KR102364539B1 - Resin compositions - Google Patents

Abstract

[Problem] To provide a resin composition capable of obtaining a cured product having a high glass transition temperature, good adhesion to a conductor layer, and low dielectric loss tangent.
[Solutions] A resin composition containing (A) an epoxy resin, (B) an active ester compound having a carbon-carbon unsaturated bond, and (C) a resin having an unsaturated hydrocarbon group.

Description

Resin composition {RESIN COMPOSITIONS}

The present invention relates to a resin composition. Moreover, it is related with the printed wiring board containing the sheet-like laminated material containing the said resin composition, the insulating layer formed with the hardened|cured material of the said resin composition, and a semiconductor device.

As a manufacturing technique of a printed wiring board, the manufacturing method by the build-up method which piles up an insulating layer and a conductor layer alternately on an inner-layer board|substrate is known. An insulating layer is generally formed by hardening a resin composition.

For example, in Patent Document 1, at least the epoxy resin (A) and the naphthalene structure when the nonvolatile component in the resin composition containing the active ester compound (B) containing the naphthalene structure is 100% by mass. The thermosetting epoxy resin composition is disclosed whose content of the active ester compound (B) to be used is 0.1-30 mass %.

Moreover, in patent document 2, (A) radically polymerizable compound, (B) epoxy resin, (C) hardening|curing agent, and (D) a roughening component are contained, The resin composition characterized by the above-mentioned is disclosed.

As described above, although many proposals have been made for an epoxy resin composition suitable for forming an insulating layer of an inner circuit board, a resin composition capable of forming an insulating layer having a well-balanced characteristic of low dielectric loss tangent and excellent heat resistance and adhesion. The demand for it is getting higher.

Patent Document 1: Japanese Patent Laid-Open No. 2014-47318 Patent Document 2: Japanese Patent Laid-Open No. 2014-34580

An object of the present invention is to provide a resin composition capable of forming an insulating layer having a low dielectric loss tangent, a high dielectric transition temperature, and high adhesion.

As a result of earnest examination of the above subject, the present inventors have found that (A) an epoxy resin, (B) an active ester compound having a carbon-carbon unsaturated bond, and (C) a resin composition comprising a resin having an unsaturated hydrocarbon group in combination By this, it discovered that said subject could be solvable, and came to complete this invention.

That is, the present invention includes the following contents.

[1] (A) an epoxy resin (hereinafter also referred to as “component (A)” in this specification), (B) an active ester compound having a carbon-carbon unsaturated bond (hereinafter also referred to as “component (B)” in this specification) and (C) a resin having an unsaturated hydrocarbon group (hereinafter, also referred to as “component (C)” in the present specification), a resin composition containing.

[2] The resin composition according to [1], wherein the content of the component (B) is 10% by mass to 60% by mass when the resin component is 100% by mass.

[3] The content of the component (A) is 10% by mass to 50% by mass when the resin component is 100% by mass, and the content of the component (C) is 3% by mass when the resin component is 100% by mass. % to 30 mass%, the resin composition according to the above [1] or [2].

[4] The resin composition according to any one of [1] to [3], wherein the component (B) is an active ester compound having a carbon-carbon double bond.

[5] The resin composition according to the above [4], wherein the component (B) is an active ester compound having a vinyl group, a methacryl group, an acryl group, an allyl group, a styryl group or a propenyl group.

[6] The resin composition according to the above [5], wherein the component (B) is an active ester compound having a styryl group.

[7] The resin composition according to [6], wherein the component (B) contains a compound represented by the following formula (1).

Formula (1)

In the above formula (1),

m represents the integer of 1-6, n represents the integer of 1-20.

[8] The resin composition according to any one of [1] to [7], wherein the component (C) is a resin having an acryl group, a methacryl group, a styryl group, or an olefin group.

[9] The resin composition according to any one of [1] to [8], which is for forming an insulating layer of a printed wiring board.

[10] A sheet-like laminated material comprising the resin composition according to any one of [1] to [9].

[11] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [9].

[12] A semiconductor device comprising the printed wiring board according to [11] above.

According to the present invention, a resin composition capable of obtaining a cured product having a high glass transition temperature, good adhesion to the conductor layer, and low dielectric loss tangent; Sheet-like laminated material containing the said resin composition; And the printed wiring board and semiconductor device containing the hardened|cured material of the said resin composition can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, about this invention, embodiment and an illustration are shown and demonstrated in detail. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily changed and implemented without departing from the scope of the claims of the present invention and their equivalents.

In the following description, the quantity of each component in a resin composition is a value with respect to 100 mass % of resin components in a resin composition, unless otherwise indicated.

In addition, in the following description, "resin component" means, unless otherwise specified, among nonvolatile components included in the resin composition, (D) inorganic filler (hereinafter also referred to as "(D) component" in this specification) excluding. say ingredients.

[One. Outline of resin composition]

The resin composition of the present invention contains (A) an epoxy resin, (B) an active ester compound having a carbon-carbon unsaturated bond, and (C) a resin having an unsaturated hydrocarbon group. The hardened|cured material formed by hardening|curing the resin composition of this invention contains the molecular structure site|part formed by reaction of the unsaturated bond site|part of (B) component, and the unsaturated hydrocarbon group of (C) component. This molecular structure site|part has small polarity by the action|action of the unsaturated bond site|part of (B) component and the unsaturated hydrocarbon group of (C) component. Therefore, the polarity of the cured product becomes small, and the value of the dielectric loss tangent can be reduced.

In addition, the cured product formed by curing the resin composition of the present invention contains not only the molecular structure portion formed by the reaction of the unsaturated bond portion of the component (B) and the unsaturated hydrocarbon group of the component (C), but also the component (B) contains an active ester moiety and a molecular structure moiety formed by the reaction of component (A). Accordingly, the crosslinking density becomes dense (ie, the structure becomes denser), and the glass transition temperature of the cured product becomes high. Moreover, since the mechanical strength of hardened|cured material improves and peeling accompanying destruction of hardened|cured material becomes difficult to generate|occur|produce when a crosslinking density becomes dense, the adhesiveness of hardened|cured material and a conductor layer becomes excellent.

As described above, in the resin composition of the present invention, since component (B) has a reaction site capable of reacting with component (A) and component (C) in a compound, component (A) and component (C) are used alone It is possible to form a cured product that simultaneously exhibits the effect that can be expressed when used as a

In addition, compared with the case where the ester compound which can react with (A) component, and the compound which has an unsaturated bond which can react with (C) component are used separately, when (B) component is used, (A ) component, (B) component, and the miscibility of (C) component can be improved. Therefore, since the uniformity of the composition in hardened|cured material can be improved, the said effect can be acquired at a higher level.

[2. (A) Epoxy resin]

The resin composition of this invention contains (A) component. When the cured product has a molecular structure portion formed by reaction of the active ester portion of the component (A) and the component (B), the structure is dense, the glass transition temperature of the cured product is high, and the adhesion is excellent.

(A) As a component, a bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol is, for example, Type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, Glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, butadiene structure epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclo A hexanedimethanol-type epoxy resin, a naphthylene ether-type epoxy resin, a trimethylol-type epoxy resin, a tetraphenylethane-type epoxy resin, and a halogenated epoxy resin are mentioned.

Among these, as (A) component, from a viewpoint of improving adhesiveness, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin , a glycidyl ester type epoxy resin and an anthracene type epoxy resin are preferable, and the epoxy resin containing an aromatic skeleton from a viewpoint of reducing an average coefficient of linear thermal expansion is preferable. Here, the aromatic skeleton is a concept including polycyclic aromatics and aromatic heterocycles. The epoxy resin containing an aromatic skeleton is selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, and naphthol type epoxy resin At least one epoxy resin is preferably used, and at least one epoxy resin selected from the group consisting of a bisphenol A type epoxy resin, a biphenyl type epoxy resin, and a naphthalene type epoxy resin is more preferable.

Moreover, it is preferable that the resin composition contains the epoxy resin which has two or more epoxy groups in 1 molecule as (A) component. (A) The ratio of the epoxy resin having two or more epoxy groups in one molecule with respect to 100% by mass of the nonvolatile component of the component is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70 mass % or more. Among them, it is preferable that the resin composition contains, as component (A), three or more epoxy groups in one molecule and a solid epoxy resin (sometimes referred to as "solid epoxy resin" below) at a temperature of 20°C.

(A) A component may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios. Therefore, the resin composition may contain only a solid-state epoxy resin as (A) component, and may contain it combining a solid-state epoxy resin and other epoxy resins. Among them, the resin composition contains, as component (A), a solid epoxy resin, two or more epoxy groups in one molecule, and a liquid epoxy resin at a temperature of 20° C. (hereinafter referred to as “liquid epoxy resin”). It is preferable to include them in combination. (A) As a component, the flexibility of a resin composition can be improved or the breaking strength of the hardened|cured material of a resin composition can be improved by using combining a liquid epoxy resin and a solid epoxy resin.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin , an alicyclic epoxy resin having an ester skeleton, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a glycidylamine type epoxy resin, a bisphenol A type epoxy resin , a bisphenol F-type epoxy resin, a bisphenol AF-type epoxy resin, and a naphthalene-type epoxy resin are more preferable.

As a liquid epoxy resin, For example, "HP4032", "HP4032D", "HP4032SS" by DIC Corporation (naphthalene type epoxy resin); "YL980", "828US", "jER828EL", "825", "Epicoat 828EL" by Mitsubishi Chemical Corporation (bisphenol A epoxy resin); "jER806H", "jER807", "YL983U", "1750" by Mitsubishi Chemical Corporation (bisphenol F-type epoxy resin); "jER152" by Mitsubishi Chemical Corporation (phenol novolak type epoxy resin); "630", "630LSD" by Mitsubishi Chemical Corporation (glycidylamine type epoxy resin); "ZX1059" (mixture of a bisphenol A epoxy resin and a bisphenol F type epoxy resin) by the Shin-Nippon Sumikin Chemical Company; "EX-721" by the Nagase Chemtex company (glycidyl ester type epoxy resin); "Serokiside 2021P" by Daicel (alicyclic epoxy resin which has ester skeleton); "PB-3600" by Daicel (epoxy resin which has a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1, 4- glycidyl cyclohexane type epoxy resin) by a Nippon-Steel Chemicals company are mentioned. These may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

Examples of the solid-state epoxy resin include a naphthalene-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a cresol novolak-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, and a naphtha. A thylene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol A type epoxy resin, a tetraphenylethane type epoxy resin, and a bixylenol type epoxy resin are preferable, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a naphthol type epoxy resin, A bixylenol-type epoxy resin and a biphenyl-type epoxy resin are more preferable.

As a solid-state epoxy resin, For example, "HP4032H" by DIC (naphthalene type epoxy resin); "HP-4700", "HP-4710" by DIC company (naphthalene type tetrafunctional epoxy resin); "N-690", "N-695" (cresol novolak-type epoxy resin) by DIC company; "HP-7200", "HP-7200HH", and "HP-7200H" by DIC (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" by DIC company (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol-type epoxy resin) by Kayaku, Japan; "NC7000L" (naphthol novolak type epoxy resin) by Kayaku, Japan; "NC3000H", "NC3000", "NC3000L", and "NC3100" (biphenyl type epoxy resin) by the Nippon Kayaku company; "ESN475V" (naphthol naphthalene type epoxy resin) by the Shin-Nittetsu Sumikin Chemical Company; "ESN485" (naphthol novolak-type epoxy resin) by the Shin-Nittetsu Sumikin Chemical Company; "YL6121" by Mitsubishi Chemical Corporation (biphenyl type epoxy resin); "YX4000H", "YX4000", "YX4000HK" by Mitsubishi Chemical Corporation (bixylenol type epoxy resin); "YX8800" by Mitsubishi Chemical Corporation (anthracene type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" by Mitsubishi Chemical Corporation (bisphenol AF type|mold epoxy resin); "YL7800" by Mitsubishi Chemical Corporation (fluorene type epoxy resin); "jER1010" by Mitsubishi Chemical Corporation (solid bisphenol A epoxy resin); "jER1031S" by Mitsubishi Chemical Corporation (tetraphenylethane type epoxy resin) is mentioned. These may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

As component (A), when a liquid epoxy resin and a solid epoxy resin are used in combination, their mass ratio (liquid epoxy resin:solid epoxy resin) is preferably 1:0.1 to 1:15, more preferably 1 :0.5 to 1:10, particularly preferably 1:1 to 1:8.

When the mass ratio of the liquid epoxy resin is in this range, sufficient flexibility can be obtained when used in the form of an adhesive film, handleability is improved, and sufficient fluidity at the time of lamination can be obtained.

When the mass ratio of the solid epoxy resin is in this range, the viscosity of the epoxy resin is reduced, and when used in the form of an adhesive film, the degassing property at the time of vacuum lamination can be improved. Moreover, the peelability of a protective film and a support body can be made favorable at the time of vacuum lamination, and the heat resistance after hardening can be improved.

The epoxy equivalent of (A) component becomes like this. Preferably it is 50-5000, More preferably, it is 50-3000, More preferably, it is 80-2000, Especially preferably, it is 110-1000. When the epoxy equivalent of component (A) exists in the said range, the crosslinking density of the hardened|cured material of a resin composition becomes sufficient, and the insulating layer with small surface roughness can be obtained.

Epoxy equivalent is the mass of resin containing an epoxy group of 1 equivalent, and can be measured according to JISK7236.

(A) The weight average molecular weight of component is a viewpoint from which the desired effect of this invention can be acquired remarkably, Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500.

(A) The weight average molecular weight of component can be measured as a polystyrene conversion value by the gel permeation chromatography (GPC) method. For example, the weight average molecular weight of the resin uses LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, Shodex K-800P/K-804L/K-804L manufactured by Showa Denko as a column, and a mobile phase. Using chloroform or the like, it can be measured at a column temperature of 40°C and calculated using a standard polystyrene calibration curve.

The amount of component (A) in the resin composition is preferably 5% by mass or more, more preferably 5% by mass or more, based on 100% by mass of the resin component in the resin composition from the viewpoint of obtaining an insulating layer exhibiting high dielectric transition temperature and high adhesion. is 10 mass % or more, More preferably, it is 20 mass % or more. (A) The upper limit of the amount of component is arbitrary as long as the effect of the present invention is shown, preferably 70 mass % or less, more preferably 65 mass % or less, still more preferably 60 mass % or less, particularly preferably It is 50 mass % or less.

[3. (B) an active ester compound having a carbon-carbon unsaturated bond]

The resin composition of this invention contains (B) component. (B) A component reacts with both components of (A) component and (C)component, and forms hardened|cured material.

When the cured product has an unsaturated bond portion of component (B) and a molecular structure portion formed by reaction of component (C), the polarity of the cured product becomes small and the value of dielectric loss tangent can be reduced.

In addition, when the cured product has an active ester moiety of component (B) and a molecular structure moiety formed by reaction of component (A), the structure becomes dense, the glass transition temperature of the cured product is high, and adhesion is excellent.

Conventionally, when two resins having different reactivity were used together, the miscibility of each resin was poor, and it was difficult to form a cured product uniformly. Therefore, it was difficult to simultaneously express the above effects at a high level.

On the other hand, in the resin composition of this invention, (B) component has two reactive resin and each reactive site|part in the same compound. Therefore, (B) component can form a hardened|cured material by connecting each resin, and can form a uniform hardened|cured material. Accordingly, the above properties can be simultaneously expressed at a high level, and the desired effect of the present invention can be exhibited.

Moreover, when (B) component is used, the miscibility of (A) component, (B) component, and (C)component can be improved. Therefore, since the uniformity of the composition in hardened|cured material can be improved, the said effect can be acquired at a higher level.

A carbon-carbon unsaturated bond is an aliphatic unsaturated bond normally, For example, a carbon-carbon double bond and a carbon-carbon triple bond are mentioned. Among them, a carbon-carbon double bond is preferable. As a preferable component (B) which has a carbon-carbon double bond, the active ester compound which has a vinyl group, a methacryl group, an acryl group, an allyl group, a styryl group, or a propenyl group is mentioned, for example. Especially, a styryl group is especially preferable from a viewpoint of being excellent in heat resistance.

(B) It is preferable that the compound represented by following formula (1) is included as a component.

the above formula (1)

In the above formula (1),

m represents the integer of 1-6, n represents the integer of 1-20.

In general formula (1), m becomes like this. Preferably it is an integer of 1-6, More preferably, it is an integer of 1-3. Moreover, n becomes like this. Preferably it is an integer of 1-10, More preferably, it is an integer of 1-5, Especially preferably, it is an integer of 1-3. By being within such a numerical range, component (B) reacts with component (C) in an appropriate ratio, and the fall of a dielectric loss tangent can be implement|achieved.

The component (B) may be a mixture of compounds having different values of m and n of the compound represented by the general formula (1). In the case of a mixture, the component (B) is a compound in which n is 0 in the formula (1) (a compound represented by the following formula (0-1)), as long as it includes the compound represented by the formula (1), but n is It is an integer of 1 to 20, and m may include a compound of 0 (a compound represented by the following formula (0-2)).

Further, the ratio of the total of the compound represented by the formula (0-1) and the compound represented by the formula (0-2) with respect to 100% by mass of the component (B) is preferably 10% by mass or less, more preferably is 5 mass% or less, more preferably 3 mass% or less, particularly preferably 1 mass% or less, and 0 mass%. By being in such a range, component (B) reacts with component (C) in an appropriate ratio, and the fall of a dielectric loss tangent can be implement|achieved.

Formula (0-1)

Formula (0-2)

In the above formula (0-2),

n represents the integer of 1-20.

A commercial item may be used for the compound represented by General formula (1), and a synthetic product may be used for it. As a commercial item, a brand name "PC1300-02-65MA" (made by Air Water Corporation) is mentioned, for example.

The amount of component (B) in the resin composition is preferably 5% by mass or more with respect to 100% by mass of the resin component in the resin composition from the viewpoint of obtaining an insulating layer exhibiting low dielectric loss tangent, high dielectric transition temperature, and high adhesion. , More preferably, it is 10 mass % or more, More preferably, it is 20 mass % or more. (B) The upper limit of the quantity of component is arbitrary as long as the effect of this invention is shown, Preferably it is 70 mass % or less, More preferably, it is 65 mass % or less, More preferably, it is 60 mass % or less.

[4. (C) Resin having an unsaturated hydrocarbon group]

The resin composition of this invention contains (C)component. When the cured product has a molecular structure portion formed by the reaction of the unsaturated bond portion of the component (C) and the component (B), the polarity of the cured product becomes small and the value of the dielectric loss tangent can be reduced.

(C) As a component, if it has an unsaturated hydrocarbon group, it will not specifically limit. By using an unsaturated hydrocarbon group, the dielectric loss tangent of hardened|cured material can be reduced. As an unsaturated hydrocarbon group, it is preferable that they are aliphatic unsaturated hydrocarbon groups, such as an acryl group, a methacryl group, a styryl group, and an olefin group. Especially, a styryl group is more preferable from a viewpoint of being excellent in heat resistance.

Here, the "olefin group" refers to an aliphatic hydrocarbon group having a carbon-carbon double bond in the molecule. For example, an allyl group, a vinyl group, and a propenyl group are mentioned.

(C) As a component, the compound represented by following formula (2) is preferable.

Formula (2)

In the formula (2), R ¹ to R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. A represents a structure represented by the following general formula (3) or the following general formula (4).

Formula (3)

In the formula (3), B represents a structure represented by the following formula (B-1), (B-2) or (B-3).

Formula (4)

In the formula (4), D represents a structure represented by the following formula (5).

Formula (5)

In the formula (5), R ⁷ to R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and preferably a hydrogen atom or a methyl group. In particular, R ⁷ , R ⁸ , R ¹³ , and R ¹⁴ are more preferably a methyl group. a and b are integers from 0 to 100 in which at least one of them is not 0. B represents a structure represented by the following formula (B-1), (B-2) or (B-3).

Formula (B-1)

Formula (B-2)

Formula (B-3)

In the formula (B-1), R ¹⁵ to R ¹⁸ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and preferably a hydrogen atom or a methyl group.

In the formula (B-2), R ¹⁹ to R ²⁶ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and preferably a hydrogen atom or a methyl group.

In the formula (B-3), R ²⁷ to R ³⁴ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and preferably a hydrogen atom or a methyl group. E represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

(C) As a component, it is more preferable that it is a compound represented by following formula (6), following formula (7), or following formula (8).

Formula (6)

In the formula (6), R ¹ to R ⁶ are the same as R ¹ to R ⁶ in the formula (2), B has the same definition as B in the formula (3), a and b are a in the formula (5); agree with b.

Formula (7)

Formula (8)

As the commercially available component (C), for example, styrene-modified polyphenylene ether resin (“OPE-2St 1200 (number average molecular weight 1200)” manufactured by Mitsubishi Gas Chemical Co., Ltd., equivalent to formula (6)), bixylenol diallyl Ether resin ("YL7776 (number average molecular weight 331)" by Mitsubishi Chemical Corporation, equivalent to Chemical Formula (7)), dioxane acrylic monomer glycol diacrylate ("A-DOG (number average molecular weight 326)" by Shin-Nakamura Chemical Industry Co., Ltd.) ', the formula (8) equivalent) is mentioned.

(C) The number average molecular weight of the component is preferably in the range of 100 to 10000, more preferably 200 to 3000, from the viewpoint of preventing volatilization during drying of the resin varnish and preventing the melt viscosity of the resin composition from rising too much. is the range of In addition, the number average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). As the number average molecular weight by GPC method, for example, Shimadzu Corporation LC-9A/RID-6A as a measuring device and Shodex K-800P/K-804L/K-804L by Showa Denko as a column were used. , can be measured at a column temperature of 40°C using chloroform or the like as a mobile phase, and calculated using a standard polystyrene calibration curve.

The amount of component (C) in the resin composition is preferably 3% by mass or more, more preferably 5% by mass or more, based on 100% by mass of the resin component in the resin composition from the viewpoint of reducing the dielectric loss tangent value of the cured product. , More preferably, it is 10 mass % or more. (C) The upper limit of the quantity of component is arbitrary as long as the effect of this invention appears, Preferably it is 50 mass % or less, More preferably, it is 40 mass % or less, More preferably, it is 30 mass % or less.

[5. hardener]

The resin composition may contain a hardening|curing agent different from (B) component, unless the effect of this invention is impaired. The curing agent is not particularly limited, and examples thereof include a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, and a carbodiimide-based curing agent. Especially, from a viewpoint of obtaining the insulating layer excellent in adhesiveness with a conductor layer, an active ester type hardening|curing agent is preferable. In addition, a hardening|curing agent may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

As the phenolic curing agent or naphthol curing agent, from the viewpoint of heat resistance and water resistance, a phenolic curing agent having a novolak structure or a naphthol curing agent having a novolak structure is preferable. Further, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. Among them, a triazine skeleton-containing phenol novolak curing agent or a triazine skeleton-containing naphthol novolak curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer.

As a phenol-type hardening|curing agent and a naphthol-type hardening|curing agent, For example, Meiwa Kasei Corporation "MEH-7700", "MEH-7810", "MEH-7851", Nippon Kayaku Corporation "NHN", "CBN", "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375" manufactured by Shin-Nittetsu Sumikin Co., Ltd. ', "SN-395", "TD-2090" manufactured by DIC, "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", etc. are mentioned.

It does not specifically limit as an active ester type hardening|curing agent. For example, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, can be used. . It is preferable that the said active ester type hardening|curing agent is obtained by the condensation reaction of at least any compound of a carboxylic acid compound and a thiocarboxylic acid compound, and at least any compound of a hydroxy compound and a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable.

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac, etc. are mentioned. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol to one molecule of dicyclopentadiene.

Examples of the active ester curing agent include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoyl product of phenol novolac. An active ester compound containing is preferable, and an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

As a commercial item of an active ester type hardening|curing agent, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "EXB-8000L-65TM", "HPC-8000H-65M" by DIC Corporation are, for example, ' (active ester compound containing a dicyclopentadiene type diphenol structure), "EXB-9416L-70BK" manufactured by DIC (active ester compound containing a naphthalene structure), "DC808" manufactured by Mitsubishi Chemical Corporation (phenol An active ester compound containing an acetylated product of novolac), "YLH1026" manufactured by Mitsubishi Chemical Corporation (an active ester compound containing a benzoyl product of phenol novolac), "EXB-9050L-62M" manufactured by DIC Corporation (phosphorus atom) containing active ester compound) and the like.

As a benzoxazine type hardening|curing agent, "HFB2006M" by a Showa Kobunshi company, "P-d" by a Shikoku Kasei Co., Ltd. product, and "F-a" are mentioned, for example.

It does not specifically limit as a cyanate ester type hardening|curing agent. For example, a novolak-type cyanate ester type|system|group hardening|curing agent, such as a phenol novolak-type and an alkylphenol novolak-type; dicyclopentadiene type cyanate ester curing agent; bisphenol type cyanate ester curing agents such as bisphenol A type, bisphenol F type, and bisphenol S type; and prepolymers in which these are partially triazined. Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), and 4,4'-methylenebis (2,6-dimethyl). Phenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cya) natephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanate) bifunctional cyanate resins such as phenyl)thioether and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially triazinated. As a commercial item, "PT30", "PT60" (all are phenol novolak-type polyfunctional cyanate ester resin), "BA230" (a part or all of bisphenol A dicyanate was triazine-ized and the prepolymer which became a trimer by the Lonza Japan company) ) can be mentioned.

As a carbodiimide type hardening|curing agent, "V-03" and "V-07" by the Nisshinbo Chemical company are mentioned, for example.

The curing agent is preferably at least one selected from a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and a carbodiimide-based curing agent, and more preferably at least one of a phenol-based curing agent and an active ester-based curing agent.

When the number of epoxy groups in component (A) is 1, from the viewpoint of obtaining a good insulating layer of mechanical strength, the lower limit of the number of reactive groups of the curing agent is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, particularly preferably 0.4 or more. The upper limit is preferably 2 or less, more preferably 1.5 or less, still more preferably 1 or less.

Here, a "curing agent reactive group" is an active hydroxyl group, an active ester group, etc., and differs with the kind of hardening|curing agent. In addition, "the number of epoxy groups of component (A)" is a value obtained by adding up the value obtained by dividing the solid content mass of each epoxy resin in the resin composition by the epoxy equivalent for all epoxy resins. In addition, "the number of reactive groups of a hardening|curing agent" is the value which divided the solid content mass of each hardening|curing agent existing in the resin composition by the reactor equivalent, and is the value summed up about all hardening|curing agents. (A) By making the ratio of an epoxy resin and a hardening|curing agent into such a range, the heat resistance of the hardened|cured material of a resin composition can be improved more.

Content of the hardening|curing agent in a resin composition is not specifically limited. For example, with respect to 100 mass % of resin components in a resin composition, an upper limit becomes like this. Preferably it is 30 mass % or less, More preferably, it is 25 mass % or less, More preferably, it is 20 mass % or less, Especially preferably, 18 mass % or less. % or less and 15 mass % or less. The lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, particularly preferably 7% by mass or more, and 10% by mass or more. By making content of a hardening|curing agent into such a range, the hardened|cured material further excellent in the coefficient of linear thermal expansion of a resin composition, a dielectric loss tangent, and adhesiveness with a conductor layer can be formed.

[6. (D) inorganic filler]

A resin composition contains (D)component normally. (D) Since the thermal expansion coefficient of the hardened|cured material of a resin composition can be made small by using a component, the reflow curvature of an insulating layer can be suppressed.

(D) The material of the component is not particularly limited, but for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, bee Mite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, Zirconium oxide, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphate tungstate are mentioned. Among these, silica is preferable, amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica are more preferable, and from the viewpoint of reducing the surface roughness of the insulating layer, fused silica and spherical silica are more preferred, and spherical fused silica is particularly preferred. (D) A component may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

Usually, (D)component is contained in a resin composition in the state of particle|grains. The average particle diameter of the particles of component (D) is preferably 5 µm or less, more preferably 3 µm or less, still more preferably from the viewpoint of improving circuit embedding properties and obtaining an insulating layer having a small surface roughness. 2 µm or less, particularly preferably 1 µm or less, 0.8 µm or less, 0.6 µm or less, or 0.4 µm or less. The lower limit of the average particle diameter is preferably 0.01 µm or more, more preferably 0.03 µm or more, and still more preferably from the viewpoint of preventing that the viscosity of the varnish increases and the handleability decreases when the resin varnish is used. Preferably it is 0.05 micrometer or more, Especially preferably, it is 0.07 micrometer or more and 0.1 micrometer or more.

As a commercial item of (D)component which has the above average particle diameters, For example, "SP60-05" by a Shin-Nittetsu Sumikin Materials company, "SP507-05"; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatex Corporation; "UFP-30" by Denka Corporation; "Silly writing NSS-3N", "Silly writing NSS-4N", "Silly writing NSS-5N" by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" by Admatex company are mentioned.

(D) The average particle diameter of particle|grains, such as a component, can be measured by the laser diffraction/scattering method based on the Mie scattering theory. For example, with a laser diffraction scattering particle size distribution measuring device, the particle size distribution of particles can be measured on a volume basis, and the average particle size can be measured as the median diameter from the particle size distribution. As a measurement sample, what disperse|distributed particle|grains in water by ultrasonic wave can be used preferably. As a laser diffraction scattering type particle size distribution analyzer, "LA-500" by Horiba Corporation, etc. can be used.

(D) The component may be surface-treated with arbitrary surface treatment agents. Examples of the surface treatment agent include an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, an alkoxysilane compound, an organosilazane compound, and a titanate-based coupling agent. By surface-treating (D)component with these surface treating agents, the moisture resistance and dispersibility of (D)component can be improved.

As a commercial item of a surface treatment agent, For example, Shin-Etsu Chemical Co., Ltd. "KBM-22" (dimethyldimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-403" (3-glycidoxypropyltrimethoxysilane) ), Shin-Etsu Chemical Co., Ltd. "KBM-803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE-903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical “KBM-573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Kogyo Co., Ltd. “SZ-31” (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd. “KBM” manufactured by Shin-Etsu Chemical Co., Ltd. -103" (phenyltrimethoxysilane) and Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane coupling agent) are mentioned. In addition, a surface treatment agent may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

The grade of the surface treatment by a surface treating agent can be evaluated by the amount of carbon per unit surface area of (D)component. The amount of carbon per unit surface area of the component (D) is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, particularly preferably 0.2 mg from the viewpoint of improving the dispersibility of the component (D). /m2 or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin composition and the melt viscosity in a sheet form, the carbon content is preferably 1 mg/m 2 or less, more preferably 0.8 mg/m 2 or less, particularly preferably is 0.5 mg/m 2 or less.

(D) The amount of carbon per unit surface area of component can be measured, after washing-processing (D)component after surface treatment with a solvent. As a solvent, methyl ethyl ketone (it may abbreviate as "MEK" hereafter) can be used, for example. For example, a sufficient amount of methyl ethyl ketone and the component (D) surface-treated with a surface treatment agent are mixed, followed by ultrasonic cleaning at 25° C. for 5 minutes. Then, after removing a supernatant and drying solid content, the carbon amount per unit surface area of (D)component can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" by Horiba Corporation can be used.

The lower limit of the amount of component (D) in the resin composition is preferably 100 parts by mass or more, more preferably 200 parts by mass or more with respect to 100 parts by mass of the resin component in the resin composition from the viewpoint of obtaining an insulating layer with a low coefficient of thermal expansion. It is mass part or more, More preferably, it is 250 mass parts or more. From a viewpoint of the mechanical strength of an insulating layer, especially elongation, Preferably an upper limit is 500 mass parts or less, More preferably, it is 400 mass parts or less, More preferably, it is 350 mass parts or less.

[7. (E) curing accelerator]

The resin composition of this invention may further contain the (E) hardening accelerator (henceforth "(E) component" in this specification") as needed. By using (E) component, when hardening a resin composition, hardening can be accelerated|stimulated.

(E) As a component, a phosphorus type hardening accelerator, an amine type hardening accelerator, an imidazole type hardening accelerator, a guanidine type hardening accelerator, a metal type hardening accelerator, a peroxide type hardening accelerator, etc. are mentioned, for example. Among them, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, peroxide-based curing accelerators or metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators, peroxide-based curing accelerators or metal-based curing accelerators are preferred. more preferably.

In addition, (E) component may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

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

Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8 -diazabicyclo[5,4,0]-undecene is mentioned. Among them, 4-dimethylaminopyridine and 1,8-diazabicyclo[5,4,0]-undecene are preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl- 2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole , 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimida Zolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-undecylimidazolyl-(1′)]-ethyl-s-triazine, 2,4 -diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl -(1')]-ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-Methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium The adduct body of the imidazole compound of a chloride, 2-methylimidazoline, and 2-phenyl imidazoline, and an imidazole compound, and an epoxy resin is mentioned. Among them, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As an imidazole-type hardening accelerator, you may use a commercial item, for example, "P200-H50" by a Mitsubishi Chemical Company, etc. are mentioned.

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

As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, and a tin, is mentioned, for example. Examples of the organometallic complex include organocobalt complexes such as cobalt(II)acetylacetonate and cobalt(III)acetylacetonate; organic copper complexes such as copper (II) acetylacetonate; organic zinc complexes such as zinc (II) acetylacetonate; organic iron complexes such as iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; Organic manganese complexes, such as manganese (II) acetylacetonate, are mentioned. Examples of the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Examples of the peroxide-based curing accelerator include cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, diisopropyl Benzene hydroperoxide, cumene hydroperoxide, and tert- butyl hydroperoxide are mentioned.

As a peroxide type hardening accelerator, you may use a commercial item, for example, "Percumyl D" by a Nichiyo Corporation is mentioned.

The amount of component (E) in the resin composition is preferably in the range of 0.01% by mass to 3% by mass relative to 100% by mass of the resin component in the resin composition from the viewpoint of significantly obtaining the desired effect of the present invention.

[8. (F) Thermoplastic resin]

The resin composition of the present invention may further contain (F) a thermoplastic resin (hereinafter, also referred to as “component (F)” in this specification). As the component (F), for example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, poly phenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, and indencumarone resin are mentioned. Especially, from a viewpoint of a compatibility improvement, indencumarone resin is preferable. In addition, (F) component may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

(F) The range of 8,000-70,000 is preferable, as for the weight average molecular weight of polystyrene conversion of component, the range of 10,000-60,000 is more preferable, The range of 20,000-60,000 is still more preferable.

(F) The weight average molecular weight of polystyrene conversion of a component is measured by the gel permeation chromatography (GPC) method. For example, the weight average molecular weight in terms of polystyrene of component (F) is LC-9A/RID-6A by Shimadzu Corporation as a measuring device and Shodex K-800P/K-804L/ by Showa Denko as a column K-804L can be measured at a column temperature of 40°C using chloroform or the like as a mobile phase, and calculated using a standard polystyrene calibration curve.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene. and phenoxy resins having at least one skeleton selected from the group consisting of skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. Any one of functional groups, such as a phenolic hydroxyl group and an epoxy group, may be sufficient as the terminal of a phenoxy resin. A phenoxy resin may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

As phenoxy resin, For example, "1256" and "4250" by Mitsubishi Chemical Corporation (both are bisphenol A frame|skeleton containing phenoxy resin); "YX8100" by Mitsubishi Chemical Corporation (bisphenol S skeleton containing phenoxy resin); "YX6954" by Mitsubishi Chemical Corporation (bisphenolacetophenone skeleton-containing phenoxy resin); "FX280" and "FX293" manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd.; "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7891BH30" and "YL7482" by Mitsubishi Chemical Corporation, etc. are mentioned.

As indencumaron resin, For example, "H-100", "WS-100G", "WS-100H", "WS-120V", "WS-100GC" by Nitto Chemical Co., Ltd.; "C10", "C30", and "CA80" by a Novares Rutogaz company are mentioned.

Preferably the minimum of the quantity of (F) component in a resin composition is 0.1 mass % or more with respect to 100 mass % of resin components in a resin composition, More preferably, it is 0.5 mass % or more. Moreover, the upper limit becomes like this. Preferably it is 10 mass % or less, More preferably, it is 5 mass % or less. By being in such a range, the effect of film moldability and mechanical strength improvement can be exhibited, and also a rise in melt viscosity and the roughness of the surface of the insulating layer after a wet roughening process can be reduced.

[9. optional ingredients]

The resin composition of the present invention may contain optional components in addition to the components described above. As such an optional component, for example, a flame retardant; organic fillers; organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds; thickener; antifoam; leveling agent; adhesion imparting agent; Resin additives, such as a coloring agent, are mentioned.

<Flame retardant>

The resin composition of the present invention can further improve the glass transition temperature of the cured product of the resin composition by using a flame retardant.

Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. As a flame retardant, you may use a commercial item, for example, "HCA-HQ" by Sanko Corporation, "HCA-HQ-HS", and "PX-200" by Daihachi Chemical Industry Co., Ltd. are mentioned. In addition, a flame retardant may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

The amount of the flame retardant in the resin composition, from the viewpoint of imparting heat resistance, with respect to 100 mass% of the resin component in the resin composition, preferably in the range of 0.5 mass% to 20 mass%, more preferably in the range of 0.5 mass% to 15 mass% It is preferable, and the range of 0.5 mass % - 10 mass % is more preferable.

<Organic Filling Material>

Since the resin composition of this invention can improve the flexibility of the hardened|cured material of a resin composition by using an organic filler, it can improve the extensibility of an insulating layer.

As the organic filler, any organic filler that can be used when forming the insulating layer of a printed wiring board can be used. For example, a rubber particle, a polyamide particle, and a silicone particle are mentioned. Moreover, as a rubber particle, you may use a commercial item, for example, "EXL-2655" by the Dow Chemical Corporation, and "AC3816N" by the Aika Corporation are mentioned. In addition, an organic filler may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

From the viewpoint of excellent dispersibility in the resin composition, the average particle diameter of the particles of the organic filler is preferably 5 µm or less, more preferably 4 µm or less, still more preferably 3 µm or less. The lower limit of the average particle diameter of the organic filler is preferably 0.05 µm or more, more preferably 0.08 µm or more, and particularly preferably 0.10 µm or more.

The amount of the organic filler in the resin composition is preferably in the range of 0.1% by mass to 20% by mass relative to 100% by mass of the resin component in the resin composition, from the viewpoint of adjusting the mechanical properties of the cured product of the resin composition to an appropriate range, 0.2% by mass % - 10 mass % is more preferable, the range of 0.3 mass % - 5 mass % is still more preferable, The range of 0.5 mass % - 3 mass % is especially preferable.

[10. Preparation and Characteristics of Resin Composition]

The preparation method of the resin composition of this invention is not specifically limited, For example, the method of adding a solvent etc. to a compounding component as needed, and mixing and dispersing using a rotary mixer etc. is mentioned.

The resin composition of the present invention can bring a cured product having a high glass transition temperature. The glass transition temperature of the cured product of the resin composition of the present invention can be measured by the method described in <Measurement of the glass transition temperature> described later. Specifically, by performing thermomechanical analysis by a tensile weighting method, it can be measured at a load of 1 g and a temperature increase rate of 5° C./min. The cured product of the resin composition of the present invention may exhibit a glass transition temperature of preferably 158°C or higher, more preferably 160°C or higher, and still more preferably 162°C or higher. The upper limit of the glass transition temperature is not particularly limited, and is usually 250°C or less.

The resin composition of the present invention can bring a cured product having a low dielectric loss tangent. The dielectric loss tangent of the cured product of the resin composition of the present invention can be measured by the method described in <Measurement of dielectric loss tangent> described later. Specifically, measurement can be performed at a frequency of 5.8 GHz and a measurement temperature of 23°C by the cavity resonator perturbation method. The value of the dielectric loss tangent is preferably 0.0037 or less, more preferably 0.0035 or less, from the viewpoint of preventing heat generation at high frequencies, and reducing signal delay and signal noise. The lower limit of the value of dielectric loss tangent is so preferable that it is low, and can be normally set as 0.0001 or more.

The resin composition of this invention can form hardened|cured material with high adhesiveness with a conductor layer. The adhesiveness of the hardened|cured material of the resin composition of this invention can be evaluated by the method as described in the below-mentioned <Adhesive measurement>. The adhesiveness of the obtained conductor layer and insulating layer becomes like this. Preferably it is 0.60 kgf/cm or more, More preferably, it is 0.70 kgf/cm or more. The upper limit of adhesiveness is not specifically limited, Usually, it can be set as 1.2 kgf/cm or less, etc.

The resin composition of the present invention can form a cured product having a high glass transition temperature, a low dielectric loss tangent, and good adhesion to the conductor layer. Accordingly, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board), and a resin composition for forming an interlayer insulating layer of a printed wiring board (printed wiring board) of the resin composition for an interlayer insulating layer) can be used more suitably. The resin composition of the present invention is also used for applications required by the resin composition, such as adhesive films and sheet-like laminated materials such as prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, and component embedding resins. can be used extensively in

[11. Sheet-like laminated material]

Although the resin composition of this invention can be apply|coated and used in the state of varnish, it is industrially generally suitable to use it in the form of the sheet-like laminated material containing the said resin composition.

As a sheet-like laminated material, the adhesive film and prepreg shown below are preferable.

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

The thickness of the resin composition layer is preferably 100 µm or less, more preferably 80 µm or less, still more preferably 60 µm or less, particularly preferably 50 µm or less, and 40 µm or less from the viewpoint of reducing the thickness of the printed wiring board. . The lower limit of the thickness of the resin composition layer is not particularly limited, and is usually 1 µm or more, preferably 5 µm or more, more preferably 10 µm or more.

As a support body, the film which consists of a plastic material, metal foil, and a release paper are mentioned, for example, The film which consists of a plastic material, and metal foil are preferable.

When using the film which consists of a plastic material as a support body, As a plastic material, For example, Polyester, such as a polyethylene terephthalate (PET) and a polyethylene naphthalate (PEN); acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA); Cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and a polyimide are mentioned. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When using metal foil as a support body, copper foil and aluminum foil are mentioned as metal foil, for example. Especially, copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, or a foil made of an alloy of copper and another metal (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) is used. also good

A support body may give a mat treatment and corona treatment to the surface of the side to join with a resin composition layer. Moreover, as a support body, you may use the support body with a mold release layer which has a mold release layer on the surface of the side joined with a resin composition layer. As a mold release agent used for the mold release layer of a support body with a mold release layer, 1 or more types of mold release agents are mentioned from the group which consists of an alkyd resin, an olefin resin, a urethane resin, and a silicone resin, for example. As a commercial item of a mold release agent, "SK-1", "AL-5", and "AL-7" by Lintec which are alkyd resin mold release agents are mentioned, for example.

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

The adhesive film can be produced by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying this resin varnish to a support using a die coater or the like, and drying it to form a resin composition layer. .

As an organic solvent, For example, ketones, such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

You may perform drying by well-known methods, such as heating and hot-air spraying. Drying conditions are not specifically limited, Content of the organic solvent in a resin composition layer is 10 mass % or less, Preferably it is made to dry so that it may become 5 mass % or less. Although it changes depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of an organic solvent, by drying at 50°C to 150°C for 3 minutes to 10 minutes, the resin composition layer can be formed.

In the adhesive film, a protective film conforming to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface on the opposite side to the support). The thickness of a protective film is not specifically limited, For example, it is 1 micrometer - 40 micrometers. By laminating|stacking a protective film, adhesion of dust, etc. to the surface of a resin composition layer, and a flaw can be prevented. The adhesive film can be wound and stored in a roll shape. When an adhesive film has a protective film, it becomes usable by peeling off a protective film.

In one embodiment, the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.

The sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as the base material for prepregs, such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric, can be used. From a viewpoint of thickness reduction of a printed wiring board, the thickness of a sheet-like fiber base material becomes like this. Preferably it is 50 micrometers or less, More preferably, it is 40 micrometers or less, More preferably, it is 30 micrometers or less, Especially preferably, it is 20 micrometers or less. The lower limit of the thickness of a sheet-like fiber base material is not specifically limited. Usually, it is 10 micrometers or more.

A prepreg can be manufactured by well-known methods, such as a hot melt method and a solvent method.

The thickness of a prepreg can be made into the range similar to the resin composition layer in the above-mentioned adhesive film.

In the present invention using a resin composition comprising a combination of component (A), component (B), and component (C), a cured product having a high glass transition temperature, low dielectric loss tangent, and good adhesion to the conductor layer is obtained. It is possible to realize a sheet-like laminate material which is very useful in the production of a printed wiring board to be formed.

The sheet-like laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board) It can be used more suitably.

[12. printed wiring board]

The printed wiring board of this invention contains the insulating layer obtained by thermosetting the resin composition of this invention or the sheet-like laminated material of this invention.

In one embodiment, the printed wiring board of this invention can be manufactured by the method including the process of following (I) and (II) using the above-mentioned adhesive film.

(I) a step of laminating an adhesive film on the inner layer substrate so that the resin composition layer of the adhesive film is bonded to the inner layer substrate

(II) Step of thermosetting the resin composition layer to form an insulating layer

The "inner-layer substrate" used in the step (I) is mainly a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or one side of the substrate or It refers to a circuit board in which a patterned conductor layer (circuit) is formed on both sides. In addition, when manufacturing a printed wiring board, an inner-layer circuit board as an intermediate product in which at least one of an insulating layer and a conductor layer is to be formed is also included in the "inner-layer board" in the present invention. When the printed wiring board is a circuit board with built-in components, an inner-layer board with built-in components may be used.

Lamination of the inner layer substrate and the adhesive film can be performed, for example, by heat-compressing the adhesive film to the inner layer substrate from the support side. As a member (hereinafter also referred to as "thermal compression member") which heat-compresses an adhesive film to an inner-layer board|substrate, a heated metal plate (SUS mirror plate etc.), a metal roll (SUS roll), etc. are mentioned, for example. In addition, it is preferable to press through an elastic material, such as a heat-resistant rubber, so that an adhesive film may fully follow the surface unevenness|corrugation of an inner-layer board|substrate, rather than directly pressing a heat-compression-compression-bonding member to an adhesive film.

You may perform lamination|stacking of an inner-layer board|substrate and an adhesive film by the vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C. The thermocompression pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination|stacking becomes like this. Preferably it is performed under reduced pressure conditions of pressure 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. As a commercially available vacuum laminator, the vacuum pressurization laminator by the Meiki Seisakusho company, the vacuum applicator by the Nikko Materials company, etc. are mentioned, for example.

The smoothing treatment of the laminated adhesive film may be performed under normal pressure after lamination (under atmospheric pressure), for example, by pressing the thermocompression-bonding member from the support side. The press conditions of the smoothing process can be made into the conditions similar to the thermocompression-bonding conditions of the said lamination|stacking. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination|stacking and a smoothing process continuously using the above-mentioned commercially available vacuum laminator.

The support may be removed between the steps (I) and (II), or may be removed after the step (II).

Step (II) WHEREIN: The resin composition layer is thermosetted and the insulating layer is formed.

The thermosetting conditions of a resin composition layer are not specifically limited, When forming the insulating layer of a printed wiring board, you may use the conditions normally employ|adopted.

For example, the thermosetting conditions of a resin composition layer also differ with the kind etc. of a resin composition. For example, the curing temperature is usually in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably in the range of 170°C to 200°C). The curing time is usually in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before thermosetting a resin composition layer, you may preheat a resin composition layer at temperature lower than hardening temperature. For example, prior to thermosetting the resin composition layer, usually at a temperature of 50°C or more and less than 120°C (preferably 60°C or more and 110°C or less, more preferably 70°C or more and 100°C or less), the resin composition layer may be preheated for usually 5 minutes or longer (preferably 5 to 150 minutes, more preferably 15 to 120 minutes).

When manufacturing a printed wiring board, you may perform further the process of (III) drilling in an insulating layer, (IV) the process of roughening an insulating layer, and (V) the process of forming a conductor layer in the insulating layer surface. You may implement these processes (III)-(V) according to various methods well-known to those skilled in the art used for manufacture of a printed wiring board. In addition, when the support is removed after the step (II), the removal of the support is performed between the steps (II) and (III), between the steps (III) and (IV), or between the steps (IV) and the step ( It may be carried out between V).

In another embodiment, the printed wiring board of the present invention can be manufactured using the prepreg described above. The manufacturing method is basically the same as in the case of using an adhesive film.

Step (III) is a step of drilling in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, or plasma depending on the composition of the resin composition used for forming the insulating layer, for example. You may determine the dimension and shape of a hole suitably according to the design of a printed wiring board.

Process (IV) is a process of roughening an insulating layer. The procedure and conditions of a roughening process are not specifically limited, When forming the insulating layer of a printed wiring board, the well-known procedure and conditions normally used are employable. For example, the insulating layer can be roughened by performing the swelling process by a swelling liquid, the roughening process by an oxidizing agent, and the neutralization process by a neutralizing liquid in this order.

It does not specifically limit as a swelling liquid. For example, an alkali solution and surfactant solution are mentioned. It is preferably an alkali solution, and as the alkali solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. As a commercially available swelling liquid, "Swelling Deep Security P" and "Swelling Deep Security SBU" by Atotech Japan are mentioned, for example. The swelling treatment by swelling liquid is not specifically limited. For example, it can be carried out by immersing the insulating layer in a swelling solution of 30 ° C. to 90 ° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the cured body in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes.

It does not specifically limit as an oxidizing agent. For example, the alkaline permanganic acid solution which melt|dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 80°C for 10 minutes to 30 minutes. Moreover, as for the density|concentration of the permanganate in an alkaline permanganic acid solution, 5 mass % - 10 mass % are preferable. As a commercially available oxidizing agent, alkaline permanganic acid solutions, such as "Concentrate Compact CP" and "Dosing Solution Securigans P" by Atotech Japan, are mentioned, for example. Moreover, as a neutralization liquid, acidic aqueous solution is preferable, and as a commercial item, "Reduction Solution Seculigant P" by Atotech Japan Co., Ltd. is mentioned, for example.

The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in a neutralizing solution at 30°C to 80°C for 5 minutes to 30 minutes. The method of immersing the object to which the roughening process by an oxidizing agent was made|formed in the neutralization liquid of 40 degreeC - 70 degreeC from points, such as workability|operativity, for 5 minutes - 20 minutes is preferable.

Process (V) is a process of forming a conductor layer.

The conductor material used for a conductor layer is not specifically limited. In a suitable embodiment, the conductor layer comprises at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. do. The conductor layer may be a single metal layer or an alloy layer. As an alloy layer, the layer formed from the alloy (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy) of 2 or more types of metals selected from said group is mentioned, for example. Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, a copper-nickel alloy , a copper/titanium alloy alloy layer is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel/chromium alloy is more preferable, and a single metal layer of copper This is more preferable.

The conductor layer may have a single-layer structure, or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of a nickel-chromium alloy.

Although the thickness of a conductor layer depends on the design of a desired printed wiring board, it is 3 micrometers - 35 micrometers generally, Preferably they are 5 micrometers - 30 micrometers.

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full additive method.

In another embodiment, the conductor layer may be formed using metal foil. When forming a conductor layer using metal foil, it is suitable to implement a process (V) between a process (I) and a process (II). For example, after a process (I), a support body is removed and metal foil is laminated|stacked on the surface of the exposed resin composition layer. You may perform lamination|stacking of a resin composition layer and metal foil by the vacuum lamination method. The lamination conditions may be the same as those described for the step (I). Next, step (II) is performed to form an insulating layer. Then, the conductor layer which has a desired wiring pattern can be formed by conventionally well-known techniques, such as a subtractive method and a modified semi-additive method, using the metal foil on an insulating layer.

Metal foil can be manufactured by well-known methods, such as an electrolytic method and a rolling method, for example. As a commercial item of metal foil, HLP foil, JXUT-III foil, 3EC-III foil by a Mitsui Kinzoku Kozan company, TP-III foil etc. are mentioned, for example by JX Nikko Nisseki Kinzoku.

When a printed wiring board is manufactured using the resin composition of the present invention comprising (A) component, (B) component, and (C) component in combination, it is possible to determine whether the conductor layer is formed by plating or using metal foil. Without distinction, the adhesion between the conductor layer and the insulating layer can be remarkably improved.

[13. semiconductor device]

The semiconductor device of this invention contains the printed wiring board of this invention.

Examples of the semiconductor device include various semiconductor devices provided for electric appliances (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trams, ships and aircraft, etc.) can

The semiconductor device of this invention can be manufactured by mounting a component (semiconductor chip) in the conduction|electrical_connection location of a printed wiring board. A "conduction location" is "a location through which an electric signal is transmitted in a printed wiring board", and the location may be a surface, a buried location, or any. In addition, a semiconductor chip will not be specifically limited if it is an electric circuit element which uses a semiconductor as a material.

The semiconductor chip mounting method at the time of manufacturing the semiconductor device of this invention is not specifically limited as long as the semiconductor chip functions effectively. For example, a wire bonding mounting method, a flip chip mounting method, a mounting method using a bump-free build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF) are mentioned. there is. Here, "a mounting method using a bump-free build-up layer (BBUL)" refers to "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board, and the semiconductor chip and wiring on the printed wiring board are connected".

[Example]

Hereinafter, an Example is shown and this invention is demonstrated concretely. However, this invention is not limited to the Example shown below. In the following description, "parts" and "%" indicating quantities are based on mass unless otherwise specified.

<Example 1>

While stirring 25 parts of bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 185), 10 parts of bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 180) with 25 parts of solvent naphtha. It melted by heating, and then cooled to room temperature. 315 parts of inorganic fillers ("SO-C2" manufactured by Admatex Co., Ltd., average particle diameter of 0.5 µm, carbon amount per unit area of 0.38 mg/m 2 ) were mixed, kneaded with three rolls and dispersed. There, 69.2 parts of an active ester curing agent having a vinyl group (“PC1300-02-65MA” manufactured by Air Water Corporation, a solution of methyl amyl ketone having an active group equivalent of about 199 and a nonvolatile content of 65%), a resin having a vinyl group (Mitsubishi Gas Chemical Company) Manufactured "OPE-2St 1200", toluene solution of 60% nonvolatile matter) 25 parts, Indencumarone resin ("H-100" manufactured by Nitto Chemicals) 15 parts, 4-dimethylaminopyridine (DMAP) 5 as a curing accelerator % MEK solution 2 parts and dicumyl peroxide ("Percumyl D" manufactured by Nichiyo Co., Ltd.) 0.13 parts were mixed and uniformly dispersed with a rotary mixer to prepare a resin varnish 1.

Resin varnish 1 is uniformly applied with a die coater so that the thickness of the resin composition layer after drying becomes 40 µm on the release surface of a polyethylene terephthalate film with an alkyd release treatment (“AL-5” manufactured by Lintec, 38 µm in thickness) and dried at 80° C. to 110° C. (average 95° C.) for 5 minutes to prepare an adhesive film 1.

<Example 2>

In Example 1, 30.8 parts out of 69.2 parts of an active ester curing agent having a vinyl group (“PC1300-02-65MA” manufactured by Air Water Corporation, a solution of methyl amyl ketone having an active group equivalent of about 199 and 65% non-volatile content) of an active ester curing agent ( "HPC-8000-65T" manufactured by DIC, toluene solution of 65% of nonvolatile matter of about 223 active group equivalent) was changed to 30.8 parts. A resin varnish 2 and an adhesive film 2 were produced in the same manner as in Example 1 except for the above.

<Example 3>

In Example 1, 5 parts out of 25 parts of a bixylenol-type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) a resin having a vinyl group ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, 60% nonvolatile matter) of toluene solution) was changed to 8.3 parts. Except for the above, in the same manner as in Example 1, a resin varnish 3 and an adhesive film 3 were produced.

<Example 4>

In Example 1, 25 parts of a resin having a vinyl group (“OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Company, a toluene solution containing 60% of a nonvolatile matter) dioxane acrylic monomer (“A-DOG” manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) It was changed to 15 parts. Except for the above, in the same manner as in Example 1, a resin varnish 4 and an adhesive film 4 were produced.

<Comparative Example 1>

In Example 1, an active ester curing agent having a vinyl group (“PC1300-02-65MA” manufactured by Air Water Corporation, a methyl amyl ketone solution having an active group equivalent weight of about 199 and 65% nonvolatile content) was mixed with an active ester curing agent (manufactured by DIC ““ HPC-8000-65T", a toluene solution containing 65% of nonvolatile matter with an active group equivalent of about 223). Except for the above, in the same manner as in Example 1, a resin varnish 5 and an adhesive film 5 were produced.

<Comparative Example 2>

In Example 1, an active ester curing agent having a vinyl group (“PC1300-02-65MA” manufactured by Air Water Corporation, a methyl amyl ketone solution having an active group equivalent weight of about 199 and 65% nonvolatile content) was mixed with an active ester curing agent (manufactured by DIC ““ EXB-8000L-65TM", a toluene solution containing 65% of nonvolatile matter with an active group equivalent of about 220). Except for the above, in the same manner as in Example 1, a resin varnish 6 and an adhesive film 6 were produced.

<Comparative Example 3>

In Example 1. 69.2 parts of an active ester curing agent having a vinyl group (“PC1300-02-65MA” manufactured by Air Water Corporation, a solution of methyl amyl ketone having an active group equivalent weight of about 199 and 65% nonvolatile matter) 69.2 parts of an active ester curing agent (“EXB-9416L-” manufactured by DIC) 70BK", a toluene solution of 70% of nonvolatile matter with an active group equivalent of about 330) was changed to 64.3 parts. Except for the above, in the same manner as in Example 1, a resin varnish 7 and an adhesive film 7 were produced.

[Assessment Methods]

The adhesive films obtained in Examples and Comparative Examples described above were evaluated by the following method.

<Production of samples for evaluation of curing properties>

The adhesive films obtained in Examples and Comparative Examples were heat-cured at 190° C. for 90 minutes, and the PET film as a support was peeled off to prepare a sheet-like sample for evaluation of cured properties.

<Measurement of dielectric loss tangent>

A test piece having a width of 2 mm and a length of 80 mm was cut out from the sample for evaluation of cured properties. With respect to the cut test piece, the dielectric loss tangent was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by a cavity resonance perturbation method using a measuring device “HP8362B” manufactured by Agilent Technologies.

Moreover, the case of 0.0035 or less was evaluated as "excellent", the case of 0.0037 or less was evaluated as "good", and the case of 0.0037 or more was evaluated as "poor".

<Measurement of glass transition temperature>

A test piece having a width of about 5 mm and a length of about 15 mm was cut out of a sample for evaluation of cured properties, and thermomechanical analysis was performed by a tensile weighting method using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Corporation). In detail, after the test piece was mounted on the said thermomechanical analysis apparatus, it measured twice successively under the measurement conditions of 1 g of load and 5 degreeC/min of temperature increase rate. And in the second measurement, the glass transition temperature (Tg; ℃) was calculated.

Moreover, the case where it was 138 degreeC or more was evaluated as "good|favorableness", and the case where it was 138 degrees C or less was evaluated as "poor".

<Measurement of adhesion>

(1) Base work of copper foil

The glossy surface of Mitsui Kinzoku Kozan Co., Ltd. "3EC-III" (electric field copper foil, 35 µm) was immersed in Mech's Mech Etch Bond "CZ-8101", and roughening treatment (Ra value = 1 µm) was performed on the copper surface. Then, a rust prevention treatment (CL8300) was performed. This copper foil is called CZ copper foil. Moreover, it heat-processed in 130 degreeC oven for 30 minutes.

(2) Lamination of copper foil and formation of an insulating layer

The adhesive films produced in Examples and Comparative Examples were laminated on both sides of the inner circuit board so that the resin composition layer was bonded to the inner circuit board using a batch vacuum pressurized laminator (“MVLP-500” manufactured by Makey Co., Ltd.). . The lamination treatment was carried out by reducing the pressure for 30 seconds to set the atmospheric pressure to 13 hPa or less, and then compressing it at 100° C. and a pressure of 0.74 MPa for 30 seconds. The PET film as a support was peeled from the laminated adhesive film. On the resin composition layer, the treated surface of CZ copper foil of "3EC-III" was laminated under the same conditions as above. And the sample was produced by hardening|curing the resin composition layer on 190 degreeC, hardening conditions for 90 minutes, and forming an insulating layer.

(3) Measurement of copper foil peel strength (adhesiveness)

The produced sample was cut into 150 x 30 mm pieces. In the copper foil part of the small piece, the cutout of the part of width 10mm and length 100mm was put using the cutter. One end of the portion of the copper foil was peeled off, held with tongs (manufactured by TSE Co., Ltd., Autocom-type testing machine, "AC-50C-SL"), and peeled in the vertical direction. This peeling was performed using an Instron universal testing machine at room temperature at a speed of 50 mm/min. The load at the time of peeling 35 mm was measured based on JISC6481, and it was set as "adhesion property".

Moreover, the case of 0.3 kgf/cm or more was evaluated as "good|favorableness", and the case of 0.3 kgf/cm or less was evaluated as "poor".

<Result>

The results of the above-described Examples and Comparative Examples are shown in the table below. The meanings of the abbreviations in the table below are as follows.

YX4000HK: Bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation)

828US: Bisphenol A type epoxy resin (“828US” manufactured by Mitsubishi Chemical Corporation)

PC1300-02: Active ester curing agent having a vinyl group (“PC1300-02-65MA” manufactured by Air Water Corporation)

HPC-8000: Active ester curing agent (“HPC-8000-65T” manufactured by DIC)

EXB-8000L: Active ester curing agent (“EXB-8000L-65TM” manufactured by DIC)

EXB-9416: Active ester curing agent (“EXB-9416L-70BK” manufactured by DIC)

OPE-2St 1200: a resin having a vinyl group (“OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Company)

A-DOG: dioxane acrylic monomer (“A-DOG” manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.)

H-100: Indencumaron resin (“H-100” manufactured by Nitto Chemical)

SOC2: spherical silica (“SO-C2” manufactured by Admatex)

Percumyl D: dicumyl peroxide ("Percumyl D" manufactured by Nichiyu Corporation)

DMAP: 4-dimethylaminopyridine

In addition, in a table|surface, a compounding quantity is a solid content conversion value.

[examine]

Comparative Examples 1 to 3 using the active ester curing agent are inferior in glass transition temperature and adhesiveness. In particular, in the active ester-based curing agent containing a naphthalene structure used in Comparative Example 3, the dielectric loss tangent was also slightly inferior.

On the other hand, Examples 1 to 4 using the component (B) made the glass transition temperature high while keeping the dielectric loss tangent low, and exhibited good adhesion. Therefore, from the results of Examples 1 to 4 and Comparative Examples 1 to 3, by combining component (A), component (B), and component (C), the dielectric loss tangent is low, the glass transition temperature is high, and the conductive layer is It was confirmed that the resin composition which can obtain the insulating layer with favorable adhesiveness with can be implement|achieved.

Claims (12)

(A) an epoxy resin, (B) an active ester compound having a carbon-carbon unsaturated bond, and (C) a resin having an unsaturated hydrocarbon group;
The resin composition in which the said (B) component contains the compound represented by following formula (1).
Formula (1)

In the above formula (1),
m represents the integer of 1-6, n represents the integer of 1-20. The resin composition according to claim 1, wherein the content of the component (B) is 10% by mass to 60% by mass when the resin component is 100% by mass. According to claim 1, wherein the content of the component (A) is 10% by mass to 50% by mass when the resin component is 100% by mass,
The resin composition whose content of the said (C)component is 3 mass % - 30 mass %, when a resin component is 100 mass %. The resin composition according to claim 1, wherein the component (C) is a resin having an acryl group, a methacryl group, a styryl group, or an olefin group. The resin composition according to claim 1, which is for forming an insulating layer of a printed wiring board. The sheet-like laminated material containing the resin composition in any one of Claims 1-5. The printed wiring board containing the insulating layer formed with the hardened|cured material of the resin composition in any one of Claims 1-5. A semiconductor device comprising the printed wiring board according to claim 7. delete delete delete delete