used for a thermoplastic elastomer. 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 acryl group, a methacryl group, and a vinyl group. By having these reactive functional groups in the molecular terminals or molecular chains, 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, it is possible to significantly reduce the warpage of the substrate.
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 from the viewpoint of heat resistance and insulation reliability, an epoxy group, A hydroxyl group and an amino group are more preferred.

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

<(F) Curing accelerator>
The thermosetting resin composition of the present invention may further contain (F) a curing accelerator. (F) The shrinkage rate and the amount of warpage can be further reduced by using a curing accelerator in combination.
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, from the viewpoint of reactivity, imidazoles are preferable, and an adduct of hexamethylene diisocyanate and 2-ethyl-4-methylimidazole represented by the following general formula (3) is more preferable. The compound represented by the following general formula (3) is available, for example, as “G-8809L” (trade name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

  When the thermosetting resin composition of the present invention contains (F) a curing accelerator, the content of (F) the curing accelerator is, for example, 100 mass of the resin component total amount in solid content in the thermosetting resin composition. It is preferable that it is 0.1-5 mass parts per part, and it is more preferable that it is 0.5-2 mass parts. (F) By making content of a hardening accelerator into the said range, the low shrinkability of a hardened | cured material, low thermal expansibility, and the outstanding dielectric characteristic can be expressed more effectively.

<Other ingredients>
The thermosetting resin composition of the present invention is within the range that does not impair the effects of the present invention. (E) Thermoplastic resin other than thermoplastic elastomer, flame retardant, ultraviolet absorber, antioxidant, photopolymerization initiator, fluorescent It may contain a whitening agent, an adhesion improver 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, poly Examples include ether ether ketone resins, polyether imide resins, siloxane resins, and tetrafluoroethylene resins.

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

(UV absorber, etc.)
As an ultraviolet absorber, a benzotriazole type ultraviolet absorber is mentioned, for example. Examples of the antioxidant include hindered phenol-based and hindered amine-based antioxidants. Examples of the photopolymerization initiator include photopolymerization initiators such as benzophenones, benzyl ketals, and thioxanthones. Examples of the fluorescent whitening agent include a fluorescent whitening agent of a stilbene derivative. Examples of the adhesion improver include urea compounds such as urea silane, coupling agents such as silane, titanate, and aluminate.

(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 dilution and easy manufacture of a prepreg and a film with a resin described later. The varnish is preferably used.
Although it does not restrict | limit especially as an organic solvent used for preparation of a varnish, For example, Ketone type solvents, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; Alcohol solvents, such as methyl cellosolve; Ether type solvents, such as tetrahydrofuran; Toluene, And aromatic solvents such as xylene and mesitylene. 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, based on the entire varnish. By setting the content of the thermosetting resin composition within the above range, it is possible to obtain a prepreg and a resin-coated film in which an appropriate amount of the thermosetting resin composition is adhered while maintaining good coating properties.

[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 substrate and then semi-curing (B-stage). More specifically, after applying the thermosetting resin composition of the present invention to a substrate by a method such as impregnation, spraying, extrusion, etc., for example, by semi-curing (B-stage) by heating or the like, A prepreg of the present invention comprising a substrate 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 a base material used for the prepreg of this invention, the well-known thing used for the laminated board for various electrical insulation materials can be used, for example. 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 mixtures thereof.
These base materials have shapes, such as a woven fabric, a nonwoven fabric, a robink, a chopped strand mat, a surfacing mat, for example. What is necessary is just to select the material and shape of a base material with the use and performance of the target molded object, and if necessary, it can combine individually or two or more types of materials and shapes.
Moreover, as a base material, the thing surface-treated with the silane coupling agent etc. or the thing which performed the fiber opening process is suitable from the surface of heat resistance, moisture resistance, and workability.
The thickness in particular of a base material is not restrict | limited, For example, it can be set as the range of 0.03-0.5 mm.

The content (adhesion amount) of the thermosetting resin composition in the prepreg of the present invention is preferably 20 to 90 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, impregnated or coated on a substrate with a thermosetting resin composition so that the content of the thermosetting resin composition in the prepreg falls within the above range, and then 100 to 200 ° C. It can be manufactured by heating and drying at a temperature of 1 to 30 minutes and semi-curing (B-stage).

[Film with resin]
The film with a resin of the present invention contains the thermosetting resin composition of the present invention.
The film with resin of the present invention can be obtained, for example, by applying the thermosetting resin composition of the present invention to a support. Specifically, the organic solvent in the varnish is volatilized by applying a varnish containing the thermosetting resin composition of the present invention to a support and drying, and the thermosetting resin composition is semi-cured (B stage). And a resin composition layer comprising the thermosetting resin composition of the present invention is formed 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. Is. 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 embedding property of the circuit pattern substrate is also ensured. It is desirable that the (fluidity) is ensured.

  As a method (coating machine) for applying the thermosetting resin composition to the support, a die coater, comma coater, bar coater, kiss coater, 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, methods such as heating and hot air blowing can be applied.
As drying conditions, for example, the content of the organic solvent in the resin composition layer after formation can be 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., 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. Moreover, it is preferable to set suitable drying conditions as appropriate by simple experiments in advance.

  In general, the thickness of the resin composition layer in the film with resin is preferably equal to or greater 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 and more preferably 5 to 30 μm from the viewpoint of reducing the thickness and thickness of the multilayer printed wiring board. Therefore, the thickness of the resin composition layer can be, for example, 5 μm or more, and is, for example, in the range of 80 μm or less, preferably 60 μm or less, more preferably 40 μm or less. The thickness can be selected.

The support in the resin-coated film of the present invention is, for example, a film made of polyolefin such as polyethylene, polypropylene or polyvinyl chloride, polyethylene terephthalate (hereinafter also referred to as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide or the like; Release paper; metal foil such as copper foil and aluminum foil. These supports and protective films described later may be subjected to mat treatment, corona treatment, mold release treatment, and the like.
The thickness of the support is, for example, preferably 10 to 150 μm, and more preferably 25 to 50 μm.
A protective film according to the support can be further laminated on the surface of the resin composition layer on which the support is not in close contact. By laminating the protective film, foreign matter can be prevented from being mixed. The thickness of the protective film is, for example, 1 to 40 μm. The film with resin can also be wound and stored in a roll.

[Laminated board]
The laminated board of this invention contains the hardened | cured material of the cured product of the prepreg of this invention, and / or the film with a resin of this invention.
Hereinafter, the manufacturing method of the laminated board of this invention is explained in full detail. In addition, the layer which consists of the hardened | cured material of the prepreg of this invention or a film with a resin in the laminated board of this invention may be called an "insulating resin layer."

As a method of forming a laminated board using the film with resin of this invention, the method of laminating the film with resin of this invention on the single side | surface or both surfaces of a circuit board using a vacuum laminator is mentioned, for example.
Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means the thing in which the conductor layer (circuit) patterned by the one side or both surfaces of the above boards was formed. Moreover, in the laminated board which laminates | stacks a conductor layer and an insulating layer alternately, and the multilayer printed wiring board manufactured from this laminated board, the conductor layer by which the one or both surfaces of the outermost layer of this multilayer printed wiring board were patterned What is (circuit) is also included in the circuit board here. Note that the surface of the conductor layer may be previously roughened by blackening or the like.

In the above laminate, if the film with resin has a protective film, after removing the protective film, preheat the film with resin and the circuit board as necessary, while pressing and heating the film with resin Crimp to circuit board.
In the film with resin of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used. The laminating conditions are, for example, that the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., the pressure bonding pressure is preferably 0.1 to 1.1 MPa, and the lamination is performed under a reduced pressure of air pressure 20 mmHg (26.7 hPa) or less. preferable. The laminating method may be a batch method or a continuous method using a roll.

  After laminating the resin-coated film on the circuit board, after cooling to around room temperature, when the support is peeled off, the insulating resin layer can be formed on the circuit board by peeling and thermosetting. 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. For example, the temperature is 150 ° C. to 220 ° C. for 20 minutes to 180 minutes. It is preferably selected within the range of 160 to 200 ° C. for 30 to 120 minutes.

When the support was not peeled off before the resin composition layer was cured, it was peeled off after the formation of the insulating resin layer, and then, if necessary, the insulating resin layer formed on the circuit board was perforated, A via hole, a through hole, or the like may be formed.
Drilling can be performed by, for example, a drill, laser, plasma, or a combination of these. Among these, drilling with a laser such as a carbon dioxide laser or a YAG laser is a common method.

  Next, a conductor layer may be formed on the insulating resin layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. In the case of wet plating, first, the surface of the cured insulating resin layer is made of permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, etc. Roughening treatment is performed with an oxidizing agent to form uneven anchors. As the oxidizing agent, an aqueous sodium hydroxide solution (alkaline permanganate aqueous solution) such as potassium permanganate and sodium permanganate is particularly preferably used. Next, a conductor layer is formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. As a subsequent pattern formation method, for example, a known subtractive method or semi-additive method can be used.

Next, the manufacturing method of the laminated board of this invention using the prepreg of this invention is demonstrated.
The laminate of the present invention can be produced by laminating the prepreg of the present invention. In this case, the laminated board of the present invention includes an insulating resin layer formed 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 forming a metal foil such as copper or aluminum on one or both sides thereof. . A metal foil will not be restrict | limited especially if it is used with the laminated board for electrical insulation materials.
As the molding conditions, for example, a method of a laminated plate for an electrical insulating material and a multilayer plate can be applied. For example, using a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc., a temperature of 100 to 250 ° C., a pressure of 0 It can be molded under conditions of 2 to 10 MPa and a heating time of 0.1 to 5 hours. Further, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce the laminated board of the present invention.

[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 produced by subjecting a conductor layer (metal foil) disposed on one or both sides of the insulating resin layer in the laminated board of the present invention to circuit processing.
Specifically, first, the conductor layer of the laminate of the present invention is subjected to wiring processing by a normal etching method, and then, a plurality of laminates that have been subjected to wiring processing via the prepreg of the present invention are laminated and subjected to hot press processing. Multi-layered at once. Thereafter, the multilayer printed wiring board of the present invention can be manufactured through formation of through holes or blind via holes by drilling or laser processing, and 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.
In addition, the resin board and copper clad laminated board obtained by the following example measured and evaluated the characteristic using the following methods.

[Evaluation method]
(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 apparatus (TA instrument) Thermomechanical analysis was performed by a compression method using Q400). After mounting the resin plate on the device in the X direction, load 5G, temperature increase rate 45 ° C / min, temperature profile from 20 ° C (5 minutes hold) to 260 ° C (2 minutes hold) to 20 ° C (5 minutes hold) Measured with The amount of dimensional change in the X direction before and after the temperature increase was determined from the 20 ° C. dimension before the temperature increase start and the 20 ° C. dimension after the temperature increase, and the shrinkage rate of the resin plate was calculated using the following equation. .
Curing shrinkage (%) = {(20 ° C. dimension before starting temperature rise (mm) −20 ° C. dimension after temperature rise (mm)) / 20 ° C. dimension before temperature rise (mm)} × 100

(2) Thermal expansion coefficient 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 apparatus (TA instrument) Thermomechanical analysis was performed by the compression method using Q400) manufactured by Mentor. After mounting the resin plate on the device in the X direction, load 5G, temperature increase rate 45 ° C / min, temperature profile from 20 ° C (5 minutes hold) to 260 ° C (2 minutes hold) to 20 ° C (5 minutes hold) Measured with An average coefficient of thermal expansion of 50 to 120 ° C. during cooling was calculated and used as the coefficient of thermal expansion of the resin plate.

(3) Mounting warpage amount The warpage amount of the copper clad laminate was evaluated by 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 copper-clad laminate was heated from room temperature (25 ° C.) to 260 ° C., and then the amount of warpage when cooled to 50 ° C. was measured.

[(B) Production of amino-modified siloxane]
Production Example 1: (B1) Production of Aromatic Azomethine Skeleton-Containing Amino-Modified Siloxane Compound A terephthalaldehyde (300 ml) reaction vessel equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser is charged with terephthalaldehyde ( Toray Fine Chemical Co., Ltd.) 22.75 g, 4,4′-diamino-3,3′-diethyldiphenylmethane (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 having a thermometer, a stirrer, a moisture quantifier with a reflux condenser and a capacity of 500 ml that can be heated and cooled, 22.15 g of the LCA prepared above, both-end diamine-modified siloxane (Shin-Etsu Chemical Co., Ltd.) (Product name: X-22-161B, manufactured by Co., Ltd.) 96.14 g and PGM 144.21 g were added and refluxed for 2 hours. The mixture was further heated to 130 ° C. and concentrated at normal pressure. A solution containing a siloxane compound (hereinafter also referred to as “AZS”) containing an aromatic azomethine structural unit and a siloxane structural unit represented by the following formula (5) and having amino groups at both ends is obtained. (Content of resin component: 70% by mass).

Production Example 2: Aromatic azomethine skeleton-containing siloxane-modified imide resin Into a reaction vessel having a volume of 5 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 2,2-bis (4- (4-maleimidophenoxy) 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, After 43.4 g of 4′-diamino-3,3′-diethyldiphenylmethane (Nippon Kayaku Co., Ltd., KAYAHARD A-A) and PGM 1387.13 g were reacted at 115 ° C. for 4 hours, further to 130 ° C. The temperature is increased and atmospheric pressure concentration is performed, and an aromatic azomethine skeleton-containing siloxane-modified imide resin (hereinafter also referred to as “AZS-modified imide resin”) is used. To obtain a solution having (content of resin component: 63 wt%).

Examples 1-13, Comparative Examples 1-5
Various components shown below were mixed in the proportions 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 varnish is applied onto a PET film having a thickness of 30 μm using a film applicator (Yoshimitsu Seiki Co., Ltd., trade name: YBA type baker applicator) so that the thickness after drying becomes 30 μm. Dry 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. for 60 hours. Press-molded for minutes. Thereafter, the electrolytic copper foils on both sides were removed by peeling to obtain a resin plate. When press molding, the copper foil was arranged so that the surface on the resin powder side was a glossy surface.

The varnish was impregnated with 0.1 mm thick S glass cloth and dried by heating at 110 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 50 mass%.
Four prepregs were stacked, 18 μm electrolytic copper foils were placed one above the other, and press-molded 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 used in Examples and Comparative Examples and product names are described below.
(1) (A1) Plate-like filler MEG160FY-M01 [manufactured by Nippon Sheet Glass Co., Ltd .; sample name]
Glass composition: E glass Average thickness: 0.7 μm
Loss on ignition (LOI): 0.7%
Average particle size: 160 μm
・ Sambrari [AGC S-Tech Co., Ltd .; product name]
Glass composition: SiO ₂
Average particle diameter (tertiary aggregated particles): 4.0 to 6.0 μm

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

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

(4) (C) Thermosetting resin BMI-4000: 2,2-bis [4- (4-maleimidophenoxy) 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., Ltd .; trade name]

(6) (F) Curing accelerator G-8809L: Adduct of hexamethylene diisocyanate and 2-ethyl-4-methylimidazole represented by the general formula (3) (Daiichi Kogyo Seiyaku Co., Ltd .; trade name)

(7) Curing agent KAYAHARD AA: 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 a low shrinkage, a low shrinkage, a thermal expansion coefficient and a warp amount. It turns out that it is excellent in low thermal expansibility and can suppress the curvature at the time of mounting.
On the other hand, as the filler (A), (A1) the resin plates and copper clad laminates of Comparative Examples 1 to 5 obtained from a thermosetting resin not containing a plate-like filler are compared with Examples 1 to 13. It can be seen that the shrinkage rate, thermal expansion coefficient and warpage amount are all inferior.

Claims (17)

  A thermosetting resin composition comprising (A) a filler, (B) an amino-modified siloxane, and (C) a thermosetting resin, wherein (A) the filler comprises (A1) a plate-like filler. A thermosetting resin composition comprising.   The thermosetting resin composition according to claim 1, wherein the (A) filler further comprises (A2) a spherical filler.   The thermosetting resin composition according to claim 1, wherein the content of the (A1) plate filler in (A) filler is 20 to 100% by mass.   (A1) The thermosetting resin composition according to any one of claims 1 to 3, wherein the plate-like filler has an average particle diameter of 0.05 to 300 µm.   (A1) The thermosetting resin composition according to any one of claims 1 to 4, wherein the plate-like filler contains one or more selected from the group consisting of talc, mica, clay, montmorillonite, silica and glass. .   (C) The thermosetting resin composition according to any one of claims 1 to 5, comprising (C1) a maleimide resin having at least two N-substituted maleimide groups in one molecule as the thermosetting resin. object.   The thermosetting resin composition according to any one of claims 1 to 6, comprising (B1) an aromatic azomethine skeleton-containing amino-modified siloxane as (B) amino-modified siloxane.   The component (B1) comprises (b-1) a structural unit derived from an aromatic azomethine compound having at least one aldehyde group in one molecule, and (b-2) at least two primary amino groups at the molecular end. The thermosetting resin composition of Claim 7 containing the structural unit derived from the siloxane compound which has.   Furthermore, (D) The thermosetting resin composition of any one of Claims 1-8 containing the amine compound which has an acidic substituent.   (B1) an aromatic azomethine skeleton-containing amino-modified siloxane as the component (B), (C1) a maleimide resin having at least two N-substituted maleimide groups in one molecule as the component (C), and (D) An aromatic azomethine skeleton-containing siloxane comprising 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 thermosetting resin composition according to any one of claims 1 to 9, which is contained as a modified imide resin.   Furthermore, (E) Thermosetting resin composition of any one of Claims 1-10 containing a thermoplastic elastomer.   Furthermore, the thermosetting resin composition of any one of Claims 1-11 containing (F) hardening accelerator.   The prepreg containing the thermosetting resin composition of any one of Claims 1-12.   The film with resin containing the thermosetting resin composition of any one of Claims 1-12.   A laminate comprising a cured product of the prepreg according to claim 13.   The laminated board containing the hardened | cured material of the film with a resin of Claim 14.   The multilayer printed wiring board containing the laminated board of Claim 15 or 16.