KR102325456B1 - Resin composition - Google Patents

Abstract

[Problem] To provide a resin composition with good compatibility and melt viscosity that forms an insulating layer having a low dielectric loss tangent and excellent in plating adhesion and substrate adhesion.
[Solution means] A resin composition containing (A) an epoxy resin, (B) a curing agent, (C) a resin having a vinyl group, and (D) an indene coumarone resin, wherein the content of the component (D) is 100 When it is set as mass %, it is 5 mass % - 20 mass %, The resin composition.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition. It also relates to an adhesive film, a printed wiring board, and a semiconductor device.

As a manufacturing technique of a printed wiring board, the manufacturing method by the buildup system which laminates|stacks 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, patent document 1 contains a specific epoxy resin and a hardening|curing agent, and describes the resin composition of low dielectricity and high heat resistance.

Patent Document 1: Japanese Patent Laid-Open No. 2015-57465

In recent years, miniaturization and performance enhancement of electronic devices are progressing, and in a multilayer printed wiring board, a buildup layer is multilayered, and miniaturization and high density of wiring are calculated|required. In order to achieve further miniaturization and high density of wiring, a resin composition with good compatibility and melt viscosity that forms an insulating layer with a low dielectric loss tangent and excellent adhesion to plating and adhesion to the substrate is required. What is not is the current situation.

An object of the present invention is to provide a resin composition with good compatibility and melt viscosity that forms an insulating layer having a low dielectric loss tangent and excellent in plating adhesion and substrate adhesion.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the said subject, the present inventors discovered that the said subject could be solved by using in combination the resin which has a vinyl group, and a predetermined amount of indene coumarone resin, and came to complete this invention.

That is, the present invention includes the following contents.

[1] A resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) a resin having a vinyl group, and (D) an indene coumarone resin,

(D) The resin composition whose content of a component is 5 mass % - 20 mass %, when a resin component is 100 mass %.

[2] The resin composition according to [1], wherein at least one of the component (C) has an aromatic ring.

[3] The resin composition according to [1] or [2], wherein the content of the component (C) is 5% by mass to 20% by mass when the resin component is 100% by mass.

[4] The resin composition according to any one of [1] to [3], wherein at least one of the component (B) is an active ester curing agent.

[5] The resin composition according to any one of [1] to [4], further comprising (E) an inorganic filler.

[6] The resin composition according to [5], wherein the content of the component (E) is 50% by mass or more when the nonvolatile component of the resin composition is 100% by mass.

[7] The resin composition according to any one of [1] to [6], wherein the component (D) is a copolymer of indene, coumarone, and styrene.

[8] The resin composition according to any one of [1] to [7], which is for forming an insulating layer of a printed wiring board.

[9] An adhesive film having a support and a resin composition layer formed on the support and comprising the resin composition according to any one of [1] to [8].

[10] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [8].

[11] A semiconductor device comprising the printed wiring board according to [10].

ADVANTAGE OF THE INVENTION According to this invention, a resin composition with favorable compatibility and melt viscosity which forms the insulating layer which has a low dielectric loss tangent and is excellent in plating adhesiveness and base|substrate adhesiveness can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, the resin composition of this invention, an adhesive film, a printed wiring board, and a semiconductor device are demonstrated in detail.

[resin composition]

The resin composition of the present invention includes (A) an epoxy resin, (B) a curing agent, (C) a resin having a vinyl group, and (D) an indene coumarone resin, and the content of the component (D) is 100 When it is set as mass %, it is 5 mass % - 20 mass %. In addition, in this invention, a "resin component" means the component except the (E) inorganic filler mentioned later among the nonvolatile components which comprise a resin composition. Hereinafter, each component contained in the resin composition of this invention is demonstrated in detail.

<(A) Epoxy resin>

The resin composition of this invention contains (A) an epoxy resin. Examples of the epoxy resin include a bixylenol-type epoxy resin, a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, a bisphenol S-type epoxy resin, a bisphenol AF-type epoxy resin, a dicyclopentadiene-type epoxy resin, and a trisphenol-type epoxy resin. 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, glycidyl amine type epoxy resin, glycidyl Cydyl 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, cyclohexane A dimethanol-type epoxy resin, a naphthylene ether-type epoxy resin, a trimethylol-type epoxy resin, a tetraphenylethane-type epoxy resin, etc. are mentioned. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. The component (A) is preferably an aromatic skeleton-containing epoxy resin from the viewpoint of reducing the average coefficient of linear thermal expansion, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, and dicyclo It is more preferable that it is 1 or more types chosen from a pentadiene type epoxy resin, and a biphenyl type epoxy resin is still more preferable. The aromatic skeleton is a chemical structure generally defined as aromatic, and includes polycyclic aromatics and aromatic heterocycles.

It is preferable that an epoxy resin contains the epoxy resin which has two or more epoxy groups in 1 molecule. When the nonvolatile component of an epoxy resin is 100 mass %, it is preferable that at least 50 mass % or more is an epoxy resin which has two or more epoxy groups in 1 molecule. Among them, it is preferable to have three or more epoxy groups in one molecule and to contain a solid epoxy resin (hereinafter referred to as "solid epoxy resin") at a temperature of 20°C. The epoxy resin may contain only a solid epoxy resin, has two or more epoxy groups in one molecule, and may contain a liquid epoxy resin (hereinafter referred to as "liquid epoxy resin") and a solid epoxy resin at a temperature of 20°C. As the epoxy resin, a resin composition having excellent flexibility can be obtained by using a liquid epoxy resin and a solid epoxy resin together. Moreover, the breaking strength of the hardened|cured material of a resin composition also improves.

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, glycidyl amine type epoxy resin, phenol novolac type epoxy resin , an alicyclic epoxy resin having an ester skeleton, a cyclohexanedimethanol type epoxy resin, a glycidyl amine type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a glycidyl amine 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. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC Corporation, "828US", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation. , "Epicoat 828EL" (bisphenol A type epoxy resin), "jER807", "1750" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (Gly Cydyl amine type epoxy resin), "ZX1059" (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd., "EX-" manufactured by Nagase Chemtex Co., Ltd. 721" (glycidyl ester-type epoxy resin), "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Co., Ltd., "PB-3600" (epoxy resin having a butadiene structure), shinnit "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Tetsu Chemical Co., Ltd., "630LSD" manufactured by Mitsubishi Chemical Co., Ltd. (glycidyl amine type epoxy resin), etc. can be heard These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the solid-state epoxy resin include 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 naphthylene ether-type epoxy resin. , anthracene-type epoxy resins, bisphenol A-type epoxy resins, and tetraphenylethane-type epoxy resins are preferable, and naphthalene-type tetrafunctional epoxy resins, naphthol-type epoxy resins, and biphenyl-type epoxy resins are more preferable. As a specific example of a solid-state epoxy resin, "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation, "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol) Novolac type epoxy resin), "N-695" (cresol novolak type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP-7200HH", "HP-7200H", "EXA" -7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN" manufactured by Nippon Kayaku Co., Ltd. -502H" (trisphenol-type epoxy resin), "NC7000L" (naphthol novolac-type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl-type epoxy resin), New Nittetsu Sumikin "ESN475V" (naphthalene-type epoxy resin), "ESN485" (naphthol novolac-type epoxy resin) manufactured by Kagaku Co., Ltd., "YX4000H", "YX4000", and "YL6121" by Mitsubishi Chemical Co., Ltd. (non phenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), Osaka Gas Chemical Co., Ltd. "PG-100", "CG-500", Mitsubishi Chemical "YL7760" (bisphenol AF type epoxy resin), "YL7800" (fluorene type epoxy resin) manufactured by Co., Ltd., "jER1010" manufactured by Mitsubishi Chemical Co., Ltd. (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin) etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

As an epoxy resin, when using a liquid epoxy resin and a solid epoxy resin together, those ratios (liquid epoxy resin:solid epoxy resin) are mass ratio, and the range of 1:0.1 - 1:15 is preferable. By setting the ratio of the liquid epoxy resin and the solid epoxy resin to this range, i) when used in the form of an adhesive film, adequate adhesion can be formed, and ii) when used in the form of an adhesive film, sufficient flexibility can be obtained, , handling is improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii), the amount ratio of the liquid epoxy resin and the solid epoxy resin (liquid epoxy resin:solid epoxy resin) is, in terms of mass ratio, more preferably in the range of 1:0.5 to 1:10, 1 The range of :1 to 1:8 is more preferred.

The content of the epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, when the resin component is 100% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. More preferably, it is 20 mass % or more. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention appears, Preferably it is 60 mass % or less, More preferably, it is 50 mass % or less, More preferably, it is 40 mass % or less.

The epoxy equivalent of an epoxy resin becomes like this. Preferably it is 50-5000, More preferably, it is 50-3000, More preferably, it is 80-2000, More preferably, it is 110-1000. By being in this range, the crosslinking density of hardened|cured material becomes enough, and the insulating layer with small surface roughness can be formed. In addition, an epoxy equivalent can be measured according to JISK7236, and is the mass of resin containing 1 equivalent of an epoxy group.

The weight average molecular weight of an epoxy resin becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of an epoxy resin is the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) method.

<(B) curing agent>

The resin composition of this invention contains (B) hardening|curing agent. The curing agent is not particularly limited as long as it has a function of curing the epoxy resin, and for example, 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. A hardening|curing agent etc. are mentioned. A hardening|curing agent may be used individually by 1 type, or may use 2 or more types together. The component (B) is preferably at least one selected from a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a carbodiimide-based curing agent, and a cyanate ester-based curing agent, and is preferably an active ester-based curing agent.

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

As a specific example of a phenol type hardening|curing agent and a naphthol type hardening|curing agent, For example, Meiwa Kasei Co., Ltd. product "MEH-7700", "MEH-7810", "MEH-7851", "MEH-7851H", Nippon Kayaku "NHN", "CBN", "GPH" manufactured by KK, "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", manufactured by Shin-Nittetsu Sumikin Co., Ltd. "SN375", "SN395", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" manufactured by DIC Corporation ' and the like.

From a viewpoint of obtaining an insulating layer excellent in adhesiveness with a conductor layer, an active ester type hardening|curing agent is preferable. Although there is no restriction|limiting in particular as an active ester type hardening|curing agent, Generally, ester groups with high reaction activity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compound esters, are contained in 1 molecule. A compound having two or more is preferably used. It is preferable that the said active ester type hardening|curing agent is obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound, and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol compound, 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.

Specifically, 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 is preferable, and among these, the active ester compound containing a naphthalene structure and the active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Commercially available active ester curing agents are active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM" ', "EXB-8000L-65TM" (manufactured by DIC Corporation), "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, an active ester containing an acetylated product of phenol novolac "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as a compound, "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing a benzoyl product of phenol novolac, an active ester that is an acetylated product of phenol novolac “DC808” (manufactured by Mitsubishi Chemical Co., Ltd.) as a curing agent, “YLH1026” (manufactured by Mitsubishi Chemical Co., Ltd.) and “YLH1030” (Mitsubishi Chemical Co., Ltd.) as an active ester curing agent that is a benzoyl product of phenol novolac. ), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.), and the like.

As a specific example of a benzoxazine type hardening|curing agent, "HFB2006M" by Showa Kobunshi Co., Ltd., "P-d" by Shikuko Kasei Kogyo Co., Ltd. product, and "F-a" are mentioned.

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6- Dimethylphenyl cyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4- cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cya Bifunctional cyanate resins such as natephenyl)thioether and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolac and cresol novolac, etc., in which these cyanate resins are partially triazined A prepolymer etc. are mentioned. As a specific example of a cyanate ester type hardening|curing agent, "PT30" and "PT60" (both phenol novolak-type polyfunctional cyanate ester resin) manufactured by Ronza Japan Co., Ltd., "BA230", "BA230S75" (bisphenol A dicia) and a prepolymer in which a part or all of the nate was triazined and became a trimer) and the like.

As a specific example of a carbodiimide type hardening|curing agent, "V-03", "V-07" by Nisshinbo Chemical Co., Ltd., etc. are mentioned.

The amount ratio of the epoxy resin and the curing agent is a ratio of [the total number of epoxy groups in the epoxy resin]: [the total number of reactive groups in the curing agent], preferably in the range of 1:0.1 to 1:10, and 1:0.5 to 1:5 is more preferable, and 1:1 to 1:3 are still more preferable. Here, a reactive group of a hardening|curing agent is an active hydroxyl group, an active ester group, etc., and differs with the kind of hardening|curing agent. In addition, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is the solid content mass of each curing agent equal to the reactor equivalent. It is a value obtained by dividing the value by the sum of all curing agents. 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 improves more.

Although content of the hardening|curing agent in a resin composition is not specifically limited, When the resin component is 100 mass %, Preferably it is 60 mass % or less, More preferably, it is 55 mass % or less, More preferably, it is 50 mass % or less. Moreover, although there is no restriction|limiting in particular as for a minimum, Preferably it is 30 mass % or more, More preferably, it is 35 mass % or more, More preferably, it is 40 mass % or more.

<(C) Resin having a vinyl group>

The resin composition of this invention contains resin which has (C) vinyl group. By including the component (C) in combination with the component (D) described later, a resin composition with good compatibility and melt viscosity that forms an insulating layer having a low dielectric loss tangent and excellent plating adhesion and substrate adhesion can be obtained. (C) A component may be used individually by 1 type, and may be used 2 or more types.

(C) Although it will not specifically limit if component has a vinyl group, It is preferable to have an aromatic ring, Especially, it is preferable that it is resin represented by following formula (1) from a viewpoint of storage stability.

(In Formula 1, R ¹ to R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and A represents a group represented by Formula 2 or Formula 3 below)

(In Formula 2, E represents the following Formula E-1, E-2 or E-3)

(In Formula 3, R ⁷ to R ¹⁴ each independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and E represents the following Formula E-1, E-2 or E-3. a, b represents an integer from 0 to 100 in which at least one is not 0)

[ Formula 4 ]
[Formula E-1]

[Formula E-2]

[Formula E-3]

(In the formulas E-1 to E-3, R ¹⁵ to R ³⁴ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. G is a straight chain having 20 or less carbon atoms, minute represents a gaseous or cyclic divalent hydrocarbon group)

In Formula 1, R ¹ to R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and preferably a hydrogen atom. A methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group etc. are mentioned as a C1-C4 alkyl group.

^{R 7} to R ¹⁴ in the formula (3) ^{and R 15} to R ³⁴ in the formulas (E-1 to E-3) each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. Examples of the alkyl group having 6 or less carbon atoms include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, pentyl group, and hexyl group. As R ⁷ to R ¹⁴ , a hydrogen atom or a methyl group is preferable.

a and b represent the integer of 0-100 in which at least one is not 0. The condition that at least one of a and b is not 0, the integer of 0-50 is preferable and the integer of 0-10 is more preferable.

G represents a C20 or less linear, branched or cyclic divalent hydrocarbon group. Examples of the divalent hydrocarbon group include an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkynylene group having 2 to 20 carbon atoms. Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of the alkenylene group having 2 to 20 carbon atoms include a vinylene group, a propenylene group, and a butenylene group. Examples of the alkynylene group having 2 to 20 carbon atoms include an ethynylene group, a propynylene group, and a butynylene group.

The vinyl group in resin which has a vinyl group may have a substituent. Moreover, the said alkyl group, a phenyl group, and a divalent hydrocarbon group may also have a substituent.

The substituent is not particularly limited, for example, a halogen atom, -OH, -OC _{1 -6} alkyl, -N (C _{1 -6} alkyl) _2, C _{1 -6} alkyl, C _{6 -10} aryl groups, -NH _2, -CN, it can be given a -C (O) OC _{1 -6} alkyl, -COOH, -C (O) H , -NO 2 or the like.

Here, the term "C _{p -q} " (p and q are positive integers and satisfy p < q) indicates that the number of carbon atoms in the organic group described immediately after this term is p to q. For example, "C _{1 -6} alkyl group" is the representation, an alkyl group of 1 to 6 carbon atoms.

The above-described substituent may further have a substituent (hereinafter, sometimes referred to as a "secondary substituent"). As the secondary substituent, the same substituents as described above may be used unless otherwise specified.

Hereinafter, although the specific example of (C)component is illustrated, this invention is not limited to this.

(In the formula (5), R ¹ to R ⁶ , E, a, and b are the same as those of the symbols of the formula (1) or the formula (3), and their preferred ranges are also the same)

(C) As a component, you may use a commercial item, As a specific example of a commercial item, "OPE-2St 2200 (number average molecular weight 2200)" manufactured by Mitsubishi Gas Chemical Co., Ltd., "OPE-2St 1200 (number average molecular weight 2200)" " (Styrene-modified polyphenylene ether resin), Mitsubishi Chemical Co., Ltd. "YL7776 (number average molecular weight 331)", (bixylenol diallyl ether resin), etc. are mentioned.

(C) The number average molecular weight of the component is preferably in the range of 100 to 10000, and in the range of 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. more preferably. In addition, the number average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the number average molecular weight by GPC method is LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P/K-804L manufactured by Showa Denko Co., Ltd. as a column as a column. /K-804L can be calculated using chloroform or the like as a mobile phase, measured at a column temperature of 40°C, and using a standard polystyrene calibration curve.

(C) The detail of component can consider description of Paragraph 0010 of Unexamined-Japanese-Patent No. 2014-34580 - 0022, and this content is integrated in this specification.

(C) The content of the component is preferably 30 mass% or less, more preferably 25 mass% or less, still more preferably when the resin component is 100 mass% from the viewpoint of obtaining a resin composition with good compatibility. is 20 mass % or less, or 15 mass % or less. The lower limit of the content of the component (C) is preferably 1% by mass or more, more preferably 1% by mass or more, when the resin component is 100% by mass from the viewpoint of achieving the desired effect in combination with the component (D) described later. Preferably it is 3 mass % or more, More preferably, it is 5 mass % or more.

<(D) Indene Coumarone Resin>

The resin composition of the present invention contains a predetermined amount of (D) indene coumarone resin. By including a predetermined amount of component (D), compatibility is improved and a resin composition having a good balance of physical properties can be obtained. (D) The coumarone skeleton contained in the component has good compatibility with epoxy resins and curing agents with high polarity, and the indene skeleton and coumarone skeleton have good compatibility with vinyl resins with low polarity. Therefore, it acts as a compatibilizer between high polarity resin and low polarity resin, and it is thought that the compatibility of the whole resin composition is improved.

(D) As a component, the copolymer of indene and coumarone, the copolymer of indene, coumarone, and styrene, etc. are mentioned, for example.

The content of the coumarone component in the indene coumarone resin is preferably 5 mol% or more, more preferably 8 mol% or more, and still more preferably 10 mol% or more. The upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and still more preferably 30 mol% or less.

The content of the indene component in the indene coumarone resin is preferably 30 mol% or more, more preferably 35 mol% or more, and still more preferably 40 mol% or more. The upper limit is preferably 80 mol% or less, more preferably 75 mol% or less, and still more preferably 70 mol% or less.

When the indene coumarone resin is a copolymer of indene, coumarone and styrene, the content of the styrene component is preferably 20 mol% or more, more preferably 25 mol% or more, still more preferably 30 mol% or more. The upper limit is preferably 70 mol% or less, more preferably 65 mol% or less, and still more preferably 60 mol% or less.

As a specific example of indene coumarone resin, "H-100", "V-120S", "V-120" by Nitto Chemical Co., Ltd. product, etc. are mentioned.

(D) Content of component is 5 mass % or more when a resin component is 100 mass % from a viewpoint of obtaining a compatible resin composition, Preferably it is 8 mass % or more, More preferably, it is 10 mass %. % or more (D) The upper limit of the content of the component is 20% by mass or less, preferably 18% by mass or less, more preferably from the viewpoint of obtaining a resin composition having a good melt viscosity, and from the viewpoint of obtaining an insulating layer excellent in adhesion to the substrate. is 16% by mass or less or 15% by mass or less.

<(E) Inorganic filler>

The resin composition of this invention may contain the (E) inorganic filler further. Although the material of the inorganic filler is not particularly limited, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate , barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungsten phosphate. Among these, silica is particularly suitable. Moreover, as a silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

The average particle diameter of the inorganic filler is preferably 5 µm or less, more preferably 2.5 µm or less, still more preferably 2 µm or less, from the viewpoint of improving circuit embedding properties and obtaining an insulating layer with low surface roughness. Preferably it is 1.5 micrometers or less. Although the lower limit of the said average particle diameter is not specifically limited, Preferably it is 0.01 micrometer or more, More preferably, it is 0.05 micrometer or more, More preferably, it is 0.1 micrometer or more, 0.5 micrometer or more, or 1 micrometer or more. As a commercial item of the inorganic filler which has such an average particle diameter, For example, Shin-Nitetsu Sumikin Materials Co., Ltd. product "SP60-05", "SP507-05", Adomatex Co., Ltd. product "YC100C", " YA050C", "YA050C-MJE", "YA010C", Denka Co., Ltd. "UFP-30", Tokuyama Co., Ltd. "Silver NSS-3N", "Silver NSS-4N", "Silver NSS-5N" , "SC2500SQ" manufactured by Adomatex Co., Ltd., "SO-C4", "SO-C2", "SO-C1", etc. are mentioned.

The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, it can measure by creating the particle size distribution of an inorganic filler on a volume basis with a laser diffraction scattering type particle size distribution analyzer, and making the median diameter into an average particle diameter. As a measurement sample, what disperse|distributed the inorganic filler in water by ultrasonic wave can be used preferably. As a laser diffraction scattering type particle size distribution analyzer, "LA-500" manufactured by Horiba Corporation, etc. can be used.

From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler is one such as 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. It is preferable that it is treated with more than one kind of surface treatment agent. As a commercial item of a surface treatment agent, for example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyl trimethoxysilane), Shin-Etsu Chemical Co., Ltd. product "KBM803" (3-mercapto) Propyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltri methoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM-103" (phenyltrimethoxysilane), Shin-Etsu Chemical Kogyo Co., Ltd. product "KBM-4803" (long-chain epoxy type silane coupling agent) etc. are mentioned.

The grade of the surface treatment by a surface treating agent can be evaluated by the amount of carbon per unit surface area of an inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and still more preferably 0.2 mg/m 2 or more. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the melt viscosity in the sheet form, 1 mg/m 2 or less is preferable, 0.8 mg/m 2 or less is more preferable, and 0.5 mg/m 2 or less is still more preferable.

The amount of carbon per unit surface area of an inorganic filler can be measured, after washing-processing the inorganic filler after surface treatment with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, MEK in a sufficient amount as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, followed by ultrasonic cleaning at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Corporation, etc. can be used.

When content of the inorganic filler in a resin composition makes the nonvolatile component in a resin composition 100 mass % from a viewpoint of obtaining an insulating layer with a low coefficient of thermal expansion, Preferably it is 50 mass % or more, More preferably, it is 55 mass %. or more, more preferably 60 mass % or more, or 65 mass % or more. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, or 80% by mass or less from the viewpoint of mechanical strength, particularly elongation, of the insulating layer.

<(F) curing accelerator>

The resin composition of this invention may contain the (F) hardening accelerator. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, organic peroxide curing accelerators, and the like, phosphorus-based curing accelerators and amine-based curing accelerators. An accelerator, an imidazole type hardening accelerator, and a metal type hardening accelerator are preferable, and an amine type hardening accelerator, an imidazole type hardening accelerator, and a metal type hardening accelerator are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

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

Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8 -diazabicyclo(5,4,0)-undecene etc. are mentioned, 4-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, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl Imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s- Triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct , 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2- a] imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and mixtures of imidazole compounds and epoxy resins A duct body is mentioned, 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, Mitsubishi Chemical Co., Ltd. product "P200-H50" 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, and diphenylguanidine. , trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc. are mentioned, dicyandiamide, 1,5,7-triazabicyclo[4.4.0]deca-5-ene is preferred.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese and tin. Specific examples of the organometallic complex include organocobalt complexes such as cobalt(II)acetylacetonate and cobalt(III)acetylacetonate, organocopper complexes such as copper(II)acetylacetonate, zinc(II)acetylacetonate, and the like. organic zinc complexes, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Examples of the organic peroxide curing accelerator include dicumyl peroxide, cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butylcumyl peroxide, di-3 tert-butyl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, and the like. As an organic peroxide type|system|group hardening accelerator, you may use a commercial item, for example, "Percumyl D" by Nichiyo Corporation etc. is mentioned.

Although content of the hardening accelerator in a resin composition is not specifically limited, When a resin component is 100 mass %, 0.01 mass % - 3 mass % are preferable.

<(G) Thermoplastic resin>

The resin composition of this invention may contain the (G) thermoplastic resin. As the thermoplastic resin, for example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polycarbonate resin , polyether ether ketone resin and polyester resin are mentioned, and phenoxy resin is preferable. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

The range of 8,000-70,000 is preferable, as for the weight average molecular weight of polystyrene conversion of a thermoplastic resin, the range of 10,000-60,000 is more preferable, The range of 20,000-60,000 is still more preferable. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight in terms of polystyrene of the thermoplastic resin is LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P/K manufactured by Showa Denko Co., Ltd. as a column as a column. -804L/K-804L can be calculated by using chloroform or the like as a mobile phase, measuring the column temperature at 40°C, and 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 skeleton , an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a phenoxy resin having at least one skeleton selected from the group consisting of trimethylcyclohexane skeleton. Any functional group, such as a phenolic hydroxyl group and an epoxy group, may be sufficient as the terminal of a phenoxy resin. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. As a specific example of a phenoxy resin, Mitsubishi Chemical Co., Ltd. product "1256" and "4250" (both bisphenol A skeleton containing phenoxy resin), "YX8100" (bisphenol S skeleton containing phenoxy resin), and "YX6954" (Bisphenolacetophenone skeleton-containing phenoxy resin) is mentioned, In addition, "FX280" and "FX293" by Shin-Nippon Sumikin Chemical Co., Ltd., "YX6954BH30" by Mitsubishi Chemical Co., Ltd., " YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7891BH30", "YL7482", etc. are mentioned.

As polyvinyl acetal resin, polyvinyl formal resin and polyvinyl butyral resin are mentioned, for example, Polyvinyl butyral resin is preferable. As a specific example of polyvinyl acetal resin, "Telephone Butyral 4000-2", "Telephone Butyral 5000-A", "Telephone Butyral 6000-C", "Telephone Butyral 4000-2" manufactured by Denki Chemical Co., Ltd. as a specific example of polyvinyl acetal resin, for example Butyral 6000-EP", Sekisui Kagaku Kogyo Co., Ltd. S-Rec BH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series and the like.

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

As a specific example of polyamideimide resin, Toyo Boseki Co., Ltd. product "Viromax HR11NN" and "Viromax HR16NN" are mentioned. Specific examples of the polyamideimide resin include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing polysiloxane skeleton) manufactured by Hitachi Kasei Kogyo Co., Ltd.

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

As a specific example of polysulfone resin, Solvay Advanced Polymers Co., Ltd. product polysulfone "P1700", "P3500", etc. are mentioned.

Especially, as a thermoplastic resin, a phenoxy resin and polyvinyl acetal resin are preferable. Therefore, in one suitable embodiment, the thermoplastic resin includes at least one selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin.

When the resin composition of this invention contains a thermoplastic resin, when content of a thermoplastic resin makes a resin component 100 mass %, Preferably it is 0.5 mass % - 15 mass %, More preferably, it is 0.6 mass % - 12 mass % %, more preferably 0.7 mass % to 10 mass %.

<(H) Flame Retardant>

The resin composition of this invention may contain the (H) 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. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

A commercial item may be used as a flame retardant, For example, "HCA-HQ" by Sanko Co., Ltd. product, "PX-200" by Daihachi Chemical Industry Co., Ltd., etc. are mentioned.

When the resin composition of the present invention contains a flame retardant, the content of the flame retardant is not particularly limited, but when the resin component is 100% by mass, preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15 mass %, More preferably, 0.5 mass % - 10 mass % are still more preferable.

<(I) organic filler>

The resin composition of this invention may contain the (I) organic filler. As an organic filler, you may use arbitrary organic fillers which can be used when forming the insulating layer of a printed wiring board, For example, a rubber particle, polyamide microparticles|fine-particles, a silicone particle, etc. are mentioned.

A commercial item may be used as a rubber particle, for example, "EXL2655" by Dow Chemical Nippon Co., Ltd., "AC3816N" by Aika Kogyo Co., Ltd., etc. are mentioned.

When the resin composition of this invention contains an organic filler, when content of an organic filler makes a resin component 100 mass %, Preferably it is 0.1 mass % - 20 mass %, More preferably, 0.2 mass % - 10 mass % %, more preferably 0.3 mass % to 5 mass %, or 0.5 mass % to 3 mass %.

<(J) Other additives>

The resin composition of the present invention may further contain other additives as necessary. Examples of such other additives include organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds, thickeners, antifoaming agents, Resin additives, such as a leveling agent, an adhesion-imparting agent, and a coloring agent, etc. are mentioned.

The resin composition of this invention has a low dielectric loss tangent, and can form the insulating layer excellent in plating adhesiveness and base|substrate adhesiveness, and compatibility and melt viscosity are also favorable. Therefore, the resin composition of this invention can be used suitably as a resin composition for forming the insulating layer of a printed wiring board (resin composition for insulating layers of a printed wiring board), The resin composition for forming the 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. Moreover, since the resin composition of this invention forms an insulating layer with good component embedding property, when a printed wiring board is a component built-in circuit board, it can be used suitably.

[Adhesive Film]

The adhesive film of this invention has a support body and the resin composition layer formed on the said support body and containing the resin composition of this invention.

The thickness of a resin composition layer becomes like this. Preferably it is 900 micrometers or less, More preferably, it is 800 micrometers or less, More preferably, it is 700 micrometers or less, More preferably, it is 600 micrometers or less. Since especially this invention can suppress the plating penetration depth small, 30 micrometers or less are preferable, 20 micrometers or less are more preferable, and 10 micrometers or less are still more preferable. Although the lower limit of the thickness of a resin composition layer is not specifically limited, Usually, it can be 1 micrometer or more, 1.5 micrometers or more, 2 micrometers 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 a film made of a plastic material is used as the support, the plastic material is, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”). ), polyester such as polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), Polyether ketone, polyimide, etc. 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, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, 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.) may be used.

The support may be subjected to mat treatment, corona treatment, or antistatic treatment on the surface to be joined to the resin composition layer.

Moreover, as a support body, you may use the support body with a mold release layer which has a mold release layer in the surface to join 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, a polyolefin resin, a urethane resin, and a silicone resin, for example. A commercial item may be used for the support body with a release layer, For example, Lintec Co., Ltd. product which is a PET film which has a release layer which has an alkyd resin type release agent as a main component, "SK-1", "AL-5", " AL-7", Toray Co., Ltd. product "Lumirer T6AM", etc. are mentioned.

Although it does not specifically limit as thickness of a support body, The range of 5 micrometers - 75 micrometers is preferable, and the range of 10 micrometers - 60 micrometers is more preferable. Moreover, when using 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, etc., and drying it to form a resin composition layer. .

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitols such as cellosolve and butylcarbitol; aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used individually by 1 type, or may be used in combination of 2 or more type.

You may perform drying by well-known methods, such as a heating and hot air spraying. Although 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. 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, drying at 50°C to 150°C for 3 minutes to 10 minutes, A resin composition layer can be formed.

An adhesive film WHEREIN: On the surface which is not joined to the support body of a resin composition layer (that is, the surface on the opposite side to a support body), the protective film according to a support body can be laminated|stacked further. Although the thickness of a protective film is not specifically limited, For example, they are 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 roll shape. When an adhesive film has a protective film, it becomes usable by peeling off a protective film.

The minimum melt viscosity of the resin composition layer (or resin composition) in the adhesive film is preferably 1000 poise or more, more preferably 1500 poise or more, and further desirable. The upper limit of the minimum melt viscosity is preferably 12000 poise or less, more preferably 10000 poise or less, still more preferably 8000 poise or less and 5000 poise or less from the viewpoint of obtaining good circuit embedding properties.

The minimum melt viscosity of a resin composition layer means the minimum viscosity which a resin composition layer shows when resin of a resin composition layer melts. Specifically, when the resin composition layer is heated at a constant temperature increase rate to melt the resin, in the initial stage, the melt viscosity decreases with the temperature rise, and then, when it exceeds a certain level, the melt viscosity rises with the temperature rise. The minimum melt viscosity means the melt viscosity of such a minimum point. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelasticity method, for example, according to the method described in <Measurement of the minimum melt viscosity of a resin composition layer> mentioned later.

The resin composition layer (or resin composition) in the adhesive film of this invention shows the outstanding compatibility. That is, the resin composition layer (or resin composition) in the adhesive film of this invention does not precipitate 50 micrometers or more of granules. Compatibility can be measured according to the method as described in <Evaluation of compatibility> mentioned later.

The insulating layer formed using the adhesive film (or resin composition) of this invention shows a low dielectric loss tangent. From the viewpoint of preventing heat generation at high frequencies, reducing signal delay and signal noise, the dielectric loss tangent is preferably 0.010 or less, more preferably 0.009 or less, and still more preferably 0.008 or less, 0.007 or less, 0.006 or less, or 0.005 or less. Although the lower limit of the dielectric loss tangent is so preferable that it is low, it can be normally set as 0.001 or more, etc. The dielectric loss tangent can be measured according to the method described in <Evaluation of dielectric loss tangent> described later.

The insulating layer formed using the adhesive film (or resin composition) of this invention shows good plating adhesiveness. That is, an insulating layer exhibiting good plating peel strength is formed. Plating peeling strength becomes like this. Preferably it is 1.5 kgf/cm or less, More preferably, it is 1 kgf/cm or less, More preferably, it is 0.5 kgf/cm or less. The upper limit can be 0.1 kgf/cm or more. Evaluation of plating peeling strength can be measured according to the method as described in [Measurement of plating adhesiveness] mentioned later.

An insulating layer formed using the adhesive film (or resin composition) of the present invention exhibits good adhesion to the underlying substrate. That is, the insulating layer which shows favorable base peeling strength is formed. Base peeling strength becomes like this. Preferably it is 1.5 kgf/cm or less, More preferably, it is 1 kgf/cm or less, More preferably, it is 0.5 kgf/cm or less. The upper limit can be 0.1 kgf/cm or more. The evaluation of the adhesion to the substrate can be measured according to the method described in [Measurement of the adhesion to the substrate] described later.

You may form a prepreg using the resin composition of this invention. A prepreg can be formed by impregnating the resin composition of this invention in a sheet-like fiber base material. Therefore, in one embodiment, the prepreg of this invention contains the sheet-like fiber base material and the resin composition of this invention impregnated in the said sheet-like fiber base material.

The sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as the base material for prepregs, such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric, can be used. From a viewpoint of thickness reduction of a printed wiring board, Preferably the thickness of a sheet-like fiber base material is 900 micrometers or less, More preferably, it is 800 micrometers or less, More preferably, it is 700 micrometers or less, More preferably, it is 600 micrometers or less. Since especially this invention can suppress the plating penetration depth small, 30 micrometers or less are preferable, 20 micrometers or less are more preferable, and 10 micrometers or less are still more preferable. Although the lower limit of the thickness of a sheet-like fiber base material is not specifically limited, Usually, it can be 1 micrometer or more, 1.5 micrometers or more, 2 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 adhesive film mentioned above.

[Printed wiring board]

The printed wiring board of this invention contains the insulating layer formed with the hardened|cured material of the resin composition of this invention.

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

(I) A step of laminating an adhesive film on an 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 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 of the substrates It refers to a circuit board in which a patterned conductor layer (circuit) is formed on one side or both sides. Moreover, when manufacturing a printed wiring board, the inner-layer circuit board of the intermediate|middle manufacture on which an insulating layer and/or a conductor layer should further be formed is also included in the "inner-layer board|substrate" referred to in this 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 thermocompression bonding 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 hard plate etc.) or a metal roll (SUS roll) etc. are mentioned, for example. In addition, it is preferable not to press the thermocompression-bonding member directly to the adhesive film, but 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.

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 compression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, and the thermocompression compression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably is in the range of 0.29 MPa to 1.47 MPa, and the heat compression time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination|stacking is preferably performed under reduced pressure conditions of pressure 26.7 hPa or less.

Lamination can be performed with a commercially available vacuum laminator. As a commercially available vacuum lamination, the vacuum pressurization laminator by the Meiki Sesakusho Co., Ltd. product, the vacuum applicator by the Nikko Materials Co., Ltd. product, etc. are mentioned, for example.

After lamination, a smoothing treatment of the laminated adhesive film may be performed under normal pressure (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 same conditions as the thermocompression-bonding conditions of the said lamination|stacking. A smoothing process can be performed with a commercially available laminator. In addition, you may perform lamination|stacking and a smoothing process continuously using said commercially available vacuum laminator.

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

In step (II), the resin composition layer is thermosetted to form an insulating layer.

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 the resin composition layer vary depending on the type of resin composition, etc., but the curing temperature is in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably 170°C). to 200°C), and the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, 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 is You may preheat for 5 minutes or more (preferably 5 minutes - 150 minutes, More preferably, 15 minutes - 120 minutes).

When manufacturing a printed wiring board, you may further implement at least any one of (III) the process of drilling in an insulating layer, (IV) the process of roughening an insulating layer, and (V) the process of forming a conductor layer. 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 (V). ) may be performed between

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

Step (III) is a step of drilling holes 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, laser, plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer and the like. 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. Although it does not specifically limit as a swelling liquid, An alkali solution, surfactant solution, etc. are mentioned, Preferably it is an alkali solution, As said alkali solution, sodium hydroxide solution and potassium hydroxide solution are more preferable. As a commercially available swelling liquid, "Swelling Deep Security P", "Swelling Deep Security SBU" etc. manufactured by Atotech Japan Co., Ltd. are mentioned, for example. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer in 30 degreeC - 90 degreeC swelling liquid for 1 minute - 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. Although 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. It is preferable to perform the roughening process by oxidizing agents, such as an alkaline permanganic acid solution, by making the insulating layer immerse for 10 minutes - 30 minutes in the oxidizing agent solution heated to 60 degreeC - 80 degreeC. 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 Securiganth P" by Atotech Japan Co., Ltd., are mentioned, for example. In addition, an acidic aqueous solution is preferable as a neutralizing liquid, and as a commercial item, "Reduction Solution Secure P" manufactured 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 target object roughened by the oxidizing agent from points, such as workability|operativity, in the neutralization liquid of 40 degreeC - 70 degreeC for 5 minutes - 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening is preferably 280 nm or less, more preferably 250 nm or less, still more preferably 200 nm or less, 140 nm or less, 130 nm or less, 120 nm or less, 110 nm or less, 100 nm or less, 95 nm or less, or 90 nm or less. Although the lower limit of Ra value is not specifically limited, 0.5 nm or more is preferable and 1 nm or more is more preferable. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact type surface roughness meter. As a specific example of a non-contact type surface roughness meter, "WYKO NT3300" by a Vico Instruments company is mentioned.

Step (V) is a step 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, and the alloy layer is, for example, an alloy of two or more metals selected from the group described above (for example, a nickel/chromium alloy, a copper/nickel alloy, and a copper/titanium alloy). ) can be mentioned. 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, An alloy layer of a copper/titanium alloy is preferable, 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 the single metal layer of copper is more preferable more preferably.

The conductor layer may have a single layer structure or a multilayer 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 it is 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. Hereinafter, an example in which the conductor layer is formed by a semi-additive method is shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, on the formed plating seed layer, a mask pattern for exposing a portion of the plating seed layer corresponding to a desired wiring pattern is formed. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

[Semiconductor device]

The semiconductor device of the present invention includes a printed wiring board. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

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

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 any surface, a buried location, or any place. 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 for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, and specifically, a wire bonding mounting method, a flip chip mounting method, and a bumpless method are used. The mounting method by a build-up layer (BBUL), the mounting method by an anisotropic conductive film (ACF), the mounting method by a nonelectroconductive film (NCF), etc. are mentioned. 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 to connect the semiconductor chip and wiring on the printed wiring board".

[Example]

Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited to these Examples. In the following description, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

[Example 1]

40 parts of biphenyl type epoxy resin (epoxy equivalent 269, Nippon Kayaku Co., Ltd. product "NC3000") was heat-dissolved while stirring 25 parts of solvent naphtha, and it cooled to room temperature after that. 330 parts of inorganic fillers ("SO-C2" manufactured by Adomatex Co., Ltd., average particle diameter of 0.5 µm, carbon amount per unit surface area of 0.38 mg/m 2 ) were mixed, kneaded with three rolls and dispersed. In addition, 92.3 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC Co., Ltd., a toluene solution having an active group equivalent of about 223 and a nonvolatile content of 65% by mass), a resin having a vinyl group (Mitsubishi Gas Chemical Co., Ltd.) 25 parts of manufacture "OPE-2St 2200" nonvolatile matter 60 mass % toluene solution), 15 parts of indene coumarone resin ("H-100" manufactured by Nitto Chemical Co., Ltd.), 4-dimethylaminopyridine (DMAP) as a curing accelerator ) of 5 mass % MEK solution 2 parts were mixed, and it was made to disperse|distribute uniformly with a rotary mixer, and the resin varnish 1 was produced.

The resin varnish 1 was placed on the release surface of a polyethylene terephthalate film with an alkyd resin release treatment (“AL-5” manufactured by Lintec Co., Ltd., 38 µm in thickness) with a die coater so that the thickness of the resin composition layer after drying was 40 µm. It applied uniformly, and it dried at 80-110 degreeC (average 95 degreeC) for 5 minutes, and the adhesive film 1 was produced.

[Example 2]

In Example 1, the resin (Mitsubishi Gas Chemical Co., Ltd. "OPE-2St 2200" toluene solution of 60 mass % of nonvolatile matter) having a vinyl group was mixed with a resin having a vinyl group (manufactured by Mitsubishi Gas Chemical Co., Ltd. " OPE-2St 1200" toluene solution of 60 mass % of non-volatile matter). Except for the above, in the same manner as in Example 1, a resin varnish 2 and an adhesive film 2 were produced.

[Example 3]

In Example 1, indene coumarone resin ("H-100" manufactured by Nitto Chemical Co., Ltd.) was changed to indene coumarone resin ("V-120S" manufactured by Nitto Chemical Co., Ltd.). 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, indene coumarone resin ("H-100" manufactured by Nitto Chemical Co., Ltd.) was changed to indene coumarone resin ("V-120" manufactured by Nitto Chemical Co., Ltd.). Except for the above, it carried out similarly to Example 1, and produced the resin varnish 4 and the adhesive film 4.

[Example 5]

In Example 1,

(1) Resin having a vinyl group (Mitsubishi Gas Chemical Co., Ltd. "OPE-2St 2200" toluene solution of 60 mass % of nonvolatile matter) 25 parts of resin having a vinyl group (Mitsubishi Gas Chemical Co., Ltd. "OPE-" 2St 2200" toluene solution with a nonvolatile content of 60% by mass) 8.3 parts, and a resin having a vinyl group ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a nonvolatile content of 60% by mass) 16.7 parts;

(2) The compounding quantity of indene coumarone resin ("H-100" manufactured by Nitto Chemical Co., Ltd.) was changed from 15 parts to 8 parts.

Except for the above, it carried out similarly to Example 1, and produced the resin varnish 5 and the adhesive film 5.

[Example 6]

In Example 1,

(1) The compounding quantity of the resin (Mitsubishi Gas Chemical Co., Ltd. "OPE-2St 2200" nonvolatile matter 60 mass % toluene solution) having a vinyl group is changed from 25 parts to 16.7 parts,

(2) The compounding quantity of indene coumarone resin ("H-100" manufactured by Nitto Chemical Co., Ltd.) was changed from 15 parts to 25 parts.

Except for the above, in the same manner as in Example 1, resin varnish 6 and adhesive film 6 were produced.

[Comparative Example 1]

In Example 1,

(1) changing the compounding quantity of resin (Mitsubishi Gas Chemical Co., Ltd. "OPE-2St 2200" toluene solution of 60 mass % non-volatile matter) having a vinyl group from 25 parts to 50 parts,

(2) The compounding quantity of indene coumarone resin ("H-100" manufactured by Nitto Chemical Co., Ltd.) was changed from 15 parts to 2 parts.

Except for the above, it carried out similarly to Example 1, and produced the resin varnish 7 and the adhesive film 7.

[Comparative Example 2]

In Example 1,

(1) The compounding quantity of resin (Mitsubishi Gas Chemical Co., Ltd. "OPE-2St 2200" nonvolatile matter 60 mass % toluene solution) having a vinyl group is changed from 25 parts to 8.3 parts,

(2) The compounding quantity of indene coumarone resin ("H-100" manufactured by Nitto Chemical Co., Ltd.) was changed from 15 parts to 34 parts.

Except for the above, it carried out similarly to Example 1, and produced the resin varnish 8 and the adhesive film 8.

[evaluation]

<Evaluation of genetic loss tangent>

The adhesive films produced in Examples and Comparative Examples were thermosetted at 190°C for 90 minutes, and the support was peeled to obtain a sheet-like cured product. The hardened|cured material was cut out to 80 mm in length and 2 mm in width, and it was set as the evaluation sample. With respect to this evaluation sample, the dielectric loss tangent was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C by the cavity resonance perturbation method using an HP8362B device manufactured by Agilent Technologies.

<Measurement of Minimum Melt Viscosity of Resin Composition Layer>

About the resin composition layer of the adhesive film produced by the Example and the comparative example, melt viscosity was measured using the dynamic viscoelasticity measuring apparatus ("Rheosol-G3000" manufactured by U.B.M Co., Ltd.). With respect to 1 g of the sample resin composition, using a parallel plate having a diameter of 18 mm, the temperature was increased from the starting temperature of 60°C to 200°C at a heating rate of 5°C/min, the measurement interval temperature was 2.5°C, the frequency was 1Hz, and the strain was 1deg. The dynamic viscoelastic modulus was measured as measurement conditions, and the minimum melt viscosity (poise) was computed.

<Evaluation of compatibility>

The resin composition layer side of the adhesive films produced in Examples and Comparative Examples was observed using a microscope (“DIGITAL MICROSCOPE KH-8700” manufactured by Hyrox Co., Ltd.), and the presence or absence of granulation was checked, and the following was evaluated on the basis of

-Criteria for compatibility-

(circle): 50 micrometers or more of granules did not precipitate in the resin composition layer of an adhesive film.

x: 50 micrometers or more of granules are deposited in the resin composition layer of an adhesive film.

[Measurement of plating adhesion]

<Preparation of evaluation substrate>

(1) Underlying treatment of inner-layer circuit board

Both sides of a glass cloth base epoxy resin double-sided copper clad laminate (copper foil thickness 18 µm, substrate thickness 0.4 mm, Panasonic Co., Ltd. "R1515A") on which an inner-layer circuit was formed was immersed in "CZ8101" manufactured by Mack Co., Ltd. and 1 µm etched to roughen the copper surface.

(2) Lamination of the adhesive film

The adhesive films produced in Examples and Comparative Examples were laminated using a batch-type vacuum pressure laminator (“MVLP-500” manufactured by Makey Co., Ltd.), so that the resin composition layer was bonded to the inner circuit board on both sides of the inner circuit board. laminated to After the lamination process was pressure-reduced for 30 second and air pressure was 13 hPa or less, it was performed by crimping|bonding at 100 degreeC and pressure 0.74 MPa for 30 second.

(3) Hardening of the resin composition layer

The PET film as a support was peeled off from the laminated adhesive film. Then, after preheating at 80°C for 30 minutes, the resin composition layer was thermosetted at 170°C for 30 minutes to form a cured product (insulating layer) on both surfaces of the inner circuit board.

(4) roughening treatment of cured product

An inner circuit board having a cured product formed on both sides is immersed in a swelling solution (Atotech Japan Co., Ltd. “Swelling Deep Secure P”, an aqueous sodium hydroxide solution containing diethylene glycol monobutyl ether) at 60° C. for 10 minutes. Then, it is immersed in the roughening solution (Atotech Japan Co., Ltd. "Concentrate Compact P", an aqueous solution having a potassium permanganate concentration of about 6% by mass and sodium hydroxide concentration of about 4% by mass) at 80° C. for 20 minutes, and finally It was immersed in the neutralization liquid (Atotech Japan Co., Ltd. product "reduction solution Securigant P", hydroxylamine sulfate aqueous solution) at 40 degreeC for 5 minutes. Then, it dried at 80 degreeC for 30 minutes.

(5) Formation of conductor layer

According to the semiadditive method, a conductor layer was formed on the roughened surface of the cured product.

That is, the substrate after the roughening treatment, the electroless containing PdCl ₂ was dipped and then immersed for 5 minutes at 40 ℃ in the plating solution, electroless copper plating solution for 20 minutes at 25 ℃. Then, after heating at 150 degreeC for 30 minute(s) and performing annealing process, the etching resist was formed and it pattern-formed by etching. Then, copper sulfate electroplating was performed, and the 30-micrometer-thick conductor layer was formed. The annealing treatment was performed at 200 degreeC for 60 minutes, and the evaluation board|substrate was obtained.

<Measurement of Peel Strength (Plating Adhesiveness) Between the Surface of the Cured Product and the Conductor Layer>

A load when a portion of 10 mm in width and 100 mm in length is cut in the conductor layer of the evaluation substrate, this end is peeled off and picked up with a clamp, and 35 mm is peeled off in the vertical direction at a rate of 50 mm/min at room temperature (25° C.) (kgf/cm) was measured and the peel strength was calculated|required. A tensile tester (Autocom type tester "AC-50C-SL" manufactured by TSE Corporation) was used for the measurement.

[Measurement of lower extremity adhesion]

(1) Base treatment of copper foil

The glossy surface of Mitsui Kinzokukozan Co., Ltd. 3EC-III (electric field copper foil, 35 μm) was immersed in MACETCH Bond CZ-8101 manufactured by MAC Co., Ltd., and roughening treatment (Ra value = 1 μm) was applied to the copper surface. Thus, a rust prevention treatment (CL8300) was performed. This copper foil is called CZ copper foil. Furthermore, it heat-processed in 130 degreeC oven for 30 minutes.

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

The same operation as "(2) Lamination of adhesive film" of the said [Measurement of plating adhesion] was performed, and the board|substrate which peeled the PET film which is a support body was prepared. On the resin composition layer, the treated surface of CZ copper foil of 3EC-III was laminated under the same conditions as in "(2) Lamination of adhesive film" in the above [Measurement of plating adhesion]. 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 (substrate adhesiveness)

The produced sample was cut into 150 x 30 mm small pieces. In the copper foil part of the small piece, an incision with a width of 10 mm and a length of 100 mm was inserted using a cutter, and one end of the copper foil was peeled off with a household tool (manufactured by TSE Co., Ltd., Autocom-type testing machine, AC-50C-SL). Using an Instron universal testing machine, the load at the time of peeling 35 mm in the vertical direction at a speed of 50 mm/min at room temperature was measured in accordance with JIS C6481, and was referred to as "substrate adhesiveness".

In a table|surface, content of (A) component, content of (B) component, content of (C)component, and content of (D)component shows content at the time of making a resin component 100 mass %.

From the table, it can be seen that Examples 1 to 6 containing component (D) in a predetermined amount and containing component (C) have high compatibility, excellent dielectric loss tangent and melt viscosity, and excellent plating adhesion and substrate adhesion. Able to know.

On the other hand, as for the comparative example 2 with much content of (D)component, the minimum melt viscosity becomes low, and it turns out that base|substrate adhesiveness is inferior compared with Examples 1-6.

Moreover, in the comparative example 1 with little content of (D)component, compatibility was bad, the crystal|crystallization precipitated on the adhesive film, and the minimum melt viscosity could not be measured. Further, the compatibility was poor, and the insulating layer could not be formed, and the dielectric loss tangent, plating adhesion, and substrate adhesion could not be measured.

Claims (11)

A resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) a resin having a vinyl group, and (D) an indene coumarone resin,
(C) When content of a component makes a resin component 100 mass %, it is 5 mass % - 20 mass %,
(D) When content of a component makes a resin component 100 mass %, it is 5 mass % - 20 mass %,
(C) The component is a resin represented by the following formula (1), the resin composition.
[ Formula 1 ]

(In Formula 1, R ¹ to R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and A represents a group represented by Formula 2 or Formula 3 below.)
[ Formula 2 ]

(In Formula 2, E represents Formula E-1, E-2, or E-3 below.)
[ Formula 3 ]

(In Formula 3, R ^{7 To} R ¹⁴ Each independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, E represents the following Formula E-1, E-2 or E-3, a, b represents an integer from 0 to 100 in which at least one of them is not 0.)
[ Formula 4 ]
[Formula E-1]

[Formula E-2]

[Formula E-3]

(In Formulas E-1 to E-3, R ¹⁵ to R ³⁴ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and G is a straight chain or branched carbon atom having 20 or less carbon atoms. or a cyclic divalent hydrocarbon group.) The resin composition according to claim 1, wherein at least one of component (C) has an aromatic ring. The resin composition according to claim 1, wherein at least one of component (B) is an active ester curing agent. The resin composition according to claim 1, further comprising (E) an inorganic filler. The resin composition of Claim 4 whose content of (E) component is 50 mass % or more, when the non-volatile component of a resin composition is 100 mass %. The resin composition according to claim 1, wherein the component (D) is a copolymer of indene, coumarone and styrene. The resin composition according to claim 1, which is for forming an insulating layer of a printed wiring board. An adhesive film having a support and a resin composition layer formed on the support and comprising the resin composition according to any one of claims 1 to 7. The printed wiring board containing the insulating layer formed with the hardened|cured material of the resin composition in any one of Claims 1-7. A semiconductor device comprising the printed wiring board according to claim 9 . delete