JP6844298B2 - Manufacturing method of prepreg, laminated board, printed wiring board, coreless board, semiconductor package and coreless board - Google Patents

Description

The present invention relates to a prepreg, a laminated board, a printed wiring board, a coreless board, a semiconductor package, and a method for manufacturing a coreless board.

In recent years, with the progress of increasing the wiring density and high integration of printed wiring boards, especially in semiconductor package substrate applications, it is caused by the difference in the coefficient of thermal expansion between the chip and the substrate at the time of component mounting and package assembly. Warpage has become a major issue. Warpage is considered to be one of the factors that cause poor connection between the semiconductor element and the printed wiring board, and reduction is required.

In particular, in recent years, as a package structure corresponding to a thinner substrate, a coreless substrate having no core substrate and mainly having a build-up layer capable of high-density wiring has been studied (for example, Patent Document 1 and 2).
Since the rigidity of the coreless substrate is reduced by thinning the coreless substrate by removing the support (core substrate), the problem that the semiconductor package warps when the semiconductor element is mounted and packaged becomes more remarkable. Therefore, in the coreless substrate, more effective reduction of warpage is desired.

One of the factors that cause the semiconductor package to warp is the difference in the coefficient of thermal expansion between the semiconductor element and the printed wiring board. In general, since the coefficient of thermal expansion of a printed wiring board is larger than the coefficient of thermal expansion of a semiconductor element, stress is generated due to the thermal history applied when the semiconductor element is mounted, and warpage occurs. Therefore, in order to suppress the warp of the semiconductor package, it is necessary to reduce the coefficient of thermal expansion of the printed wiring board to reduce the difference from the coefficient of thermal expansion of the semiconductor element.

Here, it is generally known that the coefficient of thermal expansion of the prepreg obtained by impregnating the glass cloth with the resin composition follows the Scapery formula represented by the following formula.
A ≒ (ArErFr + AgEgFg) / (ErFr + EgFg)
(In the above formula, A is the coefficient of thermal expansion of the prepreg, Ar is the coefficient of thermal expansion of the resin composition, Er is the coefficient of elasticity of the resin composition, Fr is the volume fraction of the resin composition, and Ag is the coefficient of thermal expansion of the glass cloth. , Eg represents the coefficient of elasticity of the glass cloth, and Fg represents the volume fraction of the glass cloth.)
From the above Scapery equation, it is considered that when glass cloth having the same physical characteristics at an arbitrary volume fraction is used, the prepreg can be reduced in thermal expansion by reducing the elastic modulus and the coefficient of thermal expansion of the resin composition.

As a material having excellent low thermal expansion property, a resin composition containing a modified imide resin obtained by modifying a polybismaleimide resin with a siloxane compound has been studied (see, for example, Patent Document 3). However, although this modified imide resin is excellent in heat resistance, high elastic modulus, low thermal expansion property, etc., it has a drawback in embedding property of a wiring portion (hereinafter, also referred to as "moldability"). In recent years, the thickness of each layer of a printed wiring board has become even thinner due to the sophistication of wiring density and the progress of high integration, so that further improvement in moldability is desired.

A circuit board having a multi-layer structure such as a build-up layer is formed by using, for example, two or more prepregs (for example, a first prepreg and a second prepreg). In order to do so, a wiring portion is formed on one surface of the first prepreg, and the wiring portion is embedded by the other surface of the second prepreg. In this case, one surface side of the first prepreg is required to have high adhesion for forming the wiring portion, and the other surface side of the second prepreg has formability for embedding the wiring portion. Required.
As a prepreg that achieves both thinness and moldability for embedding a wiring portion, for example, Patent Document 4 describes a prepreg that carries a resin material and has the fiber group in the thickness direction of the prepreg. A prepreg in which the material is unevenly distributed is disclosed.

Japanese Unexamined Patent Publication No. 2005-72085 JP-A-2002-26171 Japanese Unexamined Patent Publication No. 2014-129521 Patent No. 5243715

According to the prepreg described in Patent Document 4, although the moldability in the case of thinning can be improved, the warp of the package is large when the semiconductor element is mounted and packaged, and the heat resistance is not sufficient. Therefore, there is a demand for a material that has both moldability for embedding a wiring portion, low thermal expansion that enables reduction of warpage, and excellent heat resistance.

In view of these circumstances, an object of the present invention is to provide a prepreg having excellent low thermal expansion, heat resistance and moldability, and a method for manufacturing a laminated board, a printed wiring board, a coreless board, a semiconductor package and a coreless board obtained by using the prepreg. To provide.

As a result of intensive studies to achieve the above object, the present inventors have found that the above problems can be solved by the following inventions, and have completed the present invention.
That is, the present invention provides the following [1] to [12].
[1] A fiber base material layer containing a fiber base material, a first resin layer formed on one surface of the fiber base material layer, and a second resin layer formed on the other surface of the fiber base material layer. Is a prepreg with a resin layer of
The first resin layer is a layer formed by forming a resin composition (I) containing an epoxy resin (A) as a main component of a resin component.
The second resin layer has an amine compound (B) having at least two primary amino groups in one molecule and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. A prepreg, which is a layer formed by forming a resin composition (II) containing a thermoplastic elastomer (D) as a main component of a resin component.
[2] A fiber base material layer containing a fiber base material, a first resin layer formed on one surface of the fiber base material layer, and a second resin layer formed on the other surface of the fiber base material layer. Is a prepreg with a resin layer of
The first resin layer is a layer formed by forming a resin composition (I) containing an epoxy resin (A) as a main component of a resin component.
The second resin layer comprises an amine compound (B) having at least two primary amino groups in one molecule and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. A prepreg which is a layer formed by forming a resin composition (II) containing an amino-modified polyimide resin (X) as a reaction product and a thermoplastic elastomer (D) as main components of a resin component.
[3] The prepreg according to the above [1] or [2], wherein the thermoplastic elastomer (D) is a thermoplastic elastomer having a structural unit derived from styrene represented by the following general formula (D-1).

[4] The content of the thermoplastic elastomer (D) in the resin composition (II) is 5 to 80 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the resin composition (II). , The prepreg according to any one of the above [1] to [3].
[5] Any of the above [1] to [4], wherein the resin composition (II) further contains one or more thermosetting resins (H) selected from the group consisting of an epoxy resin and a cyanate resin. The prepreg described in Crab.
[6] Any one of the above [1] to [5], wherein one or more selected from the group consisting of the resin composition (I) and the resin composition (II) further contains an inorganic filler (F). The prepreg described in.
[7] A laminated board obtained by laminating and molding the prepreg according to any one of the above [1] to [6].
[8] A printed wiring board containing the laminated board according to the above [7].
[9] The prepreg according to any one of the above [1] to [6], which is for a coreless substrate.
[10] A coreless substrate containing an insulating layer formed by using the prepreg according to the above [9].
[11] A method for manufacturing a coreless substrate, which comprises a step of arranging the prepreg according to the above [9] so as to be in contact with a circuit pattern.
[12] A semiconductor package in which a semiconductor element is mounted on the printed wiring board according to the above [8] or the coreless substrate according to the above [10].

According to the present invention, it is possible to provide a prepreg having excellent low thermal expansion property, heat resistance and moldability, and a method for manufacturing a laminated board, a printed wiring board, a coreless board, a semiconductor package and a coreless board obtained by using the prepreg. ..

It is sectional drawing of the prepreg of this invention. It is a schematic diagram which shows the thickness of each layer of the prepreg of this invention. It is a schematic diagram which shows one aspect of the manufacturing method of the coreless substrate of this invention.

[Prepreg]
As shown in FIG. 1, the prepreg of the present invention comprises a fiber base material layer containing a fiber base material, a first resin layer formed on one surface of the fiber base material layer, and the fiber base material layer. A prepreg having a second resin layer formed on the other surface of the prepreg.
The first resin layer is a layer formed by forming a resin composition (I) containing an epoxy resin (A) as a main component of a resin component.
The second resin layer has an amine compound (B) having at least two primary amino groups in one molecule and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. The prepreg is a layer formed by forming a resin composition (II) containing the thermoplastic elastomer (D) as a main component of the resin component.
Here, in the present invention, the "main component" means the component having the highest content among the components. That is, the "main component of the resin component" means the resin having the highest content among the resin components contained in the resin composition.
That is, among the contents of each resin component contained in the resin composition (I), the content of the component (A) is the highest, and among the contents of each resin component contained in the resin composition (II). , (B) component, (C) component and (D) component have the highest total content.

The reason why the prepreg of the present invention is excellent in low thermal expansion property, heat resistance and moldability is not clear, but it is considered as follows.
The prepreg of the present invention has a first resin layer formed by forming a resin composition (I) mainly containing an epoxy resin exhibiting good moldability on one surface of a fiber base material layer. Therefore, when embedding the inner layer circuit using the prepreg of the present invention, it is considered that excellent embedding property (moldability) can be obtained by setting the first resin layer on the inner layer circuit side.
On the other hand, the prepreg of the present invention is a second resin obtained by forming a resin composition (II) mainly containing a specific amine compound, a maleimide compound and a thermoplastic elastomer on the other surface of the fiber base material layer. Has a layer. The cured product obtained from the resin composition (II) is excellent in heat resistance and low thermal expansion property, whereby the insulating layer formed from the prepreg of the present invention has good moldability and heat resistance. It is considered to be excellent in properties and low thermal expansion.

<Fiber base layer>
The fiber base material layer is a layer containing a fiber base material.
As the fiber base material, well-known materials used for various laminated boards for electrical insulating materials can be used. As the material of the fiber base material, natural fibers such as paper and cotton linter; inorganic fibers such as glass fiber and asbestos; organic fibers such as aramid, polyimide, polyvinyl alcohol, polyester, tetrafluoroethylene and acrylic; and a mixture thereof are used. Can be mentioned. Among these, glass fiber is preferable from the viewpoint of flame retardancy. As the base material using glass fiber, glass cloth is preferable, for example, glass cloth using E glass, C glass, D glass, S glass or the like or glass cloth in which short fibers are bonded with an organic binder; glass fiber and cellulose. Examples include glass cloth mixed with fibers. Among these, glass cloth using E glass is more preferable.
These fiber substrates have shapes such as woven fabrics, non-woven fabrics, robinks, chopped strand mats, and surfaced mats.
The material and shape of the fiber base material are appropriately selected depending on the intended use, performance, etc. of the molded product, and one type may be used alone, or two or more types of materials and shapes may be combined as necessary. You can also do it.
The thickness of the fiber base material is, for example, 10 μm to 0.5 mm, preferably 10 to 100 μm, more preferably 10 to 50 μm, still more preferably 12 to 30 μm, from the viewpoint of handleability and enabling high-density wiring. .. When two or more types of fiber base materials are used, the average thickness of the fiber base materials is the total value of the average thicknesses of the two or more types of fiber base materials.
The fiber base material is not particularly limited, but may be a fiber base material composed of one layer.
Here, the fiber base material composed of one layer means a fiber base material composed of only entangled fibers, and when a fiber base material having no entanglement exists, it is classified into a fiber base material composed of multiple layers. Will be done.
From the viewpoint of heat resistance, moisture resistance, processability, etc., these fiber base materials may be surface-treated with a silane coupling agent or the like, or may be mechanically opened.

The fiber substrate layer usually contains a resin composition.
Examples of the resin composition contained in the fiber base material layer include a resin composition (I), a resin composition (II), and a mixture thereof, which will be described later.
The prepreg of the present invention has a first resin layer on one surface thereof and a second resin layer on the other surface, but usually, a resin composition forming the first resin layer ( I) is also present inside the fiber base material layer continuously from the first resin layer, and the resin composition (II) forming the second resin layer is continuously fiber from the second resin layer. It is also present inside the base material layer. Further, there may be a mixture or the like in which the resin composition (I) and the resin composition (II) are in contact with each other.
The content of the resin composition contained in the fiber base material layer is preferably 50 to 90% by mass, more preferably 65 to 80% by mass.

The thickness of the fiber base material layer is preferably 10 to 100 μm, more preferably 10 to 50 μm, and even more preferably 12 to 30 μm from the viewpoint of handleability and enabling high-density wiring.
Here, the thickness of the fiber base material layer means the thickness indicated by the region B containing the fiber base material in the cross section orthogonal to the plane direction of the prepreg shown in FIG. The thickness of the fiber base material layer is determined by exposing the cross section of the prepreg by a known method such as mechanical polishing or ion milling, and then observing it with a scanning electron microscope (SEM). The thickness of the base material layer can be measured and averaged to obtain the thickness.

<First resin layer>
The first resin layer is a layer formed on one surface of the fiber base material layer, and is a layer formed by forming the resin composition (I).
The thickness of the first resin layer is not particularly limited, but is, for example, 5 to 100 μm, preferably 5 to 50 μm, and more preferably 5 to 30 μm.
Here, the thickness of the first resin layer means the thickness indicated by the region a1 containing no fiber base material in the cross section orthogonal to the plane direction of the prepreg shown in FIG. The thickness of the first resin layer can be measured by the same method as the thickness of the fiber base material layer.

(Resin composition (I))
The resin composition (I) contains an epoxy resin (A) as a main component of the resin component.
Here, the "resin component" in the resin composition (I) is mainly an epoxy resin (A), and the resin composition (I) contains an epoxy resin curing agent, other resin components, etc., which will be described later. If so, include these as well. Hereinafter, each component contained in the resin composition (I) will be described.

[Epoxy resin (A)]
Examples of the epoxy resin (A) 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, α-naphthol / cresol novolac type epoxy resin, and the like. Bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, stillben 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, polycyclic aromatic diglycidyl ether compounds such as polyfunctional phenols and anthracene, and phosphorus introduced with a phosphorus compound. Examples include the contained epoxy resin. These may be used alone or in combination of two or more. Among these, a biphenyl aralkyl type epoxy resin and an α-naphthol / cresol novolac type epoxy resin are preferable from the viewpoint of heat resistance and flame retardancy.
The content of the epoxy resin (A) in the resin composition (I) is based on 100 parts by mass of the solid content of the resin component in the resin composition (I) from the viewpoint of moldability, heat resistance and chemical resistance. , 50 parts by mass or more, more preferably 60 parts by mass or more, further preferably 70 parts by mass or more, and particularly preferably 80 parts by mass or more. The upper limit of the content of the epoxy resin (A) is not particularly limited, and may be, for example, 100 parts by mass or less.

[Epoxy curing agent]
The resin composition (I) may further contain an epoxy curing agent. Examples of the curing agent include polyfunctional phenol compounds such as phenol novolac resin, cresol novolac resin, and aminotriazine novolac resin; amine compounds such as dicyandiamide, diaminodiphenylmethane, and diaminodiphenylsulfone; phthalic anhydride, pyromellitic anhydride, and maleine anhydride. Examples thereof include acid anhydrides such as acids and maleic anhydride copolymers. These may be used alone or in combination of two or more.

[Inorganic filler (F)]
The resin composition (I) may further contain an inorganic filler (F).
Examples of the inorganic filler (F) include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride and calcium carbonate. , Barium sulfate, aluminum borate, potassium titanate, glass powder, hollow glass beads and the like. As the glass, E glass, T glass, D glass and the like are preferably mentioned. These may be used alone or in combination of two or more.
Among these, for example, silica is preferable from the viewpoint of dielectric properties, heat resistance and low thermal expansion. Examples of silica include precipitated silica produced by a wet method and having a high water content, and dry silica produced by a dry method and containing almost no bound water or the like. Further, as the dry method silica, crushed silica, fumed silica, molten silica (molten spherical silica) and the like can be mentioned depending on the difference in the manufacturing method. Among these, spherical silica is preferable, and molten spherical silica is more preferable, from the viewpoint of low thermal expansion and high fluidity when filled in a resin.
The inorganic filler (F) may be pretreated or integral blended with a silane-based or titanate-based coupling agent or a surface treatment agent such as a silicone oligomer.

When silica is used as the inorganic filler (F), 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 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 and defects caused by coarse particles are deteriorated. Occurrence can be suppressed. 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.

When the resin composition (I) contains the inorganic filler (F), the content thereof is preferably 20 to 300 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the resin composition (I). , 50 to 250 parts by mass is more preferable, and 70 to 150 parts by mass is further preferable. By setting the content of the inorganic filler (F) within the above range, good moldability and low thermal expansion can be maintained.

[Curing accelerator (G)]
The resin composition (I) may further contain a curing accelerator (G).
Examples of the curing accelerator (G) include organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), and trisacetylacetonate cobalt (III); Imidazoles and derivatives thereof; organic phosphorus compounds such as phosphines and phosphonium salts; secondary amines, tertiary amines, quaternary ammonium salts and the like can be mentioned. These may be used alone or in combination of two or more. Among these, for example, zinc naphthenate, an imidazole derivative, and a phosphonium salt are preferable from the viewpoint of curing promoting effect and storage stability.
When the resin composition (I) contains the curing accelerator (G), the content thereof is 0.01 to 3 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the resin composition (I). Is preferable, and 0.05 to 1.5 parts by mass is more preferable. By setting the content of the curing accelerator (G) in the above range, the curing promoting effect and the storage stability can be kept good.

[Other ingredients]
The resin composition (I) is an optionally known thermoplastic resin, organic filler, flame retardant, ultraviolet absorber, antioxidant, photopolymerization initiator, fluorescent whitening agent, within a range not contrary to its purpose. It may contain an adhesiveness improver or the like.

Examples of the thermoplastic resin include polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin, and silicone resin.

Examples of the organic filler include resin fillers made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin and the like; acrylic acid ester resin, methacrylic acid ester resin, conjugated diene resin and the like. Examples thereof include a resin filler having a core-shell structure having a core layer in a rubber state and a shell layer in a glass state made of an acrylic acid ester resin, a methacrylic acid ester resin, an aromatic vinyl resin, a vinyl cyanide resin and the like.

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, phosphoric acid ester compounds and red phosphorus; Nitrogen flame retardants such as guanidine acid, melamine sulfate, melamine polyphosphate, melamine cyanurate; phosphazene flame retardants such as cyclophosphazene and polyphosphazene; inorganic flame retardants such as antimony trioxide.

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 benzophenone-based, benzylketal-based, and thioxanthone-based photopolymerization initiators. 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.

<Second resin layer>
The second resin layer is a layer formed on the other surface of the fiber base material layer, and is a layer formed by forming the resin composition (II).
The thickness of the second resin layer is not particularly limited, but is, for example, 1 to 100 μm, preferably 5 to 50 μm, and more preferably 5 to 30 μm.
Here, the thickness of the second resin layer means the thickness indicated by the region a2 that does not contain the fiber base material in the cross section orthogonal to the plane direction of the prepreg shown in FIG. The thickness of the second resin layer can be measured by the same method as the thickness of the fiber base material layer.

In the prepreg of the present invention, the ratio of the thickness of the first resin layer to the thickness of the second resin layer [first resin layer: second resin layer] has low thermal expansion property, heat resistance and moldability. From the viewpoint, 20:80 to 80:20 is preferable, 30:70 to 70:30 is more preferable, 40:60 to 60:40 is further preferable, and 50:50 is particularly preferable.

(Resin composition (II))
The resin composition (II) has an amine compound (B) having at least two primary amino groups in one molecule (hereinafter, also referred to as “amine compound (B)” or “component (B)”), 1 A maleimide compound (C) having at least two N-substituted maleimide groups in the molecule (hereinafter, also referred to as “maleimide compound (C)” or “component (C)”) and a thermoplastic elastomer (D) (hereinafter, hereinafter. "(D) component") is contained as the main component of the resin component.
The "resin component" in the resin composition (II) is mainly an amine compound (B), a maleimide compound (C), and a thermoplastic elastomer (D), and the resin composition (II) will be described later. When the amine compound (E) having an acidic substituent, the thermosetting resin (H), and other resin components are contained, these are also included.

[Amine compound (B)]
The amine compound (B) is not particularly limited as long as it is an amine compound having at least two primary amino groups in one molecule.
The amine compound (B) is preferably a compound having two primary amino groups in one molecule, and more preferably a diamine compound represented by the following general formula (B-1).

(In the general formula (B-1), X ^B1 is a group represented by the following general formula (B1-1) or (B1-2).)

(In the general formula ^{(B1-1), R B1} are each independently, .p is an aliphatic hydrocarbon group, or a halogen atom having 1 to 5 carbon atoms is an integer of 0-4.)

(In the general formula (B1-2), R ^B2 and R ^B3 are independently aliphatic hydrocarbon groups or halogen atoms ^{having 1 to 5 carbon atoms. X B2} is an alkylene group having 1 to 5 carbon atoms and carbon. The number 2 to 5 is an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, a single bond or a group represented by the following general formula (B1-2-1). Q and r are independent of each other. Is an integer from 0 to 4.)

(In the general formula (B1-2-1), R ^B4 and R ^B5 are independently aliphatic hydrocarbon groups having 1 to 5 carbon atoms or halogen atoms. X ^B3 is an alkylene group having 1 to 5 carbon atoms. , Alkylidene group, ether group, sulfide group, sulfonyl group, carbooxy group, keto group or single bond having 2 to 5 carbon atoms. S and t are independently integers of 0 to 4).

In the general formula ^(B1-1), the aliphatic hydrocarbon group represented by ^{R B1,} for example, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, t- butyl group , N-pentyl group and the like. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group. Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Among the above, as R ^B1 is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
p is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 2 from the viewpoint of availability. When p is an integer of 2 or more, the plurality of ^RB1s may be the same or different.

In the general formula ^(B1-2), aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by ^{R B2} and ^{R B3,} the halogen atom include the same case of the ^{R B1.} The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group and an ethyl group, and further preferably an ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^B2 include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group and the like. Can be mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group, from the viewpoint of heat resistance and low thermal expansion.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X ^B2 include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group. Among these, an isopropylidene group is preferable from the viewpoint of heat resistance and low thermal expansion.
Among the above options, X ^B2 preferably has an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms. More preferred are as described above.
q and r are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably an integer of 0 to 2, more preferably 0 or 2. When q or r is an integer of 2 or more, the plurality of ^RB2s or ^RB3s may be the same or different from each other.

In the general formula ^(B1-2-1), aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by ^{R B4} and ^{R B5,} examples of the halogen atom, the same thing can be mentioned in the case of the ^{R B2} and ^{R B3} , The preferred ones are the same.
The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X ^B3 are the same as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by ^{X B2.} The same is true for the preferred ones.
Among the above options, X ^B3 is preferably an alkylidene group having 2 to 5 carbon atoms, and more preferable one is as described above.
s and t are integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0. When s or t is an integer of 2 or more, the plurality of ^RB4s or ^RB5s may be the same or different from each other.
The general formula (B1-2-1) is preferably represented by the following general formula (B1-2-1').

(X ^B3 , R ^B4 , R ^B5 , s and t in the general formula (B1-2-1') are the same as those in the general formula (B1-2-1), and the preferable ones are also the same. .)

The group represented by the general formula (B1-2) is preferably a group represented by the following general formula (B1-2'), and any of the following formulas (B1-i) to (B1-iii). The group represented by (B1-ii) is more preferable, and the group represented by (B1-ii) is further preferable.

(X ^B2 , R ^B2 , R ^B3 , q and r in the general formula (B1-2') are the same as those in the general formula (B1-2'), and the preferable ones are also the same.)

In the general formula (B1-1), X ^B1 may be any of the groups represented by the general formula (B1-1) or (B1-2), and among these, low thermal expansion property and From the viewpoint of adhesive strength with a metal circuit, it is preferable that the group is represented by the general formula (B1-2).

Specific examples of the amine compound (B) include, for example, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1,4-diaminobenzene, 2,5-dimethyl-1,4-diamino. Benzene, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4, 4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylketone, benzidine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4 , 4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 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] Aromatic diamines such as sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 9,9-bis (4-aminophenyl) fluorene; ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, hepta Methylenediamine, 2,2,4-trimethylhexamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,5-dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylheptamethylenediamine , 3-Methylheptamethylenediamine, 4,4'-dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 1,4-diaminocyclohexane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 2, Hexamethylenediamines such as 5-diamino-1,3,4-oxadiazole, bis (4-aminocyclohexyl) methane; melamine, benzoguanamine, acetoguanamine, 2,4-diamino-6-vinyl-s-triazine, 2,4-ji Examples thereof include guanamine compounds such as amino-6-allyl-s-triazine, 2,4-diamino-6-acryloyloxyethyl-s-triazine, and 2,4-diamino-6-methacryloyloxyethyl-s-triazine. Only one type of these may be used, or two or more types may be mixed and used.

Among these, for example, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3, which are aromatic diamines having high reactivity and capable of higher heat resistance. '-Dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis [4-( 4-Aminophenoxy) phenyl] propane is preferable, and from the viewpoint of low cost and solubility in a solvent, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3, 3'-diethyl-4,4'-diaminodiphenylmethane and 2,2-bis [4- (4-aminophenoxy) phenyl] propane are more preferred, and 3,3'-diethyl from the viewpoint of low thermal expansion and dielectric properties. −4,4′-diaminodiphenylmethane and 2,2-bis [4- (4-aminophenoxy) phenyl] propane are more preferred.

Further, the amine compound (B) may contain a siloxane compound having at least two primary amino groups in one molecule from the viewpoint of low thermal expansion and elastic modulus.
Hereinafter, among the amine compounds (B) having at least two primary amino groups in one molecule, the siloxane compound having at least two primary amino groups in one molecule is referred to as "amine compound (b). ) ”Or“ (b) component ”.
The amine compound (b) preferably contains a structure represented by the following general formula (b-1).

(In the formula, R ^b1 and R ^b2 each independently represent an alkyl group, a phenyl group or a substituted phenyl group, and m represents an integer of 2 to 100.)

^{Examples of the alkyl group represented by R b1} and R ^b2 in the general formula (b-1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t-butyl group. , N-pentyl group and the like. As the alkyl group, an alkyl group having 1 to 5 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is further preferable.
Examples of the substituent contained in the phenyl group in the substituted phenyl group include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an alkynyl group having 2 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include the same alkyl groups as those described above. Examples of the alkenyl group having 2 to 5 carbon atoms include a vinyl group and an allyl group. Examples of the alkynyl group having 2 to 5 carbon atoms include an ethynyl group and a propargyl group.
Both R ^b1 and R ^b2 are preferably alkyl groups having 1 to 5 carbon atoms, and more preferably methyl groups.
m is an integer of 2 to 100 from the viewpoint of low thermal expansion, and an integer of 5 to 50 is preferable from the viewpoint of compatibility and high elasticity. An integer of 10 to 40 is more preferred.

The amine compound (b) preferably has at least two primary amino groups at the molecular ends, and is more preferably a compound represented by the following general formula (b-2).

(In the formula, R ^b1 , R ^b2 , R ^b3 and R ^b4 each independently represent an alkyl group, a phenyl group or a substituted phenyl group, and X ^b1 and X ^b2 each independently have a divalent organic group. Indicates. M'indicates an integer from 1 to 100.)

The alkyl group, phenyl group or substituted phenyl group represented by ^{R b1} , R ^b2 , R ^b3 and R ^b4 are the same as those ^{of R b1} and R ^{b2 in the general formula (b-1).}
Examples of the divalent organic group represented by X ^b1 and X ^b2 include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O— or a divalent linking group in which these are combined. Examples of the alkylene group include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group and a propylene group. Examples of the alkenylene group include an alkenylene group having 2 to 10 carbon atoms. Examples of the alkynylene group include an alkynylene group having 2 to 10 carbon atoms. Examples of the arylene group include an arylene group having 6 to 20 carbon atoms such as a phenylene group and a naphthylene group.
m'is an integer of 1 to 100 from the viewpoint of low thermal expansion, and an integer of 5 to 50 is preferable from the viewpoint of compatibility and high elasticity. An integer of 10 to 40 is more preferred.

As the component (b), a commercially available product can be used, for example, "KF-8010" (functional group equivalent of amino group 430), "X-22-161A" (functional group equivalent of amino group 800), "X". -22-161B "(functional group equivalent of amino group 1,500)," KF-8012 "(functional group equivalent of amino group 2,200)," KF-8008 "(functional group equivalent of amino group 5,700) , "X-22-9409" (functional group equivalent of amino group 700), "X-22-1660B-3" (functional group equivalent of amino group 2,200) (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.), ""BY-16-853U" (functional group equivalent of amino group 460), "BY-16-853" (functional group equivalent of amino group 650), "BY-16-853B" (functional group equivalent of amino group 2,200) (Above, manufactured by Toray Dow Corning Co., Ltd.), "XF42-C5742" (functional group equivalent of amino group 1280), "XF42-C6252" (functional group equivalent of amino group 1255), "XF42-C5379" (amino) Functional group equivalent of group 745) (above, manufactured by Momentive Performance Materials Japan LLC) and the like (the unit of functional group equivalent of amino group is g / mol). Only one type of these may be used, or two or more types may be mixed and used.
Among these, for example, "X-22-161A", "X-22-161B", "KF-8012", "X-22-1660B-" because of their high reactivity during synthesis and low thermal expansion. "3", "XF42-C5379", "XF42-C6252", "XF42-C5742" are preferable, and "X-22-161A", "X-22-161B" are excellent in compatibility and high elastic modulus. , "XF42-C6252", "XF42-C5379" are more preferable.

[Maleimide compound (C)]
The maleimide compound (C) is not particularly limited as long as it is a maleimide compound having at least two N-substituted maleimide groups in one molecule.
As the maleimide compound (C), a maleimide compound having two N-substituted maleimide groups in one molecule is preferable, and a compound represented by the following general formula (C-1) is more preferable.

(In the general formula (C-1), X ^C1 is a group represented by the following general formulas (C1-1), (C1-2), (C1-3) or (C1-4)).

(In the general formula ^(C1-1), the ^{R C1} are each independently, .P1 an aliphatic hydrocarbon group, or a halogen atom having 1 to 5 carbon atoms is an integer of 0-4.)

(In the general formula ^{(C1-2), R C2} and ^{R C3} are each independently, ^{.X C2} alkylene group having 1 to 5 carbon atoms is an aliphatic hydrocarbon group, or a halogen atom having 1 to 5 carbon atoms, a carbon The number 2 to 5 is an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, a single bond or a group represented by the following general formula (C1-2-1). Q1 and r1 are independent of each other. Is an integer from 0 to 4.)

(In the general formula ^{(C1-2-1), R C4} and ^{R C5} are each independently, ^{.X C3} alkylene group of 1 to 5 carbon atoms is an aliphatic hydrocarbon group, or a halogen atom having 1 to 5 carbon atoms , Alkylidene group, ether group, sulfide group, sulfonyl group, carbooxy group, keto group or single bond having 2 to 5 carbon atoms. S1 and t1 are independently integers of 0 to 4).

(In the general formula (C1-3), n1 is an integer of 1 to 10.)

(In the general formula ^(C1-4), each independently ^{R C6} and ^{R C7, .u1} an aliphatic hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms is an integer of 1 to 8.)

In the general formula ^(C1-1), examples of the aliphatic hydrocarbon group represented by ^{R C1,} for example, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, t- butyl group , N-pentyl group and the like. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group. Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Among the above, as R ^C1 is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
p1 is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0, from the viewpoint of availability. When p1 is an integer of 2 or more, the plurality of ^RC1s may be the same or different.

In the general formula ^(C1-2), aliphatic hydrocarbon group having 1 to 5 ^carbon atoms ^{R C2} and ^{R C3} are represented, as the halogen atom include the same case of the ^{R C1.} The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group and an ethyl group, and further preferably an ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^C2 include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group and the like. Can be mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoints of copper foil adhesiveness, low thermal expansion, low curing shrinkage, heat resistance (solder heat resistance), elastic modulus and moldability. More preferably, it is a methylene group.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X ^C2 include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group. Among these, an isopropylidene group is preferable from the viewpoints of copper foil adhesiveness, low thermal expansion, low curing shrinkage, heat resistance (solder heat resistance), elastic modulus and moldability.
Among the above options, X ^C2 preferably has an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms. More preferred are as described above.
q1 and r1 are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably an integer of 0 to 2, more preferably 0 or 2. If q1 or r1 is an integer of 2 or more, plural R ^C2 together or R ^C3 together may each be the same or different.

In the general formula ^(C1-2-1), aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by ^{R C4} and ^{R C5,} a halogen atom, the same thing can be mentioned in the case of the ^{R C2} and ^{R C3} , The preferred ones are the same.
The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X ^C3 are the same as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by ^{X C2.} The same is true for the preferred ones.
Among the above options, the X ^C3 is preferably an alkylidene group having 2 to 5 carbon atoms, and more preferable ones are as described above.
s1 and t1 are integers of 0 to 4, and from the viewpoint of availability, both are preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. When s1 or t1 is an integer of 2 or more, the plurality of ^RC4s or ^RC5s may be the same or different from each other.
Further, the general formula (C1-2-1) is preferably represented by the following general formula (C1-2-1').

(Formula (C1-2-1 ') ^X C3 ^in, R ^{C4, R} C5, s1 and t1 are the same as those of the general formula (C1-2-1), and preferred ones are also the same .)

The group represented by the general formula (C1-2) has the following general formula (from the viewpoint of copper foil adhesiveness, low thermal expansion, low curing shrinkage, heat resistance (solder heat resistance), elastic modulus and moldability). It is preferably a group represented by C1-2'), more preferably a group represented by any of the following (C1-i) to (C1-iii), and the following (C1-iii). It is more preferably the group represented.

(General ^X C2 in the formula ^{(C1-2 '), R C2,} R C3, q1 and r1 are the same as those of the general formula (C1-2), and preferred ones are also the same.)

In the general formula (C1-3), n1 is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3 from the viewpoint of availability.
In the general formula ^(C1-4), aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by ^{R C6} and ^{R C7,} the halogen atom, the same as in the formula (C1-1) in the ^{R C1} The same is true for the preferred ones. u1 is an integer of 1 to 8, preferably an integer of 1 to 3, and more preferably 1.

Specific examples of the maleimide compound (C) include bis (4-maleimidephenyl) methane, polyphenylmethane maleimide, bis (4-maleimidephenyl) ether, bis (4-maleimidephenyl) sulfone, 3,3'-dimethyl-. 5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis [4- (4-maleimidephenoxy) phenyl] Examples include propane. Only one type of these may be used, or two or more types may be mixed and used. Among these, for example, from the viewpoint of high reactivity and higher heat resistance, bis (4-maleimidephenyl) methane, bis (4-maleimidephenyl) sulfone, 2,2-bis [4- (4-maleimide) Phenoxy) phenyl] propane is preferable, and bis (4-maleimidephenyl) methane and 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane are more preferable from the viewpoint of solubility in a solvent.

[Thermoplastic elastomer (D)]
Examples of the thermoplastic elastomer (D) include styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, urethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, acrylic-based thermoplastic elastomers, and silicone-based thermoplastics. Examples include plastic elastomers and derivatives thereof. These may be used alone or in combination of two or more.
The thermoplastic elastomer (D) is preferably composed of a hard segment component and a soft segment component. In general, the hard segment component contributes to heat resistance and strength, and the soft segment component contributes to flexibility and toughness.
Among these, styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and silicone-based thermoplastic elastomers are preferable, and styrene-based thermoplastic elastomers are more preferable, from the viewpoint of heat resistance and insulation reliability.
The styrene-based thermoplastic elastomer is preferably a thermoplastic elastomer having a structural unit derived from styrene represented by the following general formula (D-1).

The styrene-based thermoplastic elastomer preferably contains a structural unit other than the structural unit derived from styrene, and examples of the structural unit other than the structural unit derived from styrene include a structural unit derived from butadiene, a structural unit derived from isoprene, and maleic anhydride. Examples include acid-derived structural units and maleic anhydride-derived structural units. These may be contained alone or in combination of two or more.
The structural unit derived from butadiene and the structural unit derived from isoprene are preferably hydrogenated. When hydrogenated, the structural unit derived from butadiene is a structural unit in which ethylene units and butylene units are mixed, and the structural unit derived from isoprene is a structural unit in which ethylene units and propylene units are mixed. Among these, it is preferable to contain ethylene units and butylene units, which are structural units derived from butadiene. The molar ratio of the structural unit derived from styrene to the structural unit derived from butadiene (styrene: butadiene) is preferably 5:95 to 60:40, more preferably 10:90 to 50:50, and 20:80 to 40:60. Is even more preferable.

Styrene-based thermoplastic elastomers include hydrogenated styrene-butadiene-styrene block copolymers and styrene-isoprene-styrene from the viewpoints of low thermal expansion, adhesive strength to metal circuits, heat resistance, elasticity, and high frequency characteristics. It is preferably one or more selected from the group consisting of hydrogenated blocks copolymers, and more preferably hydrogenated styrene-butadiene-styrene block copolymers.
The hydrogenated additives of the styrene-butadiene-styrene block copolymer include SEBS in which the hydrogenation rate of the carbon-carbon double bond is usually 90% or more (preferably 95% or more), and 1 in the butadiene block. , 2-bonding site carbon-carbon double bond is partially hydrogenated SBBS (hydrogenation rate to the total carbon-carbon double bond is about 60-85%). Among these, SEBS is more preferable.

The thermoplastic elastomer (D) may have a reactive functional group at least one of the molecular terminal and the molecular chain. 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 (meth) acrylic group, a vinyl group and the like. By having the reactive functional group, the compatibility with other resin components is improved, and the internal stress generated at the time of curing of the thermosetting resin composition can be more effectively reduced, and as a result, the coreless substrate can be obtained. It is possible to remarkably reduce the warp of the. In particular, from the viewpoint of adhesive strength with a metal circuit, it is preferable to have at least one selected from the group consisting of an epoxy group, a hydroxyl group, a carboxy group, an amino group and an amide group, and from the viewpoint of heat resistance and insulation reliability, it is preferable. An epoxy group, a hydroxyl group, a carboxy group and an amino group are more preferable, and it is further preferable to have a carboxy group.
The acid value of the thermoplastic elastomer (D) is preferably from 2~50mgCH ₃ ONa / g, more preferably 4~30mgCH ₃ ONa / g, more preferably 6~20mgCH ₃ ONa / g. The acid value of the thermoplastic elastomer (D) can be measured by a titration method using _{sodium methoxide (CH 3 ONa).}

The melt flow rate (MFR; Melt Flow Rate) of the thermoplastic elastomer (D) is preferably 1 to 20 g / min, more preferably 2 to 15 g / min, still more preferably 3 to 10 g / min. The MFR is a value measured at a temperature of 200 ° C. and a load of 5 kgf in accordance with ISO1133.

[Amine compound (E) having an acidic substituent]
Even if the resin composition (II) further contains an amine compound (E) having an acidic substituent represented by the following general formula (E-1) (hereinafter, also referred to as “component (E)”). Good.

(Wherein, R ^E1 is independently a hydroxyl group is an acidic substituent represents a carboxyl group or a sulfonic acid group, R ^E2 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms Alternatively, it indicates a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.)

Specific examples of the amine compound (E) having an acidic substituent include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o. -Aminobenzene sulfonic acid, m-aminobenzene sulfonic acid, p-aminobenzene sulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like can be mentioned. Only one type of these may be used, or two or more types may be mixed and used. Among these, for example, from the viewpoint of solubility and synthetic yield, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, 3,5-dihydroxyaniline Is preferable, and m-aminophenol and p-aminophenol are more preferable from the viewpoint of heat resistance.

[Content of each component in the resin composition (II)]
The content of the amine compound (B) in the resin composition (II) is 1 to 1 to 100 parts by mass of the solid content of the resin component in the resin composition (II) from the viewpoint of copper foil adhesiveness and moldability. 40 parts by mass is preferable, 3 to 30 parts by mass is more preferable, and 5 to 20 parts by mass is further preferable.
When the resin composition (II) contains the amine compound (b) as the component (B), the content thereof is the resin in the resin composition (II) from the viewpoint of copper foil adhesiveness and chemical resistance. With respect to 100 parts by mass of the solid content of the component, 1 to 30 parts by mass is preferable, and 5 to 20 parts by mass is more preferable.
The content of the maleimide compound (C) in the resin composition (II) is based on 100 parts by mass of the solid content of the resin component in the resin composition (II) from the viewpoint of low thermal expansion, heat resistance and high elastic modulus. 20 to 95 parts by mass is preferable, 25 to 80 parts by mass is more preferable, and 30 to 70 parts by mass is further preferable.
The content of the thermoplastic elastomer (D) in the resin composition (II) is 5 with respect to 100 parts by mass of the solid content of the resin component in the resin composition (II) from the viewpoint of copper foil adhesiveness and moldability. ~ 80 parts by mass is preferable, 10 to 70 parts by mass is more preferable, and 15 to 65 parts by mass is further preferable.
When the resin composition (II) contains an amine compound (E) having an acidic substituent, the total content thereof is 100% by mass of the solid content of the resin component in the resin composition (II) from the viewpoint of low thermal expansion. With respect to parts, 0.5 to 30 parts by mass is preferable, 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable.
The total content of the component (B), the component (C), and the component (D) in the resin composition (II) is determined from the viewpoints of low thermal expansion, heat resistance, high elastic modulus, copper foil adhesiveness, and moldability. With respect to 100 parts by mass of the solid content of the resin component in the resin composition (II), 50 parts by mass or more is preferable, 60 parts by mass or more is more preferable, and 70 parts by mass or more is further preferable. The upper limit of the total content is not particularly limited, and may be, for example, 100 parts by mass or less, 95 parts by mass or less, or 85 parts by mass or less.

The component (B) and the component (C) in the resin composition (II) may be a mixture of the components (B) and the component (C) as they are, or the component (B) and the component (C) may be reacted to react with the amino-modified polyimide. Resin [hereinafter referred to as "amino-modified polyimide resin (X)". ] May be used. That is, the resin composition (II) may be a resin composition containing the component (B) and the component (C), and is an amino-modified product which is a reaction product of the component (B) and the component (C). It may be a resin composition containing a polyimide resin (X). The amino-modified polyimide resin (X) will be described below.

[Amino-modified polyimide resin (X)]
The amino-modified polyimide resin (X) is obtained by reacting an amine compound (B) with a maleimide compound (C) (hereinafter, also referred to as “pre-reaction”), and has a structure derived from the amine compound (B). It contains a unit (B') and a structural unit (C') derived from the maleimide compound (C).
Further, the amino-modified polyimide resin (X) may be further reacted with an amine compound (E) having an acidic substituent, if necessary. In that case, the amine compound (E) having an acidic substituent may be further reacted. ) Derived structural unit (E') is contained.
By the pre-reaction, the molecular weight can be controlled, and low curing shrinkage and low thermal expansion can be improved.

The pre-reaction is preferably carried out while being heated and kept warm in an organic solvent. The reaction temperature is, for example, 70 to 150 ° C, preferably 100 to 130 ° C. The reaction time is, for example, 0.1 to 10 hours, preferably 1 to 6 hours.
Examples of the organic solvent used in the pre-reaction include the same organic solvents used for the varnish described later. Among these, propylene glycol monomethyl ether is preferable because of its solubility, low toxicity, high volatility, and difficulty in remaining as a residual solvent.
From the viewpoint of solubility and reaction rate, the amount of the organic solvent used is preferably 25 to 2,000 parts by mass, preferably 40 to 1,000 parts by mass, based on 100 parts by mass of the total of each raw material component of the pre-reaction. More preferably, 40 to 500 parts by mass is further preferable.
A reaction catalyst may 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. Only one type of these may be used, or two or more types may be mixed and used.

The amount of the maleimide compound (C) used in the pre-reaction is preferably in the range in which the number of maleimide groups of the maleimide compound (C) is 2 to 10 times the number of primary amino groups of the component (B). When it is 2 times or more, excellent heat resistance is obtained without gelation, and when it is 10 times or less, excellent solubility in an organic solvent and heat resistance can be obtained. When the component (E) is also reacted, the number of maleimide groups of the maleimide compound (C) is the number of primary amino groups of the component (B) and the number of primary amino groups of the component (E) from the same viewpoint. It is preferable that the range is 2 to 10 times the total of.
The number of maleimide groups of the maleimide compound (C) is represented by [the amount of the maleimide compound (C) used / the equivalent of the maleimide groups of the maleimide compound (C)], and the number of primary amino groups of the component (B) is [(B). The amount of the component used / the primary amino group equivalent of the component (B)], and the number of primary amino groups of the component (E) is [the amount of the component used (E) / the primary amino of the component (E). Base amount].

The content of the structural unit (B') derived from the amine compound (B) in the amino-modified polyimide resin (X) is preferably 1 to 40% by mass, preferably 5 to 30% by mass, from the viewpoint of copper foil adhesiveness and moldability. % Is more preferable, and 10 to 25% by mass is further preferable.
When the amino-modified polyimide resin (X) contains a structural unit (b') derived from the amine compound (b), the content thereof is the amino-modified polyimide resin (X) from the viewpoint of copper foil adhesiveness and chemical resistance. ), 1 to 40% by mass is preferable, and 6 to 25% by mass is more preferable.
The content of the structural unit (C') derived from the maleimide compound (C) in the amino-modified polyimide resin (X) is preferably 50 to 95% by mass, preferably 60 to 95% by mass, from the viewpoint of low thermal expansion, heat resistance and high elastic modulus. ~ 90% by mass is more preferable, and 70 to 85% by mass is further preferable.
When the amino-modified polyimide resin (X) contains a structural unit (E') derived from the amine compound (E) having an acidic substituent, the content thereof is the amino-modified polyimide resin (X) from the viewpoint of low thermal expansion. ), 0.5 to 40% by mass is preferable, 1 to 15% by mass is more preferable, and 1.5 to 4% by mass is further preferable.

Further, the structural unit (B'), the structural unit (b'), the structural unit (C'), and the structural unit (E) when 100 parts by mass of the solid content of the resin component in the resin composition (II) is used as a reference. The suitable content of') is the same as the preferred embodiment of the contents of the component (B), the component (b), the component (C), and the component (E) in the resin composition (II), respectively. ..
However, the resin composition (II) is one or more selected from the group consisting of the component (B), the component (b), the component (C) and the component (E), in addition to the amino-modified polyimide resin (X). When the total content of each component and the structural unit derived from each component is suitable for the component (B), the component (b), the component (C) and the component (E) in the resin composition (II). The content is preferably high.

When the resin composition (II) contains the amino-modified polyimide resin (X), the content thereof is the resin composition (from the viewpoints of low thermal expansion property, heat resistance, high elastic modulus, copper foil adhesiveness and moldability). With respect to 100 parts by mass of the solid content of the resin component in II), 50 parts by mass or more is preferable, 60 parts by mass or more is more preferable, and 70 parts by mass or more is further preferable. The upper limit of the content of the amino-modified polyimide resin (X) is not particularly limited, and may be, for example, 100 parts by mass or less, 95 parts by mass or less, or 85 parts by mass or less. Good.

[Polymerization initiator]
The resin composition (II) has good thermosetting reactivity, but if necessary, it contains a curing agent and / or a polymerization initiator to further improve heat resistance, copper foil adhesiveness, and mechanical strength. Can be done.
As the polymerization initiator, a radical polymerization initiator is preferable, and organic peroxides such as acyl peroxide, hydroperoxide, ketone peroxide, organic peroxide having a t-butyl group, and peroxide having a cumyl group are used. Things can be mentioned. Only one type of these may be used, or two or more types may be mixed and used.

[Inorganic filler (F)]
The resin composition (II) may further contain an inorganic filler (F). Examples of the inorganic filler (F) include those similar to those mentioned in the resin composition (I), and preferred embodiments such as type and content are also the same as in the case of the resin composition (I). ..

[Thermosetting resin (H)]
The resin composition (II) further contains one or more thermosetting resins (H) selected from the group consisting of epoxy resins and cyanate resins (hereinafter, also simply referred to as “thermosetting resins (H)”). You may be doing it.
Examples of the epoxy resin include the same as the epoxy resin (A), and the preferred embodiment is the same as that of the epoxy resin (A).
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. Only one type of these may be used, or two or more types may be mixed and used.
When the resin composition (II) contains a thermosetting resin (H), the content thereof is the content of the resin component in the resin composition (II) from the viewpoint of copper foil adhesiveness, heat resistance and chemical resistance. With respect to 100 parts by mass of the solid content, 1 to 50 parts by mass is preferable, and 8 to 30 parts by mass is more preferable.
When the resin composition (II) contains a thermosetting resin (H), it may contain a curing agent, a curing accelerator, or the like exemplified in the resin composition (I).

[Other ingredients]
The resin composition (II) may further contain the other components that the resin composition (I) may contain.

[Manufacturing method of prepreg]
In the prepreg of the present invention, for example, a first resin film formed from the resin composition (I) is laminated on one surface of the fiber base material, and the resin composition ( It can be produced by a method of laminating a second resin film formed from II).

For the first resin film and the second resin film, for example, the resin composition (I) and the resin composition (II) are each applied to a release film and then semi-cured (B-staged) by heating or the like. It can be produced by.

When producing the first resin film and the second resin film, the resin composition (I) and the resin composition (II) are used from the viewpoint of facilitating handling and the productivity of the resin film and the prepreg of the present invention. From the viewpoint of improvement, if necessary, each component may be in the state of a varnish dissolved or dispersed in an organic solvent.
Examples of the organic solvent used for the varnish include alcohol solvents such as methanol, 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; acetic acid. Ester solvents such as butyl, ethyl acetate, γ-butyrolactone, propylene glycol monomethyl ether acetate; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, mesitylen; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. Nitrogen atom-containing solvent; Examples thereof include a sulfur atom-containing solvent such as dimethyl sulfoxide. Only one type of these may be used, or two or more types may be mixed and used.
Among these, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are preferable from the viewpoint of solubility, and methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity.
The solid content of the resin composition (I) or the resin composition (II) in the varnish is preferably 40 to 90% by mass, more preferably 50 to 80% by mass of the entire varnish. When the solid content is within the above range, the coatability is improved and the productivity of the resin film and the prepreg is excellent.

A known coating machine such as a die coater, a comma coater, a bar coater, a kiss coater, or a roll coater can be used for coating when producing the resin film. These coating machines may be appropriately selected depending on the desired thickness of the resin film.
Examples of the release film used for the resin film include organic films such as polyethylene terephthalate (PET), biaxially stretched polypropylene (OPP), polyethylene, polyvinylfluorate, and polyimide; films made of copper, aluminum, and alloys of these metals. Can be mentioned. These release films may be those that have been release-treated with a release agent.

Lamination may be performed by a known method such as roll laminating using a pressure roll or a vacuum laminating method, but from the viewpoint of productivity, roll laminating is preferable. The conditions for roll laminating can be, for example, a heating temperature of 50 to 150 ° C., a linear pressure of 0.1 to 1.0 MPa, and a speed of 0.5 to 5 m / min. The atmosphere at the time of laminating may be normal pressure or reduced pressure, but from the viewpoint of productivity, normal pressure is preferable.
The laminating of the first resin film and the laminating of the second resin film may be performed separately, but it is preferable to perform the laminating of the second resin film at the same time from the viewpoint of productivity. That is, the first resin film is arranged on one surface of the fiber base material, the second resin film is arranged on the other surface of the fiber base material, and the first resin film and the second resin film are formed by roll laminating or the like. It is preferable to form the first resin layer and the second resin layer while impregnating the resin composition (I) and the resin composition (II) into the fiber base material by laminating the resin films at the same time.

The surfaces of the first resin film and the second resin film in contact with the fiber base material (resin layer forming surface) may be preheated before laminating. The heating position should be adjusted so that, for example, the center of the heating surface of the heater is 10 to 50 mm before the pressure roll, and the heating temperature is 100 to 150 ° C, preferably 110 to 140 ° C at the center of the heating surface. Just do it.
Similarly, the fiber base material may be preheated before laminating. The temperature of the fiber base material may be, for example, 100 to 170 ° C, preferably 120 to 150 ° C.
For heating, for example, a halogen heater can be used.

The thickness of the entire prepreg may be appropriately adjusted according to the thickness of the inner layer circuit and the like, but from the viewpoint of thinning the substrate, moldability and workability, it is preferably 10 μm or more, more preferably 20 μm or more. The thickness is preferably 700 μm or less, more preferably 500 μm or less, still more preferably 200 μm or less, still more preferably 100 μm or less, particularly preferably 80 μm or less, and most preferably 50 μm or less.

[Laminated board]
The laminated board of the present invention is formed by laminating and molding the prepreg of the present invention.
The laminated board of the present invention can be produced, for example, by laminating 1 to 20 prepregs of the present invention and arranging metal foils 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.
The metal of the metal foil may be copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metal elements. preferable.
As the molding conditions, for example, the method of a laminated board for an electrically insulating material and a multi-layer board can be applied, and a multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine, etc. It can be molded under the conditions of 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 the prepreg.

[Printed circuit board]
The printed wiring board of the present invention contains the laminated board of the present invention.
The printed wiring board of the present invention can be manufactured by circuit processing a conductor layer (metal foil) arranged on one side or both sides of the laminated board of the present invention. The method for forming the wiring pattern is not particularly limited, but the subtractive method, the full additive method, the semi-additive method (SAP: Semi Additive Process), the modified semi-additive method (m-SAP: modified Semi Additive Process), etc. A known method of the above can be mentioned.
Specifically, first, the conductor layer of the laminated plate of the present invention is wired by the above method, and then a plurality of laminated plates wired via the prepreg of the present invention are laminated and heat-pressed. Multi-layered at once. After that, the 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.

[Coreless substrate and its manufacturing method]
The coreless substrate of the present invention is a coreless substrate containing an insulating layer formed by using the prepreg of the present invention. The prepreg of the present invention is particularly suitable as a prepreg for a coreless substrate because it has features of excellent heat resistance, low thermal expansion, and moldability.
The coreless substrate is, for example, a method of forming a build-up layer in which conductor layers and insulating layers are alternately laminated by using the prepreg of the present invention on a support (core substrate), and then separating the support. Can be manufactured by The method for forming the build-up layer is not particularly limited, and a known method can be adopted. For example, the build-up layer can be formed by the following method (see FIG. 3).
First, the prepreg 2 of the present invention is placed on the support (core substrate) 1. The prepreg 2 may be arranged after the adhesive layer is arranged on the support (core substrate) 1. Then, the prepreg 2 is heat-cured to form an insulating layer. Next, after forming the via hole 3 by a drill cutting method, a _{laser processing method using a YAG laser, a CO 2} laser, or the like, a surface roughening treatment and a desmear treatment are performed as necessary. Subsequently, the circuit pattern 4 is formed by the method described above. Next, the prepreg 2 of the present invention is arranged so as to be in contact with the circuit pattern 4 and heat-cured to form an insulating layer. By repeating the above steps, the build-up layer 5 is formed. A coreless substrate can be obtained by separating the formed build-up layer 5 from the support (core substrate) 1. The screw-up layer 5 may be formed on one side of the support (core substrate) 1 or on both sides.
As shown in FIG. 3, when the prepreg of the present invention is used for manufacturing a coreless substrate, the first resin layer of the prepreg of the present invention is further arranged on the circuit pattern 4. By arranging the circuit pattern 4 so as to be in contact with the circuit pattern 4, good moldability can be achieved.
The coreless substrate of the present invention contains one or more insulating layers obtained by curing the prepreg of the present invention, and contains an insulating layer formed by curing a prepreg, a resin film, or the like other than the prepreg of the present invention. You may.
The thickness of the coreless substrate of the present invention is usually small because it does not have a core substrate, and specifically, 40 to 300 mm is preferable, 40 to 200 mm is more preferable, and 40 to 100 mm is further preferable.

[Semiconductor package]
The semiconductor package of the present invention comprises mounting a semiconductor on a printed wiring board or a coreless substrate of the present invention. The semiconductor package of the present invention can be manufactured, for example, by mounting a semiconductor chip, a memory, or the like at a predetermined position on the printed wiring board or coreless substrate of the present invention.

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 performance of the copper-clad laminates obtained in each example was evaluated by the following method.

(1) Copper Foil Peel Strength After forming a resist having a width of 3 mm on the outer layer copper foil of the copper-clad laminate obtained in each example, the outer layer copper having a width of 3 mm is used as a peel strength measuring part by immersing the resist in a copper etching solution. An evaluation substrate having a foil was prepared. Peel off one end of the copper foil of the peel strength measuring part at the interface between the copper foil and the substrate, grasp it with a gripper, and use a tensile tester (manufactured by Shimadzu Corporation, product name: Autograph S-100) to make it vertical. The pulling speed in the direction was 50 mm / min, and the load when peeled off at room temperature was measured. The results are shown in Table 1.

(2) Coefficient of thermal expansion The copper foil was removed by immersing the copper-clad laminate obtained in each example in a copper etching solution. Length 5 mm (X direction), width 5 mm (Y direction), thickness 140 μm (Z direction) The evaluation substrate of the above was prepared, and thermomechanical analysis was performed by a compression method using a TMA test apparatus (manufactured by TA Instruments, trade name: Q400). The thermomechanical analysis is performed twice continuously under the conditions of a load of 5 g and a heating rate of 10 ° C./min after mounting the evaluation substrate on the apparatus in the X direction, and the average from 30 ° C. to 100 ° C. in the second analysis. The coefficient of thermal expansion was calculated and used as the value of the coefficient of thermal expansion. The results are shown in Table 1.

(3) Bending elastic modulus A 25 mm × 50 mm evaluation substrate from which the copper foil was removed was prepared by immersing the copper-clad laminate obtained in each example in a copper etching solution, and 5 ton tencilon (manufactured by Orientec Co., Ltd.) was produced. The measurement was performed under the conditions of a crosshead speed of 1 mm / min and an interspan distance of 20 mm. The results are shown in Table 1.

(4) Glass transition temperature (Tg)
By immersing the copper-clad laminates obtained in each example in a copper etching solution, an evaluation substrate having a length of 5 mm (X direction), a width of 5 mm (Y direction), and a thickness of 140 μm (Z direction) was prepared by removing the copper foil. , TMA test equipment (manufactured by TA Instruments, trade name: Q400) was used to perform thermomechanical analysis by the compression method. The thermomechanical analysis is performed twice continuously under the conditions of a load of 5 g and a heating rate of 10 ° C./min after mounting the evaluation substrate on the apparatus in the X direction, and is indicated by the intersection of tangents of different thermal expansion curves for the second time. The glass transition temperature (Tg) was determined. The results are shown in Table 1.

(5) Heat resistance of solder with copper A 25 mm square evaluation substrate was prepared from the copper-clad laminates obtained in each example, and the evaluation substrate was floated in a solder bath at a temperature of 288 ° C. for 10 minutes to visually check the appearance of the evaluation substrate. And evaluated according to the following criteria. The results are shown in Table 1.
A: No swelling was confirmed.
B: Slight swelling was confirmed.
C: Swelling was noticeably confirmed.

(6) Moldability (presence or absence of voids)
The prepregs obtained in each example were laminated on the circuit surface of a copper-clad laminated plate circuit-processed with a residual copper ratio of 60% so that the first resin layer was on the circuit surface side, and further on the upper surface thereof. A copper foil having a thickness of 12 μm was placed. Next, this is sandwiched between 1.8 mm thick and 530 mm square SUS end plates, and using a multi-stage vacuum press, the temperature rise rate in the region of product temperature 60 to 160 ° C., pressure 3 to 4 ° C./min, in a vacuum atmosphere. A copper-clad laminate was produced by pressing for 90 minutes under the conditions of 2.5 MPa and a maximum holding temperature of 220 ° C. The copper foil of the obtained copper-clad laminate was removed by etching, and the appearance of the cured prepreg was visually observed and evaluated according to the following criteria. The results are shown in Table 1.
A: No void was confirmed.
B: Voids were slightly confirmed.
C: Voids were noticeably confirmed.

[Manufacturing of Amino Modified Polyimide Resin (X)]
Manufacturing example 1
(Manufacture of Amino Modified Polyimide Resin (X-1))
3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd.) in a reaction vessel with a volume of 2 liters capable of heating and cooling equipped with a thermometer, a stirrer and a moisture meter with a reflux condenser. Product name: KAYAHARD (registered trademark) AA) 30.0 g and 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane (manufactured by Daiwa Kasei Kogyo Co., Ltd., product name: BMI-4000) 120 0.0 g and 250.0 g of propylene glycol monomethyl ether were added and reacted at 100 ° C. for 3 hours to obtain an amino-modified polyimide resin (X-1) -containing solution.

[Preparation of resin film]
Production Examples 2 to 17
(Preparation of resin films A1 to A8 and resin films B1 to B8)
Each component shown in Table 1 is mixed at the blending ratio shown in Table 1 (the unit of the numerical value in the table is a mass part, and in the case of a solution, it is a solid content equivalent amount), and solid using methyl ethyl ketone as a solvent. A varnish having a component concentration of 65% by mass was prepared. This varnish is applied to a 580 mm wide PET film (manufactured by Teijin DuPont Film Co., Ltd., trade name: G-2) with a coating width of 525 mm and adjusted so that the thickness of the resin layer after drying is 10 μm. Films A1 to A8 and resin films B1 to B8 were produced.

[Making prepregs and copper-clad laminates]
Examples 1 to 4, Comparative Examples 1 to 4
Resin film A on one side of glass cloth (thickness 15 μm, basis weight 13 g / m ² , IPC # 1017, base material width 530 mm, manufactured by Nitto Spinning Co., Ltd.), which is a fiber base material, and a resin film on the other side. B was arranged so that each resin layer forming surface faced the glass cloth. This was sandwiched between pressure rolls and laminated, and the resin composition was pressure-impregnated from both sides of the fiber base material. Then, it was cooled with a cooling roll and wound up to obtain a prepreg. The conditions of the pressure roll were a roll temperature of 100 ° C., a linear pressure of 0.2 MPa, and a speed of 2.0 m / min. Further, the lamination was carried out under normal pressure.
The surfaces of the resin film A and the resin film B in contact with the glass cloth (resin layer forming surface) were preheated before laminating. The heating position was adjusted so that the center of the heating surface of the heater was 30 mm before the pressure roll, and the heating temperature was 135 ° C. at the center of the heating surface. The glass cloth itself was heated in the same manner, and the temperature of the glass cloth was adjusted to 140 ° C. A halogen heater (manufactured by Ushio, Inc., device name: UH-USF-CL-700) was used for heating.
The total thickness of the obtained prepreg was 35 μm, the thickness of the first resin layer was 10 μm, and the thickness of the second resin layer was 10 μm. The thickness of each layer was measured by the above method using a scanning electron microscope (SEM) after exposing the cross section of the prepreg.
Four prepregs obtained above were stacked so that the first resin layer and the second resin layer faced each other, and electrolytic copper foils having a thickness of 12 μm were arranged one above the other, and the pressure was 3.0 MPa and the temperature was 240 ° C. Was pressed for 60 minutes to obtain a copper-clad laminate.

The raw materials used in each example are as follows.

[Amino-modified polyimide resin (X)]
-Amino-modified polyimide resin (X-1): Amino-modified polyimide resin (X-1) -containing solution prepared in Production Example 1.

[Epoxy resin (A)]
-NC-7000L: α-naphthol / cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name)

[Amine compound (B)]
-KAYAHARD A-A: 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name)

[Maleimide compound (C)]
BMI-4000: 2,2-bis [4- (4-maleimide phenoxy) phenyl] propane (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name)

[Thermoplastic elastomer (D)]
Tough Tech (registered trademark) M1913: Carboxylic acid-modified hydrogenated styrene-butadiene copolymer resin [manufactured by Asahi Kasei Chemicals Co., Ltd., molar ratio of structural units derived from styrene to structural units derived from butadiene (styrene: butadiene) = 30:70 , Acid value: 10 mgCH ₃ ONa / g, MFR (temperature 200 ° C., load 5 kgf): 4.0 g / 10 min]

[Inorganic filler (F)]
-SC2050-KNK: Fused spherical silica (manufactured by Admatex Co., Ltd., trade name)

As is clear from Table 1, the laminated plates obtained in Examples 1 to 4 are excellent in all of copper foil peel strength, coefficient of thermal expansion, bending elasticity, glass transition temperature, heat resistance to solder with copper, and moldability. It has both excellent thermal expansion coefficient, glass transition temperature, heat resistance to copper solder, and moldability. On the other hand, the laminated plates obtained in Comparative Examples 1 to 4 do not satisfy all of the performances of the coefficient of thermal expansion, the glass transition temperature, the heat resistance of the solder with copper and the moldability, and are inferior in any of the characteristics. From the above, it can be seen that the prepreg of the present invention is excellent in low thermal expansion property, heat resistance and moldability.

Since the prepreg of the present invention is excellent in low thermal expansion, heat resistance and moldability, it is useful as a highly integrated semiconductor package, a printed wiring board for electronic devices, and the like.

1 Support (core substrate)
2 prepreg (insulation layer)
3 Via hole 4 Circuit pattern 5 Build-up layer 6 Coreless board

Claims (12)

A fiber base material layer containing a fiber base material, a first resin layer formed on one surface of the fiber base material layer, and a second resin layer formed on the other surface of the fiber base material layer. And is a prepreg with
The first resin layer is a layer formed of wood fat composition (I) and the layer formed,
The resin composition (I) contains an epoxy resin (A), and the resin composition (I) contains the epoxy resin (A).
Among the total amount of the resin components contained in the resin composition (I), the content of the epoxy resin (A) is the highest.
The second resin layer, Ri layer der consisting tree fat composition (II) and the layer formed,
The resin composition (II) has an amine compound (B) having at least two primary amino groups in one molecule and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. ) And the thermoplastic elastomer (D) as resin components.
A prepreg having the highest total content of the component (B), the component (C) and the component (D) among the total amount of the resin components contained in the resin composition (II). A fiber base material layer containing a fiber base material, a first resin layer formed on one surface of the fiber base material layer, and a second resin layer formed on the other surface of the fiber base material layer. And is a prepreg with
The first resin layer is a layer formed of wood fat composition (I) and the layer formed,
The resin composition (I) contains an epoxy resin (A), and the resin composition (I) contains the epoxy resin (A).
Among the total amount of the resin components contained in the resin composition (I), the content of the epoxy resin (A) is the highest.
The second resin layer, Ri layer der consisting tree fat composition (II) and the layer formed,
The resin composition (II) has an amine compound (B) having at least two primary amino groups in one molecule and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. Amino-modified polyimide resin (X) and thermoplastic elastomer (D), which are the reactants of the above, are contained as resin components.
A prepreg having the highest total content of the component (X) and the component (D) among the total amount of the resin components contained in the resin composition (II). The prepreg according to claim 1 or 2, wherein the thermoplastic elastomer (D) is a thermoplastic elastomer having a structural unit derived from styrene represented by the following general formula (D-1).
The claim that the content of the thermoplastic elastomer (D) in the resin composition (II) is 5 to 80 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the resin composition (II). The prepreg according to any one of 1 to 3. The invention according to any one of claims 1 to 4, wherein the resin composition (II) further contains one or more thermosetting resins (H) selected from the group consisting of an epoxy resin and a cyanate resin. Prepreg. The prepreg according to any one of claims 1 to 5, wherein one or more selected from the group consisting of the resin composition (I) and the resin composition (II) further contains an inorganic filler (F). .. A laminated board obtained by laminating and molding the prepreg according to any one of claims 1 to 6. A printed wiring board containing the laminated board according to claim 7. The prepreg according to any one of claims 1 to 6, which is for a coreless substrate. A coreless substrate containing an insulating layer formed by using the prepreg according to claim 9. A method for manufacturing a coreless substrate, which comprises a step of arranging the prepreg according to claim 9 so as to be in contact with a circuit pattern. A semiconductor package in which a semiconductor element is mounted on the printed wiring board according to claim 8 or the coreless substrate according to claim 10.