Resin composition, sheet-like laminate, printed wiring board, and semiconductor device

Abstract

The problem of the present invention is to provide a resin composition with low dielectric loss tangent and good plating adhesion and substrate adhesion. The solution of the present invention is a resin composition comprising: (A) an epoxy resin, (B) a curing agent, (C) a resin having a free radical polymerizable unsaturated group, and (D) an aliphatic phosphine compound.

Description

Technical Field

[0001] The present invention relates to a resin composition and further to a sheet-like laminated material, a printed wiring board and a semiconductor device using the resin composition. Background Art

[0002] As a manufacturing technology for printed wiring boards, a manufacturing method using a build-up method in which an insulating layer and a conductor layer are alternately stacked on an inner substrate is known. In the manufacturing method using the build-up method, the insulating layer is generally formed by curing a resin composition. For example, Patent Document 1 describes a resin composition characterized in that it contains (A) a free radical polymerizable compound, (B) an epoxy resin, (C) a curing agent, and (D) a roughening component.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2014-034580 Summary of the invention

[0006] Technical problem to be solved by the invention

[0007] In recent years, there has been an increasing demand for resin compositions that can form insulating layers with low dielectric loss tangents. In addition, electronic devices have been increasingly miniaturized and improved in performance, and printed wiring boards are being required to have more layers stacked, miniaturized, and denser wiring.

[0008] In order to achieve further miniaturization and high density of wiring, a resin composition having low dielectric loss tangent and good plating adhesion and base adhesion is required, but the current situation is that all these requirements cannot be fully met.

[0009] An object of the present invention is to provide a resin composition having a low dielectric loss tangent and excellent plating layer adhesion and base adhesion.

[0010] Technical solutions adopted to solve technical problems

[0011] The present inventors have conducted intensive studies on the above-mentioned subject (technical problem) and have found that the above-mentioned subject can be solved by adding (C) a resin having a free radical polymerizable unsaturated group and (D) an aliphatic phosphine compound in combination to a resin composition comprising (A) an epoxy resin and (B) a curing agent, thereby completing the present invention.

[0012] That is, the present invention includes the following contents.

[0013] [1] A resin composition comprising: (A) an epoxy resin, (B) a curing agent, (C) a resin having a radical polymerizable unsaturated group, and (D) an aliphatic phosphine compound.

[0014] [2] The resin composition according to [1], wherein the component (D) has a phosphorus atom directly bonded to an aliphatic carbon atom.

[0015] [3] The resin composition according to [1] or [2], wherein the component (D) has 1 to 4 phosphorus atoms directly bonded to an aliphatic carbon atom in one molecule.

[0016] [4] The resin composition according to any one of [1] to [3], wherein the component (D) has 2 to 40 aliphatic carbon atoms in one molecule.

[0017] [5] The resin composition according to any one of [1] to [4], wherein the component (D) is a compound represented by formula (D1) or formula (D2):

[0018] [Chemistry 1]

[0019]

[0020] In the formula,

[0021] R d1 and R d2 Each independently represents a hydrogen atom or is of the formula: -(RO) l - a monovalent group represented by R', wherein l represents an integer of 0 to 5, R represents a divalent aromatic group which may have a substituent, or a divalent aliphatic group which may have a substituent, and R' represents a monovalent aromatic group which may have a substituent, or a monovalent aliphatic group which may have a substituent, and when there are multiple R's, they may be the same or different from each other;

[0022] R d3 Expressed in the formula: -(R"-O) m - a monovalent group represented by R"', wherein m represents an integer of 0 to 5, R" represents a divalent aliphatic group which may have a substituent, and R"' represents a monovalent aliphatic group which may have a substituent, and when there are multiple R", they may be the same or different from each other;

[0023] [Chemistry 2]

[0024]

[0025] In the formula,

[0026] R d1 and R d2 Synonymous with above;

[0027] L represents the formula: -(R"-O) n -R"- represents a divalent group, wherein n represents an integer of 0 to 5, R" has the same meaning as above, and when there are multiple R", they may be the same as or different from each other;

[0028] R d4 and R d5 Each independently represents a hydrogen atom, with the formula: -(RO) l -R' represents a monovalent group or a monovalent group of the formula: -LP(-R d1 )(-R d2 ) represents a monovalent group, where l, R, R', L, R d1 and R d2 Synonymous with above.

[0029] [6] The resin composition according to any one of [1] to [5], wherein the component (D) includes a compound represented by any one of the following formulae.

[0030] [Chemistry 3]

[0031]

[0032]

[0033] [7] The resin composition according to any one of [1] to [6], wherein the content of the component (D) is 0.001% by mass to 10% by mass when the resin component is 100% by mass.

[0034] [8] The resin composition according to any one of [1] to [7], wherein the component (A) contains a biphenyl epoxy resin.

[0035] [9] The resin composition according to any one of [1] to [8], wherein the component (B) contains an active ester curing agent.

[0036]

[10] The resin composition according to any one of [1] to [9], wherein the component (C) has a carbon-carbon double bond.

[0037]

[11] The resin composition according to any one of [1] to

[10] , wherein the component (C) has one or more groups selected from the group consisting of an acryloyl group, a methacryloyl group, a styryl group, an allyl group, a vinyl group, a propenyl group and a maleimide group.

[0038]

[12] The resin composition according to any one of [1] to

[11] , further comprising (E) an inorganic filler.

[0039]

[13] The resin composition according to

[12] , wherein the content of the (E) inorganic filler is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass.

[0040]

[14] The resin composition according to any one of [1] to

[13] , which is used for an insulating layer for forming a conductor layer.

[0041]

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

[14] .

[0042]

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

[14] .

[0043]

[17] A semiconductor device comprising a cured product of the resin composition according to any one of [1] to

[14] .

[0044] According to the present invention, it is possible to provide a resin composition having a low dielectric loss tangent and excellent plating adhesion and substrate adhesion. DETAILED DESCRIPTION

[0045] <Explanation of terms>

[0046] In this specification, "aliphatic phosphine compounds" refer to compounds in which at least one of the organic groups bonded (combined) to the phosphorus atom in an organic phosphine compound is an aliphatic group. In this specification, an aliphatic group broadly represents a non-aromatic organic group, and in addition to (i) a non-aromatic hydrocarbon group, it also includes (ii) a non-aromatic organic group containing heteroatoms such as oxygen atoms, nitrogen atoms, sulfur atoms, boron atoms and silicon atoms. In the case where the aliphatic group is a non-aromatic organic group containing heteroatoms, the carbon atom of the organic group is bonded to the phosphorus atom. Therefore, the "aliphatic phosphine compounds" in the present invention are characterized in that they contain a phosphorus atom directly bonded to an aliphatic carbon atom.

[0047] In the present specification, the phrase “may have a substituent” immediately before a group refers to both the case where hydrogen atoms of the group are not substituted by a substituent and the case where part or all of the hydrogen atoms of the group are substituted by a substituent.

[0048] In the present specification, unless otherwise specified, the term "substituent" means a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a monovalent heterocyclic group, an alkylidene group, an amino group, a silyl group, a phosphino group, a mercapto group, a formyl group, an acyl group, an acyloxy group, a carboxyl group, a cyano group, a nitro group, a hydroxyl group and an oxo group.

[0049] As the halogen atom which can be used as a substituent, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be mentioned. The alkyl group which can be used as a substituent may be either linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 3. The number of carbon atoms of the cycloalkyl group which can be used as a substituent is preferably 3 to 12, and more preferably 3 to 6. The alkoxy group which can be used as a substituent may be either linear or branched. The number of carbon atoms of the alkoxy group is preferably 1 to 12, and more preferably 1 to 6. The number of carbon atoms of the cycloalkyloxy group which can be used as a substituent is preferably 3 to 12, and more preferably 3 to 6. The number of carbon atoms of the aryl group which can be used as a substituent is preferably 6 to 14, and more preferably 6 to 10. The number of carbon atoms of the aryloxy group which can be used as a substituent is preferably 6 to 14, and more preferably 6 to 10. The number of carbon atoms of the arylalkyl group which can be used as a substituent is preferably 7 to 15, and more preferably 7 to 11. The number of carbon atoms of the arylalkoxy group which can be used as a substituent is preferably 7 to 15, more preferably 7 to 11. The monovalent heterocyclic group which can be used as a substituent refers to a group obtained by removing one hydrogen atom from the heterocycle of a heterocyclic compound. The number of carbon atoms of the monovalent heterocyclic group is preferably 3 to 15, more preferably 3 to 9. The monovalent heterocyclic group also includes a monovalent aromatic heterocyclic group (heteroaryl). The alkylidene group which can be used as a substituent refers to a group obtained by removing two hydrogen atoms from the same carbon atom of an alkane. The number of carbon atoms of the alkylidene group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. The amino group, silyl group, phosphino group and mercapto group which can be used as a substituent refer to a group represented by the formula: -NH2, a group represented by the formula: -SiH3, a group represented by the formula: -PH2, and a group represented by the formula: -SH, respectively. The acyl group which can be used as a substituent refers to a group represented by the formula: -C(=O)-R S The group represented by (wherein R S is an alkyl or aryl group). S The alkyl group represented by may be straight chain or branched. The number of carbon atoms in the acyl group is preferably 2 to 13, more preferably 2 to 7. The acyloxy group which can be used as a substituent is a group of the formula: -OC(=O)-R S The group represented by (wherein R S The acyloxy group preferably has 2 to 13 carbon atoms, more preferably 2 to 7 carbon atoms. The above substituents may further have a substituent (sometimes referred to as a "secondary substituent"). As the secondary substituent, the same groups as the above substituents may be used unless otherwise specified. As a substituent having a secondary substituent, for example, dimethylamino can be mentioned.

[0050] Hereinafter, the present invention will be described in detail in conjunction with its preferred embodiments.

[0051] [Resin composition]

[0052] The resin composition of the present invention is characterized by comprising (A) an epoxy resin, (B) a curing agent, (C) a resin having a radical polymerizable unsaturated group, and (D) an aliphatic phosphine compound.

[0053] The resin composition of the present invention, in which (C) a resin having a free radical polymerizable unsaturated group and (D) an aliphatic phosphine compound are combined in a resin composition comprising (A) an epoxy resin and (B) a curing agent, can produce a cured product having a low dielectric loss tangent, good plating adhesion (adhesion to the plated conductor layer) and good base adhesion (adhesion to the base conductor layer).

[0054] <(A) Epoxy resin>

[0055] The resin composition of the present invention contains an epoxy resin as component (A). Examples of the epoxy resin include bisphenol epoxy resin, dicyclopentadiene epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butylcatechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro-containing epoxy resin, cyclohexane epoxy resin, cyclohexanedimethanol epoxy resin, naphthylene ether epoxy resin, trimethylol epoxy resin, and tetraphenylethane epoxy resin. One epoxy resin may be used alone or in combination of two or more. Bisphenol epoxy resin refers to an epoxy resin having a bisphenol structure, and examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and bisphenol AF epoxy resin. Biphenyl epoxy resin refers to an epoxy resin having a biphenyl structure; here, the biphenyl structure may have substituents such as alkyl, alkoxy, and aryl groups. Therefore, bixylenol epoxy resin and biphenyl aralkyl epoxy resin are also included in biphenyl epoxy resin.

[0056] As epoxy resin, aromatic epoxy resin is preferred. Here, aromatic epoxy resin refers to epoxy resin having aromatic ring in its molecule. Aromatic includes not only monocyclic structures such as benzene ring, but also polycyclic aromatic structures and aromatic heterocyclic structures such as naphthalene ring. Among them, from the viewpoint of achieving good coating adhesion and substrate adhesion in the combination with (C) component and (D) component, (A) component is preferably selected from bisphenol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, naphthalene type tetrafunctional epoxy resin and naphthol type epoxy resin. One or more, more preferably selected from bisphenol type epoxy resin and biphenyl type epoxy resin, further preferably biphenyl type epoxy resin. In a preferred embodiment, (A) component contains biphenyl type epoxy resin.

[0057] The epoxy resin preferably has two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more.

[0058] Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter also referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter also referred to as "solid epoxy resins"). In the resin composition of the present invention, as component (A), a liquid epoxy resin may be included alone, a solid epoxy resin may be included alone, or a liquid epoxy resin and a solid epoxy resin may be included in combination. Among them, in the resin composition of the present invention, as component (A), it is preferred to include a solid epoxy resin, and it is more preferred to include a solid epoxy resin alone, or a liquid epoxy resin and a solid epoxy resin may be included in combination.

[0059] The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule.

[0060] As solid epoxy resins, preferred are biphenyl type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol type epoxy resins, and tetraphenylethane type epoxy resins; more preferred are dimethylphenol type epoxy resins, biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, naphthalene type tetrafunctional epoxy resins and naphthol type epoxy resins; and further preferred is dimethylphenol type epoxy resins.

[0061] Specific examples of solid epoxy resins include: "HP4032H" manufactured by DIC Corporation (naphthalene-type epoxy resin); "HP-4700" and "HP-4710" manufactured by DIC Corporation (naphthalene-type tetrafunctional epoxy resin); "N-690" manufactured by DIC Corporation (cresol novolac-type epoxy resin); "N-695" manufactured by DIC Corporation (cresol novolac-type epoxy resin); "HP-7200" manufactured by DIC Corporation (dicyclopentadiene-type epoxy resin); and "HP-7200" manufactured by DIC Corporation (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-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol phenolic type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl aralkyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.; "ESN485" (naphthol phenolic type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (biphenyl phenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "YX8800" (anthracene type epoxy resin) manufactured by Osaka Gas Chemical Co., Ltd.; "PG-100" and "CG-500" (bisphenol AF type epoxy resin) manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These solid epoxy resins may be used alone or in combination of two or more.

[0062] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule, more preferably an aromatic liquid epoxy resin having two or more epoxy groups in one molecule.

[0063] As liquid epoxy resins, preferred are bisphenol type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure. More preferred are glycidyl amine type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins and naphthalene type epoxy resins, and particularly preferred is bisphenol A type epoxy resin.

[0064] Specific examples of liquid epoxy resins include: "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "jER828US", "jER828EL", "825", and "EPIKOTE 828EL" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" and "630LSD" (glycidylamine-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemicals Corporation; Nagase "EX-721" (glycidyl ester type epoxy resin) manufactured by ChemteX; "CELLOXIDE 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel Corporation; "PB-3600" (epoxy resin with butadiene structure) manufactured by Daicel Corporation; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation. These liquid epoxy resins can be used alone or in combination of two or more.

[0065] When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the mass ratio of them (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:15, more preferably 1:0.5 to 1:10, and particularly preferably 1:1 to 1:8. By making the mass ratio of the liquid epoxy resin to the solid epoxy resin within the above range, it is possible to obtain the following effects: i) moderate adhesion when used in the form of a sheet-like laminated material, ii) sufficient flexibility and improved operability when used in the form of a sheet-like laminated material, and iii) an insulating layer having sufficient breaking strength.

[0066] The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, further preferably 80 to 2000, and particularly preferably 110 to 1000. By making the epoxy equivalent of the epoxy resin within the above range, the crosslinking density of the cured product of the resin composition becomes sufficient, and an insulating layer with a small surface roughness can be obtained. It should be noted that the epoxy equivalent is the mass of the resin containing 1 equivalent of epoxy groups, and can be measured according to JIS K7236.

[0067] The weight average molecular weight of the epoxy resin is preferably from 100 to 5000, more preferably from 250 to 3000, further preferably from 400 to 1500. The weight average molecular weight of a resin such as an epoxy resin is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0068] From the viewpoint of obtaining the cured product showing good mechanical strength and insulation reliability, the content of (A) component in resin combination is preferably more than 3 mass %, more preferably more than 5 mass %, further more preferably more than 8 mass %.As long as the effect of the present invention is brought into play, the upper limit of the content of (A) component is not particularly limited, but preferably below 70 mass %, more preferably below 50 mass %, further more preferably below 30 mass % or below 20 mass %.

[0069] In addition, in this invention, the content of each component which comprises a resin composition is a value when the total amount of the non-volatile component in a resin composition is set to 100 mass %.

[0070] <(B) Curing agent>

[0071] The resin composition of the present invention includes a curing agent as component (B). The curing agent is not particularly limited as long as it has the function of curing the epoxy resin, and examples thereof include phenol curing agents, naphthol curing agents, active ester curing agents, benzoxazine curing agents, cyanate curing agents, and carbodiimide curing agents. The curing agent may be used alone or in combination of two or more.

[0072] As phenolic curing agent and naphthol curing agent, from the viewpoint of heat resistance and water resistance, preferably, there is a phenolic curing agent of phenolic (novolac) structure or a naphthol curing agent with phenolic structure. In addition, from the viewpoint of the adhesion strength (peel strength) with the conductor layer, preferably, there is a nitrogen-containing phenolic curing agent or a nitrogen-containing naphthol curing agent, and more preferably, there is a phenolic curing agent containing a triazine skeleton or a naphthol curing agent containing a triazine skeleton. Among them, from the viewpoint of making heat resistance, water resistance and the adhesion strength with the conductor layer highly satisfied, preferably, there is a phenolic novolac resin containing a triazine skeleton. Specific examples of phenol-based curing agents and naphthol-based curing agents include: "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemicals Co., Ltd., "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", and "SN-395" manufactured by Nippon Steel & Sumitomo Metal Chemicals Corporation, and "LA-7052", "LA-7054", "LA-3018", "LA-1356", and "TD2090" manufactured by DIC Corporation.

[0073] As active ester curing agent, there is no particular limitation, and generally preferably used are compounds having ester groups with more than 2 high reactive activities in 1 molecule, such as phenol ester, thiophenol ester, N-hydroxylamine ester, ester of heterocyclic hydroxy compound, etc. The active ester curing agent is preferably a compound obtained by the condensation reaction of carboxylic acid compound and / or thiocarboxylic acid compound with hydroxy compound and / or thiol compound. In particular, from the viewpoint of improving heat resistance, it is preferably an active ester curing agent obtained by carboxylic acid compound and hydroxy compound, and more preferably an active ester curing agent obtained by carboxylic acid compound and phenol compound and / or naphthol compound. As carboxylic acid compound, for example: benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. can be cited. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, 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, phloroglucinol, pyrogallol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0074] Specifically, preferred are active ester compounds containing dicyclopentadiene-type diphenol structures, active ester compounds containing naphthalene structures, active ester compounds containing acetylated products of phenol novolacs, and active ester compounds containing benzoylated products of phenol novolacs, and more preferred are active ester compounds containing naphthalene structures and active ester compounds containing dicyclopentadiene-type diphenol structures. "Dicyclopentadiene-type diphenol structures" means a divalent structural unit formed of phenylene-dicyclopentylene-phenylene.

[0075] As commercially available products of active ester curing agents, active ester compounds containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (manufactured by DIC Corporation), etc.; active ester compounds containing a naphthalene structure include "EXB9416-70BK" (manufactured by DIC Corporation), etc.; active ester compounds containing acetylated products of phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation), etc.; active ester compounds containing benzoylated products of phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), etc.

[0076] Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Highpolymer Co., Ltd. and "Pd" and "Fa" manufactured by Shikoku Chemicals Co., Ltd.

[0077] Examples of the cyanate curing agent include difunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyl dicyanate, 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-(methylethylene))benzene, bis(4-cyanatephenyl)sulfide, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers obtained by triazinizing a portion of these cyanate resins. Specific examples of cyanate curing agents include "PT30" and "PT60" manufactured by Lonza Japan Co., Ltd. (both are phenol novolac-type multifunctional cyanate resins), and "BA230" (a prepolymer in which a part or all of bisphenol A dicyanate is triazine-formulated to form a trimer).

[0078] Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

[0079] The component (B) preferably contains an active ester curing agent from the viewpoint of obtaining a cured product having good heat resistance and achieving good plating adhesion and base adhesion in combination with the component (C) and the component (D).

[0080] The amount ratio of (A) epoxy resin to (B) curing agent is preferably in the range of 1:0.2 to 1:2, more preferably in the range of 1:0.3 to 1:1.5, and further preferably in the range of 1:0.4 to 1:1.2, in terms of the ratio of [the total number of epoxy groups of the epoxy resin]:[the total number of reactive groups of the curing agent]. Here, the reactive group of the curing agent refers to an active hydroxyl group, an active ester group, etc., which varies depending on the type of curing agent. In addition, the total number of epoxy groups of the epoxy resin refers to the value obtained by summing up the values ​​obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins. The total number of reactive groups of the curing agent refers to the value obtained by summing up the values ​​obtained by dividing the solid content mass of each curing agent by the reactive group equivalent for all curing agents. By making the amount ratio of the epoxy resin to the curing agent within such a range, the heat resistance of the resulting insulating layer is further improved.

[0081] <(C) Resin having a radically polymerizable unsaturated group>

[0082] In the resin composition of the present invention, a resin having a free radical polymerizable unsaturated group (also referred to as an olefinic or acetylenic unsaturated group) is included as component (C). In the following description, the "resin having a free radical polymerizable unsaturated group" as component (C) is sometimes referred to as an "unsaturated resin". For a carbon-carbon unsaturated bond (olefinic or acetylenic unsaturated bond) having free radical polymerizability, one molecule of the unsaturated resin (C) may contain only one or more. The cured product of the resin composition containing the unsaturated resin (C) usually contains a molecular structure portion formed by the reaction of the unsaturated bond portion of the unsaturated resin (C). As a result, the polarity of the cured product is reduced, and the value of the dielectric loss tangent can be reduced. Component (C) can be used alone or in combination of two or more.

[0083] The free radical polymerizable unsaturated group possessed by the (C) unsaturated resin is preferably an ethylenically unsaturated group having a carbon-carbon double bond. Therefore, in one embodiment, the (C) component has a carbon-carbon double bond. In a more preferred embodiment, the free radical polymerizable unsaturated group is preferably a group selected from one or more of acryloyl, methacryloyl, styryl, alkenyl and maleimide. As a preferred example of alkenyl, allyl, vinyl and propenyl can be cited. Therefore, in a preferred embodiment, the (C) component has a group selected from one or more of acryloyl, methacryloyl, styryl, allyl, vinyl, propenyl and maleimide.

[0084] The unsaturated resin (C) is preferably a resin having a cyclic ether structure with 5 or more ring members (hereinafter also referred to as "unsaturated resin containing a cyclic ether structure"). The unsaturated resin containing a cyclic ether structure generally has restricted molecular motion, and thus can effectively reduce dielectric loss tangent.

[0085] The unsaturated resin containing a cyclic ether structure may contain only one cyclic ether structure or may contain a plurality of cyclic ether structures.

[0086] The cyclic ether structure may have a monocyclic structure including only one ring, may have a polycyclic structure including two or more rings, or may have a condensed ring structure including condensed rings.

[0087] From the viewpoint of remarkably obtaining the desired effect of the present invention, the number of oxygen atoms contained in one cyclic ether structure is preferably at least 1, more preferably at least 2, and is preferably at most 5, more preferably at most 4, further preferably at most 3.

[0088] The cyclic ether structure is preferably a 5- to 10-membered ring, more preferably a 5- to 8-membered ring, and further preferably a 5- to 6-membered ring. Specific examples of cyclic ether structures having more than 5-membered rings include furan structure, tetrahydrofuran structure, dioxolane structure, pyran structure, dihydropyran structure, tetrahydropyran structure, and dioxane structure. Among them, from the viewpoint of improving the compatibility of the resin composition, a dioxane structure is preferred. The dioxane structure includes a 1,2-dioxane structure, a 1,3-dioxane structure, and a 1,4-dioxane structure, and a 1,3-dioxane structure is preferred.

[0089] The cyclic ether structure may have a substituent. The type of the substituent is not particularly limited, and may be any of the substituents described above, for example, an alkyl group and an alkoxy group. The number of carbon atoms of the substituent is as described above, preferably 1 to 6, more preferably 1 to 3.

[0090] Among the unsaturated resins containing a cyclic ether structure, a resin having a vinyl group is preferred. By using an unsaturated resin having a vinyl group and a cyclic ether structure (i.e., a resin having a vinyl group as a free radical polymerizable unsaturated group and having a cyclic ether structure of more than 5-membered rings) as the unsaturated resin (C), the desired effect of the present invention can be significantly obtained. Furthermore, the dielectric loss tangent of the resin composition can usually be effectively reduced.

[0091] If we list the preferred examples of the unsaturated resin (C), we can list the compound represented by the following formula (C1), the compound represented by the following formula (C6), the compound represented by the following formula (C7), the compound represented by the following formula (C9), and the compound represented by the following formula (C10). Among them, the compound represented by the formula (C7) is an unsaturated resin containing a cyclic ether structure, which is particularly preferred. The unsaturated resin (C) can also be a benzocyclobutene resin.

[0092] [Chemistry 4]

[0093]

[0094] In formula (C1), R 1 ~R 6 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. In formula (C1), A represents a divalent group represented by the following formula (C2) or (C3).

[0095] [Chemistry 5]

[0096] -CH2-OBO-CH2- (C2)

[0097] In formula (C2), B represents a divalent group represented by the following formula (C2-1), (C2-2) or (C2-3).

[0098] [Chemistry 6]

[0099]

[0100] In formula (C2-1), R 15 ~R 18 Each independently represents a hydrogen atom, an alkyl group having at most 6 carbon atoms or a phenyl group, and preferably represents a hydrogen atom or a methyl group.

[0101] In formula (C2-2), R 19 ~R 26 Each independently represents a hydrogen atom, an alkyl group having at most 6 carbon atoms or a phenyl group, and preferably represents a hydrogen atom or a methyl group.

[0102] In formula (C2-3), R 27 ~R 34 Each independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, preferably a hydrogen atom or a methyl group. In formula (C2-3), E represents a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

[0103] [Chemistry 7]

[0104]

[0105] In formula (C3), D represents a divalent group represented by the following formula (C4).

[0106] [Chemistry 8]

[0107]

[0108] In formula (C4), R 7 ~R 14Each independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and preferably represents a hydrogen atom or a methyl group. 7 , R 8 , R 13 and R 14 , more preferably methyl. In formula (C4), a and b are integers of 0 or more and 100 or less, at least one of which is not 0. In formula (C4), B represents a divalent group represented by the above formula (C2-1), (C2-2) or (C2-3).

[0109] The compound represented by the above formula (C1) is preferably a compound represented by the following formula (C5).

[0110] [Chemistry 9]

[0111]

[0112] In formula (C5), R 1 ~R 6 and R in the formula (C1) 1 ~R 6 B has the same meaning as B in the formula (C2), and a and b have the same meaning as a and b in the formula (C4).

[0113] [Chemistry 10]

[0114]

[0115] [Chemistry 11]

[0116]

[0117] In formula (C7), ring F represents a divalent group having a cyclic ether structure having 5 or more members. The range of the cyclic ether structure is as described above. In addition, the cyclic ether structure may have a substituent as described above.

[0118] Examples of the divalent group having a cyclic ether structure having a 5-membered ring or more include furan-2,5-diyl, tetrahydrofuran-2,5-diyl, dioxolane-2,5-diyl, pyran-2,5-diyl, dihydropyran-2,5-diyl, tetrahydropyran-2,5-diyl, 1,2-dioxane-3,6-diyl, 1,3-dioxane-2,5-diyl, 1,4-dioxane-2,5-diyl, and 5-ethyl-1,3-dioxane-2,5-diyl. Among them, 5-ethyl-1,3-dioxane-2,5-diyl is preferred.

[0119] In formula (C7), B 1 and B 2 Each independently represents a single bond or a divalent linking group. 1 and B 2The divalent linking group is preferably a divalent linking group. Examples of the divalent linking group include an alkylene group which may have a substituent, an alkenylene group which may have a substituent, an alkynylene group which may have a substituent, an arylene group which may have a substituent, a heteroarylene group which may have a substituent, a group represented by -COO-, a group represented by -CO-, a group represented by -CONH-, a group represented by -NHCONH-, a group represented by -NHCOO-, a group represented by -C(=O)-, a group represented by -S-, a group represented by -SO-, a group represented by -NH-, and a group obtained by combining a plurality of these groups.

[0120] Among them, B 1 and B 2 Preferably, it is a group obtained by combining two or more groups selected from an alkylene group which may have a substituent, an alkenylene group which may have a substituent, an alkynylene group which may have a substituent, a group represented by -COO-, and a group represented by -O-. In particular, B 1 and B 2 More preferably, it is a group obtained by combining two or more groups selected from an alkylene group which may have a substituent and a group represented by -COO-.

[0121] In formula (C7), C 1 and C 2 Each independently represents a functional group. Examples of the functional group include vinyl, methacryloyl, acryloyl, allyl, styryl, propenyl, and epoxy. In a preferred embodiment, C 1 and C 2 For vinyl.

[0122] Specific examples of the compound represented by the formula (C7) include compounds represented by the following formula (C8).

[0123] [Chemistry 12]

[0124]

[0125] [Chemistry 13]

[0126]

[0127] [Chemistry 14]

[0128]

[0129] In the formula (C10), n represents 1 to 5.

[0130] Examples of the unsaturated resin (C) include “OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Co., Ltd. (styrene-modified polyphenylene ether resin, number average molecular weight 1200, corresponding to the above formula (C5)), “YL7776” manufactured by Mitsubishi Chemical Corporation (bimethylol diallyl ether resin, number average molecular weight 331, corresponding to the above formula (C6)), “A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd. (dioxane acrylic acid monomer diol diacrylate, number average molecular weight 326, corresponding to the above formula (C8)), “KAYARAD R-604” manufactured by Nippon Kayaku Co., Ltd. (equivalent to the above formula (C8)), “A-DCP” manufactured by Shin-Nakamura Chemical Co., Ltd. (tricyclodecane dimethanol diacrylate, number average molecular weight 304, equivalent to the above formula (C9)), and “MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd. (equivalent to the above formula (C10)). The (C) unsaturated resin may be used alone or in combination of two or more.

[0131] The number average molecular weight of the unsaturated resin (C) is preferably 100 or more, more preferably 200 or more, preferably 10,000 or less, and more preferably 3,000 or less. By making the number average molecular weight of the unsaturated resin (C) within the above range, the volatilization of the resin varnish during drying can be suppressed, or the melt viscosity of the resin composition can be suppressed from becoming too large. The number average molecular weight can be measured as a polystyrene-converted value by gel permeation chromatography (GPC). The determination of the number average molecular weight by the GPC method can be performed, for example, using "LC-9A / RID-6A" manufactured by Shimadzu Corporation as a measuring device, using "Shodex K-800P / K-804L / K-804L" manufactured by Showa Denko K.K. as a column, using chloroform as a mobile phase, and measuring at a column temperature of 40°C.

[0132] From the viewpoint of obtaining the resin composition that brings the low cured product of dielectric loss tangent, the content of (C) component in the resin composition is preferably more than 1 mass %, more preferably more than 3 mass % or more than 5 mass %. From the viewpoint that the compatibility of resin composition is improved, the upper limit of the content of (C) component is preferably below 20 mass %, more preferably below 15 mass % or below 10 mass %.

[0133] <(D) Aliphatic phosphine compounds>

[0134] The resin composition of the present invention contains an aliphatic phosphine compound as component (D). By combining the component (D) with the component (C), a resin composition having a low dielectric loss tangent and good coating adhesion and substrate adhesion can be obtained.

[0135] As mentioned above, by incorporating component (C), the dielectric loss tangent of the cured product of the resin composition can be reduced. However, on the other hand, the inventors found that the cured product had poor coating adhesion and substrate adhesion. The inventors have conducted a serious study on the above-mentioned subject and found that by incorporating component (D) in combination with component (C), a resin composition can be achieved, which can bring about a cured product with good coating adhesion and substrate adhesion while maintaining the advantages of using component (C) such as reducing the dielectric loss tangent of the cured product of the resin composition.

[0136] As mentioned above, the feature of component (D) is that it contains phosphorus atoms directly bonded to aliphatic carbon atoms. In this regard, the inventors of the present invention have confirmed that even if it is an organic phosphine compound, a compound without phosphorus atoms directly bonded to aliphatic carbon atoms cannot achieve the desired effect in combination with component (C) (Comparative Example 2 described later). By directly bonding aliphatic carbon atoms showing electron donating properties to phosphorus atoms, the phosphorus atoms are in an electron-rich state. The electron-rich phosphorus atoms are believed to play a role in promoting the reaction of component (A) and component (C), reproducing the cured product composition that helps to adhere to the conductor. From the viewpoint of realizing a resin composition that brings about a cured product with better coating adhesion and substrate adhesion, component (D) preferably contains phosphorus atoms directly bonded to both aliphatic carbon atoms and aromatic carbon atoms.

[0137] The number of phosphorus atoms directly bonded to an aliphatic carbon atom contained in each molecule of the component (D) is not particularly limited, and is usually 1 to 10, preferably 1 to 8, more preferably 1 to 6, 1 to 4 or 1 to 3, and further preferably 1 or 2. As long as the component (D) contains phosphorus atoms directly bonded to an aliphatic carbon atom, the component (D) may contain phosphorus atoms not directly bonded to an aliphatic carbon atom in its molecule.

[0138] The number of aliphatic carbon atoms contained in each molecule of the (D) component is not particularly limited, and is preferably 2 or more, and more preferably 3 or more or 4 or more. Here, the number of aliphatic carbon atoms refers to the total number of carbon atoms contained in the (D) component excluding aromatic carbon atoms. For example, when there are 2 phenyl groups and 1 cyclohexyl group in one molecule of the (D) component, the number of aliphatic carbon atoms is 6. In addition, when there are 1 phenyl group and 2 cyclooctyl groups in one molecule of the (D) component, the number of aliphatic carbon atoms is 16. The upper limit of the number of aliphatic carbon atoms contained in each molecule of the (D) component is not particularly limited, and is usually 100 or less, preferably 80 or less, more preferably 60 or less, and further preferably 40 or less, 20 or less, 12 or less, or 8 or less.

[0139] In one embodiment, the component (D) is a compound represented by the following formula (D1) or formula (D2).

[0140] [Chemistry 15]

[0141]

[0142] In formula (D1),

[0143] R d1 and R d2 Each independently represents a hydrogen atom or is of the formula: -(RO) l - a monovalent group represented by R', wherein l represents an integer of 0 to 5, R represents a divalent aromatic group which may have a substituent or a divalent aliphatic group which may have a substituent, and R' represents a monovalent aromatic group which may have a substituent or a monovalent aliphatic group which may have a substituent, and when there are multiple R's, they may be the same as or different from each other;

[0144] R d3 Expressed in the formula: -(R"-O) m - a monovalent group represented by R"', wherein m represents an integer of 0 to 5, R" represents a divalent aliphatic group which may have a substituent, and R"' represents a monovalent aliphatic group which may have a substituent, and when there are multiple R", they may be the same or different from each other;

[0145] [Chemistry 16]

[0146]

[0147] In formula (D2),

[0148] R d1 and R d2 Synonymous with above;

[0149] L represents the formula: -(R"-O) n -R"- represents a divalent group, wherein n represents an integer of 0 to 5, R" has the same meaning as above, and when there are multiple R", they may be the same as or different from each other;

[0150] R d4 and R d5 Each independently represents a hydrogen atom, with the formula: -(RO) l -R' represents a monovalent group or a monovalent group of the formula: -LP(-R d1 )(-R d2 ) represents a monovalent group, where l, R, R', L, R d1 and R d2 Synonymous with above.

[0151] In formula (D1), Rd1 and R d2 Each independently represents a hydrogen atom or is of the formula: -(RO) l -R' represents a monovalent group. l represents an integer of 0 to 5, R represents a divalent aromatic group that may have a substituent or a divalent aliphatic group that may have a substituent, and R' represents a monovalent aromatic group that may have a substituent or a monovalent aliphatic group that may have a substituent. When there are multiple R's, they may be the same or different from each other. In a preferred embodiment, R d1 and R d2 At least one of them is represented by the formula: -(RO) l The monovalent group represented by -R', R (when l=1 to 5) directly bonded to the phosphorus atom and R' (when l=0) respectively represent a divalent aromatic group which may have a substituent and a monovalent aromatic group which may have a substituent.

[0152] In this specification, "divalent aromatic group" refers to a group obtained by removing two hydrogen atoms from the aromatic ring of an aromatic compound. In a preferred embodiment, the divalent aromatic group includes an arylene group and a heteroarylene group. A heteroarylene group refers to a group obtained by removing two hydrogen atoms from the heterocyclic ring of an aromatic heterocyclic compound. A heterocyclic ring refers to a ring containing not only carbon atoms but also heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, boron atoms and silicon atoms as atoms constituting the ring. In addition, in this specification, a "monovalent aromatic group" refers to a group obtained by removing one hydrogen atom from the aromatic ring of an aromatic compound, and in a preferred embodiment, includes an aryl group and a heteroaryl group. A heteroaryl group refers to a group obtained by removing one hydrogen atom from the heterocyclic ring of an aromatic heterocyclic compound, and is the same as a heteroarylene group except that the number of hydrogen atoms removed from the heterocyclic ring is one.

[0153] In this specification, "divalent aliphatic group" refers to a group obtained by removing two hydrogen atoms from an aliphatic compound. Here, the aliphatic compound can be a saturated aliphatic compound or an unsaturated aliphatic compound. In a preferred embodiment, the divalent aliphatic group includes an alkylene group, an alkenylene group, a cycloalkylene group, a cycloalkenylene group, a heterocycloalkylene group, and a heterocycloalkenylene group. A heterocycloalkylene group refers to a group obtained by removing two hydrogen atoms from a heterocycle (i.e., a saturated heterocycle) of a saturated aliphatic heterocyclic compound, and a heterocycloalkenylene group refers to a group obtained by removing two hydrogen atoms from a heterocycle (i.e., an unsaturated heterocycle) of an unsaturated aliphatic heterocyclic compound having a carbon-carbon double bond. The heteroatoms contained in the heterocycle are the same as above. In addition, in this specification, a "monovalent aliphatic group" refers to a group obtained by removing one hydrogen atom from an aliphatic compound. In a preferred embodiment, a monovalent aliphatic group includes an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a heterocycloalkyl group, and a heterocycloalkenyl group. Heterocycloalkyl refers to a group obtained by removing one hydrogen atom from a heterocyclic ring of a saturated aliphatic heterocyclic compound, and is the same as heterocycloalkylene except that the number of hydrogen atoms removed from the heterocyclic ring is one. In addition, heterocycloalkenyl refers to a group obtained by removing one hydrogen atom from a heterocyclic ring of an unsaturated aliphatic heterocyclic compound having a carbon-carbon double bond, and is the same as heterocycloalkenylene except that the number of hydrogen atoms removed from the heterocyclic ring is one.

[0154] l is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, further preferably 0.

[0155] In a preferred embodiment, R represents an arylene group which may have a substituent, a heteroarylene group which may have a substituent, an alkylene group which may have a substituent, an alkenylene group which may have a substituent, a cycloalkylene group which may have a substituent, a cycloalkenylene group which may have a substituent, a heterocycloalkylene group which may have a substituent, or a heterocycloalkenylene group which may have a substituent.

[0156] The number of carbon atoms of the arylene group in R is preferably from 6 to 24, more preferably from 6 to 18, further preferably from 6 to 14, further preferably from 6 to 10. Specific examples of the arylene group include phenylene, naphthylene and anthracene.

[0157] The number of carbon atoms of the heteroarylene group in R is preferably 3 to 21, more preferably 3 to 15, further preferably 3 to 9, and further preferably 3 to 6. Specific examples of the heteroarylene group include pyrenediyl, pyrrolediyl, furandiyl, thiophenediyl, pyridinediyl, pyridazinediyl, pyrimidinediyl, pyrazinediyl, triazinediyl, pyrrolinediyl, piperidinediyl, triazolediyl, purinediyl, anthraquinonediyl, carbazolediyl, fluorenediyl, quinolinediyl and isoquinolinediyl.

[0158] The alkylene group in R may be either linear or branched, and the number of carbon atoms thereof is preferably 1 to 12, more preferably 1 to 9, and further preferably 1 to 6 or 1 to 4. Specific examples of the alkylene group include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, and dodecylene.

[0159] The alkenylene group in R may be either linear or branched, and the number of carbon atoms thereof is preferably 2 to 12, more preferably 2 to 9, and further preferably 2 to 6 or 2 to 4. Specific examples of the alkenylene group include ethenylene, propenylene, butenylene, pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene, and dodecenylene.

[0160] The number of carbon atoms of the cycloalkylene group in R is preferably 3 to 12, more preferably 3 to 10, 3 to 8 or 3 to 6. Specific examples of the cycloalkylene group include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, decahydronaphthylene, norbornylene and adamantylene.

[0161] The number of carbon atoms of the cycloalkenylene group in R is preferably from 3 to 10, more preferably from 3 to 6. Specific examples of the cycloalkenylene group include cyclopropenylene, cyclobutenylene, cyclopentenylene, cyclohexenylene and norbornenylene.

[0162] The number of carbon atoms of the heterocycloalkylene in R is preferably 2 to 21, more preferably 2 to 15, and further preferably 2 to 9, 2 to 6 or 2 to 5. As heteroatoms constituting the heterocycloalkylene, it is preferred to include one or more selected from oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, boron atoms and silicon atoms, and it is more preferred to include one or more selected from oxygen atoms, sulfur atoms and nitrogen atoms. As specific examples of the heterocycloalkylene, there can be listed: oxadiazine, aziridine, azetidine, oxadiazine, thietane, pyrrolidine, dihydrofuran, tetrahydrofuran.

[0163] The number of carbon atoms of the heterocycloalkenylene group in R is preferably 2 to 21, more preferably 2 to 15, further preferably 2 to 9, 2 to 6 or 2 to 5. Preferred heteroatoms are the same as those described for the heterocycloalkylene group. Specific examples of the heterocycloalkenylene group include oxadiyl and oxetadiyl.

[0164] The substituents which the divalent group in R may have are as described above. When the divalent group in R has a plurality of substituents, they may be the same or different.

[0165] In a preferred embodiment, R' represents an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkyl group which may have a substituent, a cycloalkenyl group which may have a substituent, a heterocycloalkyl group which may have a substituent, or a heterocycloalkenyl group which may have a substituent.

[0166] The preferred number of carbon atoms of the aryl, heteroaryl, alkyl, alkenyl, cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl groups in R' are the same as the preferred number of carbon atoms described for the arylene, heteroarylene, alkylene, alkenylene, cycloalkylene, cycloalkenylene, heterocycloalkylene and heterocycloalkenylene groups in R, respectively.

[0167] In formula (D1), R d3 Expressed in the formula: -(R"-O) m -R"' represents a monovalent group, wherein m represents an integer of 0 to 5, R" represents a divalent aliphatic group which may have a substituent, and R"' represents a monovalent aliphatic group which may have a substituent. When there are multiple R", they may be the same as or different from each other.

[0168] m is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, further preferably 0.

[0169] In a preferred embodiment, R" represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent, a cycloalkylene group which may have a substituent, a cycloalkenylene group which may have a substituent, a heterocycloalkylene group which may have a substituent, or a heterocycloalkenylene group which may have a substituent.

[0170] In a preferred embodiment, R'' represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkyl group which may have a substituent, a cycloalkenyl group which may have a substituent, a heterocycloalkyl group which may have a substituent, or a heterocycloalkenyl group which may have a substituent.

[0171] The preferred number of carbon atoms of the alkylene, alkenylene, cycloalkylene, cycloalkenylene, heterocycloalkylene and heterocycloalkenylene in R" is the same as the preferred number of carbon atoms described for the alkylene, alkenylene, cycloalkylene, cycloalkenylene, heterocycloalkylene and heterocycloalkenylene in R, respectively. In addition, the preferred number of carbon atoms of the alkyl, alkenyl, cycloalkyl, cycloalkenyl, heterocycloalkylene and heterocycloalkenylene in R'" is the same as the preferred number of carbon atoms described for the alkylene, alkenylene, cycloalkylene, cycloalkenylene, heterocycloalkylene and heterocycloalkenylene in R, respectively.

[0172] When R" is a heterocycloalkylene group (or heterocycloalkenylene group) which may have a substituent, the carbon atom constituting the heterocycloalkylene group (or heterocycloalkenylene group) is bonded to the phosphorus atom. When m is 0 and R"' is a heterocycloalkylene group (or heterocycloalkenyl group) which may have a substituent, the carbon atom constituting the heterocycloalkylene group (or heterocycloalkenyl group) is bonded to the phosphorus atom.

[0173] In one embodiment, in formula (D1),

[0174] i)R d1 and R d2 All are expressed in the formula: -(RO) l - a monovalent group represented by R', l is 0, and R' is an aromatic group which may have a substituent;

[0175] ii) R d3 Expressed in the formula: -(R"-O) m -R"' represents a monovalent group, m is an integer of 0 to 2, R" is an alkylene group which may have a substituent or a cycloalkylene group which may have a substituent, and R"' is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a cycloalkyl group which may have a substituent.

[0176] In a preferred embodiment, in formula (D1),

[0177] i)R d1 and R d2 All are expressed in the formula: -(RO) l -R' represents a monovalent group, l is 0, and R' is a phenyl group which may have a substituent;

[0178] ii) R d3 Expressed in the formula: -(R"-O) m -R'" represents a monovalent group, m is 0, and R'" is a cycloalkyl group which may have a substituent.

[0179] In another embodiment, in formula (D1),

[0180] i)R d1 Expressed in the formula: -(RO) l - a monovalent group represented by R', l is 0, and R' is an aromatic group which may have a substituent;

[0181] ii) R d2 Expressed in the formula: -(RO) l - a monovalent group represented by R', l is 0, and R' is an alkyl group which may have a substituent or an alkenyl group which may have a substituent;

[0182] iii) R d3 Expressed in the formula: -(R"-O) m-R"' represents a monovalent group, m is an integer of 0 to 2, R" is an alkylene group which may have a substituent or a cycloalkylene group which may have a substituent, and R"' is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a cycloalkyl group which may have a substituent.

[0183] In another preferred embodiment, in formula (D1),

[0184] i)R d1 Expressed in the formula: -(RO) l -R' represents a monovalent group, l is 0, and R' is a phenyl group which may have a substituent;

[0185] ii) R d1 Expressed in the formula: -(RO) l -R' represents a monovalent group, l is 0, and R' is an alkyl group which may have a substituent;

[0186] iii) R d3 Expressed in the formula: -(R"-O) m -R'" represents a monovalent group, m is 0, and R'" is an alkyl group which may have a substituent.

[0187] In formula (D2), R d1 and R d2 are synonymous with the above, that is, with R in formula (D1) d1 and R d2 Synonymous.

[0188] In formula (D2), L represents a compound of the formula: -(R"-O) n -R" represents a divalent group. n represents an integer from 0 to 5, and R" has the same meaning as above, that is, with respect to R in formula (D1) d3 The R"s described herein are synonymous, and when there are a plurality of R", they may be the same as or different from each other.

[0189] n is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, further preferably 0.

[0190] In formula (D2), R d4 and R d5 Each independently represents a hydrogen atom, with the formula: -(RO) l -R' represents a monovalent group or a monovalent group of the formula: -LP(-R d1 )(-R d2 ) represents a monovalent group, where l, R, R', L, R d1 and R d2 Synonymous with above.

[0191] In one embodiment, in formula (D2),

[0192] i)R d1 and R d2 All are expressed in the formula: -(RO) l - a monovalent group represented by R', l is 0, and R' is an aromatic group which may have a substituent;

[0193] ii) L represents the formula: -(R"-O) n -R"- represents a divalent group, n is an integer of 0 to 2, and R" is an alkylene group which may have a substituent or a cycloalkylene group which may have a substituent;

[0194] iii) R d4 and R d5 All are expressed in the formula: -(RO) l -R' represents a monovalent group, l is 0, and R' is an aryl group which may have a substituent.

[0195] In a preferred embodiment, in formula (D2),

[0196] i)R d1 and R d2 All are expressed in the formula: -(RO) l -R' represents a monovalent group, l is 0, and R' is a phenyl group which may have a substituent;

[0197] ii) L represents the formula: -(R"-O) n -R"- represents a divalent group, n is 0, and R" is an alkylene group which may have a substituent;

[0198] iii) R d4 and R d5 All are expressed in the formula: -(RO) l -R' represents a monovalent group, l is 0, and R' is a phenyl group which may have a substituent.

[0199] In one embodiment, the component (D) is a compound represented by any one of the following formulae.

[0200] [Chemistry 17]

[0201]

[0202] Examples of the component (D) include "DPPE" (1,3-bis(diphenylphosphino)ethane), "DPPP" (1,3-bis(diphenylphosphino)propane), "DPPB" (1,3-bis(diphenylphosphino)butane), "DPCP" (diphenylcyclohexylphosphine), "TCHP" (tricyclohexylphosphine), and "Amphos" ([4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine) manufactured by Hokuko Chemical Co., Ltd.

[0203] When the total (total amount) of the resin component in the resin composition is set to 100 mass %, even if the content of (D) component is as low as 0.001 mass %, it is also possible to realize the resin composition with a low dielectric loss tangent and a good cured product of coating adhesion and substrate adhesion in the combination with (C) component.From the viewpoint of the resin composition with a significantly good cured product of coating adhesion and substrate adhesion in the combination with (C) component, when the total of the resin component in the resin composition is set to 100 mass %, the content of (D) component in the resin composition is preferably more than 0.001 mass %, more preferably more than 0.01 mass %, more than 0.05 mass %, more than 0.1 mass %, more than 0.2 mass %, more than 0.3 mass % or more than 0.5 mass %.It should be noted that "resin component" refers to the component constituting the non-volatile component of the resin composition except (E) inorganic filler described later.

[0204] As mentioned above, the (D) component has a phosphorus atom directly bonded with an aliphatic carbon atom, and the electron-rich phosphorus atom is believed to promote the reaction of the (A) component and the (C) component, and reproduce the cured composition that helps the adhesion of the conductor. Due to its high reaction promotion effect, if the (D) component is added, the melt viscosity of the resin composition may increase over time. Therefore, in the case where the storage time from the preparation of the resin composition to the use is long, the viscosity (thickening) of the resin composition may be significant according to the use form. In this regard, when the total of the resin components in the resin composition is set to 100% by mass, the content of the (D) component is set to 10% by mass or less, thereby effectively suppressing viscosity. From the viewpoint of obtaining a resin composition with a good pot life, the upper limit of the content of the (D) component is preferably 10% by mass or less, and more preferably 8% by mass or less, 6% by mass or less, 5% by mass or less, or 3% by mass or less.

[0205] The resin composition of the present invention may further contain one or more additives selected from the group consisting of an inorganic filler, a curing accelerator, a coumarone-indene resin, a thermoplastic resin, a flame retardant and an organic filler, as required.

[0206] - (E) Inorganic filler -

[0207] The resin composition of the present invention may further contain an inorganic filler as the component (E). By containing the inorganic filler, a cured product having a lower linear thermal expansion coefficient and a lower dielectric loss tangent can be realized.

[0208] The material of the inorganic filler is not particularly limited, and examples thereof include: silicon dioxide, aluminum oxide, 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, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc., and silicon dioxide is particularly preferred. As silicon dioxide, examples thereof include amorphous silicon dioxide, fused silica, crystalline silicon dioxide, synthetic silicon dioxide, hollow silicon dioxide, etc. In addition, as silicon dioxide, spherical silicon dioxide is preferred. The inorganic filler can be used alone as one kind, or two or more kinds can be used in combination. Examples of commercially available spherical silica include "SO-C2" and "SO-C1" manufactured by Admatechs Co., Ltd. and "IMSIL A-8" and "IMSILA-10" manufactured by Unimin Corporation.

[0209] The average particle size of the inorganic filler is preferably less than 4 μm, more preferably less than 3 μm, further preferably less than 2.5 μm, further preferably less than 2 μm, particularly preferably less than 1 μm, less than 0.7 μm or less than 0.5 μm. The lower limit of the average particle size of the inorganic filler is preferably more than 0.01 μm, more preferably more than 0.03 μm, further preferably more than 0.05 μm, more than 0.07 μm or more than 0.1 μm. The average particle size of the inorganic filler can be measured by a laser diffraction scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be made into a volume basis by a laser diffraction particle size distribution measuring device, and the median particle size is measured as the average particle size. The sample for determination can preferably be a sample obtained by dispersing the inorganic filler in water by ultrasonic waves. As a laser diffraction particle size distribution measuring apparatus, "LA-500", "LA-750", "LA-950" or the like manufactured by Horiba, Ltd. can be used.

[0210] Furthermore, from the viewpoint of significantly obtaining the effects of the present invention, the specific surface area of ​​the inorganic filler is preferably 1 m 2 / g or more, preferably 2m 2 / g or more, particularly preferably 5m 2 There is no particular upper limit, but 60 m 2 / g or less, 50m 2 / g or below or 40m 2 The specific surface area of ​​the inorganic filler can be measured by the BET method.

[0211] From the viewpoint of improving moisture resistance and dispersibility, inorganic filler is preferably processed by more than one surface treatment agent of aminosilane coupling agent, epoxysilane coupling agent, mercaptosilane coupling agent, alkoxysilane compound, organosilazane compound, titanate coupling agent etc. As the commercially available product of surface treatment agent, for example can be listed: Shin-Etsu Chemical Co., Ltd. system " KBM403 " (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. system " KBM803 " (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. system " KBE903 " (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. system " KBM573 " (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. system " SZ-31 " (hexamethyldisilazane) etc.

[0212] The degree of surface treatment by the surface treatment agent can be evaluated by the carbon content per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m 2 More than 0.1 mg / m 2 More preferably, 0.2 mg / m 2 On the other hand, from the viewpoint of preventing the increase of the melt viscosity of the resin varnish and the melt viscosity in the sheet form, 1 mg / m 2 Below, preferably 0.8mg / m 2 Below, more preferably 0.5 mg / m 2 the following.

[0213] The amount of carbon per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is cleaned with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid component, a carbon analyzer can be used to measure the amount of carbon per unit surface area of ​​the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0214] From the viewpoint of obtaining the low cured product of linear thermal expansion coefficient and dielectric loss tangent, the content of the inorganic filler in the resin combination is preferably more than 50 mass %, more preferably more than 55 mass %, more than 60 mass %, more than 65 mass % or more than 70 mass %.From the viewpoint of the mechanical strength of the cured product of gained, the upper limit of the content of the inorganic filler in the resin combination is preferably below 90 mass %, more preferably below 85 mass %, further more preferably below 80 mass %.

[0215] - (F) Curing accelerator -

[0216] In the resin composition of the present invention, a curing accelerator may be further included as component (F). As a curing accelerator, for example, an amine curing accelerator, an imidazole curing accelerator, a guanidine curing accelerator, a metal curing accelerator, a peroxide curing accelerator, etc. may be cited. Among them, an amine curing accelerator, an imidazole curing accelerator, and a peroxide curing accelerator are preferred. A curing accelerator may be used alone or in combination of two or more. When a curing accelerator is used, the content of the curing accelerator in the resin composition is preferably 0.005% by mass to 1% by mass, and more preferably 0.01% by mass to 0.5% by mass.

[0217] -(G)Coumarone-indene resin-

[0218] The resin composition of the present invention may further include a coumarone-indene resin as the component (G). By including the coumarone-indene resin, the advantageous effects of the present invention produced by the combined incorporation of the components (C) and (D) can be further enhanced. Examples of coumarone-indene resins include copolymers of indene and coumarone; copolymers of indene, coumarone and styrene. Specific examples of coumarone-indene resins include "H-100", "V-120S" and "V-120" manufactured by Nippon Coating Chemical Co., Ltd. One type of coumarone-indene resin may be used alone, or two or more types may be used in combination. When using a coumarone-indene resin, the content of the coumarone-indene resin in the resin composition is preferably 1 to 4% by mass, more preferably 2 to 3.5% by mass, from the viewpoint of obtaining a resin composition having good compatibility.

[0219] - Thermoplastic resin -

[0220] The resin composition of the present invention may further include a thermoplastic resin. Examples of the thermoplastic resin include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamide-imide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins. The thermoplastic resins may be used alone or in combination of two or more.

[0221] The weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably in the range of 8000 to 70000, more preferably in the range of 10000 to 60000, and further preferably in the range of 20000 to 60000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by gel permeation chromatography (GPC). Specifically, the weight average molecular weight in terms of polystyrene of the thermoplastic resin can be measured using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, Shodex K-800P / K-804L / K-804L manufactured by Showa Denko K.K. as a column, chloroform or the like as a mobile phase, and the column temperature is set to 40°C for measurement, and the calibration curve of standard polystyrene is used for calculation.

[0222] As the phenoxy resin, for example, there can be mentioned a phenoxy resin having one or more skeletons selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a phenolic skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of phenoxy resins include: "1256" and "4250" (both are phenoxy resins containing a bisphenol A skeleton), "YX8100" (a phenoxy resin containing a bisphenol S skeleton) and "YX6954" (a phenoxy resin containing a bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation; in addition, there are: "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation, "YX7553", "YL6794", "YL7213", "YL7290" and "YL7482" manufactured by Mitsubishi Chemical Corporation, etc.

[0223] Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", and "Denka Butyral 6000-EP" manufactured by Denki Kagaku Kogyo Co., Ltd., and S-LEC BH series, BX series, KS series, BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

[0224] Specific examples of polyimide resins include "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Shin Nippon Rika Co., Ltd. Specific examples of polyimide resins include linear polyimides obtained by reacting difunctional hydroxy-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (polyimides described in Japanese Patent Laid-Open No. 2006-37083), polyimides containing a polysiloxane skeleton (polyimides described in Japanese Patent Laid-Open No. 2002-12667 and Japanese Patent Laid-Open No. 2000-319386, etc.), and the like. Modified polyimides.

[0225] Specific examples of the polyamideimide resin include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin include modified polyamideimides such as polyamideimide "KS9100" and "KS9300" containing a polysiloxane skeleton manufactured by Hitachi Chemical Co., Ltd.

[0226] Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. and the like.

[0227] Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd.

[0228] When a thermoplastic resin is used, the content of the thermoplastic resin in the resin composition is preferably from 0.1 mass % to 20 mass %, more preferably from 0.2 mass % to 10 mass %, further preferably from 0.3 mass % to 5 mass %.

[0229] - Flame retardant -

[0230] The resin composition of the present invention may further include a flame retardant. Examples of the flame retardant include organophosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, organosilicon flame retardants, metal hydroxides, and the like. One flame retardant may be used alone, or two or more may be used in combination. When a flame retardant is used, the content of the flame retardant in the resin composition is not particularly limited, and is preferably 0.1% to 15% by mass, and more preferably 0.5% to 10% by mass.

[0231] - Organic filling materials -

[0232] The resin composition of the present invention may further contain an organic filler. As the organic filler, any organic filler that can be used when forming an insulating layer of a printed wiring board can be used, and examples thereof include rubber particles, polyamide microparticles, silicone particles, etc., and rubber particles are preferred.

[0233] The rubber particles are not particularly limited as long as they are microparticles of a resin that is insoluble and infusible in an organic solvent by chemically crosslinking a resin exhibiting rubber elasticity, and examples thereof include acrylonitrile-butadiene rubber particles, butadiene rubber particles, acrylic rubber particles, etc. Specific examples of the rubber particles include XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), STAPHYLOID AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (manufactured by AICA Industries Co., Ltd.), and PARALOID EXL2655 and EXL2602 (manufactured by Kureha Chemical Industries Co., Ltd.).

[0234] The average particle size of the organic filler is preferably in the range of 0.005 μm to 1 μm, and more preferably in the range of 0.2 μm to 0.6 μm. The average particle size of the organic filler can be measured using a dynamic light scattering method. For example, the organic filler is uniformly dispersed in an appropriate organic solvent by ultrasound, etc., and a concentrated particle size analyzer ("FPAR-1000" manufactured by Otsuka Electronics Co., Ltd.) is used to make the particle size distribution of the organic filler on a mass basis, and the median particle size is measured as the average particle size. When an organic filler is used, when the non-volatile component in the resin composition is set to 100% by mass, the content of the organic filler in the resin composition is preferably 1% to 10% by mass, and more preferably 2% to 5% by mass.

[0235] The resin composition of the present invention may contain other components as required. Examples of such other components include organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds, and resin additives such as tackifiers, defoamers, leveling agents, adhesion-imparting agents, and colorants.

[0236] The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which a solvent or the like is added to the compounding components as necessary, and the mixture is mixed and dispersed using a rotary mixer or the like.

[0237] The resin composition of the present invention can bring about a cured product with a low dielectric loss tangent. The dielectric loss tangent of the cured product of the resin composition of the present invention can be measured according to the method described in the <Determination of Dielectric Loss Tangent> described later. Specifically, it can be measured by the resonant cavity perturbation method at a frequency of 5.8 GHz and a measurement temperature of 23°C. From the viewpoint of preventing heat generation at high frequencies, reducing signal delays and signal noise, the dielectric loss tangent is preferably less than 0.010, more preferably less than 0.009, less than 0.008, less than 0.007, less than 0.006, or less than 0.005, and further preferably less than 0.004, or less than 0.0035. The lower limit of the dielectric loss tangent is as low as possible, and can usually be set to 0.001 or more.

[0238] The resin composition of the present invention can bring about a cured product with good adhesion to the plated conductor layer (plating adhesion) and adhesion to the base conductor layer (base adhesion). The coating adhesion of the cured product of the resin composition of the present invention can be measured according to the method described in the <Determination of coating adhesion> described later. In addition, the base adhesion of the cured product of the resin composition of the present invention can be measured according to the method described in the <Determination of base adhesion> described later. The coating adhesion of the obtained cured product, that is, the adhesion strength (peel strength) with the plated conductor layer is preferably greater than 0.40kgf / cm. The base adhesion of the obtained cured product, that is, the adhesion strength (peel strength) with the base conductor layer is preferably greater than 0.50kgf / cm. The upper limit of these adhesion strengths is not particularly limited, and can usually be set to 1.2kgf / cm or less.

[0239] The resin composition of the present invention can bring about a cured product with low dielectric loss tangent, good plating adhesion and substrate adhesion. Therefore, the resin composition of the present invention can be well used as: a resin composition for forming an insulating layer that is connected to it and forms a conductor layer (including a rewiring layer) (a resin composition for forming an insulating layer of a conductor layer). In addition, it can also be well used as: a resin composition for forming an insulating layer of a printed wiring board (a resin composition for forming an insulating layer of a printed wiring board); it can be better used as: a resin composition for forming an interlayer insulating layer of a printed wiring board (a resin composition for forming an interlayer insulating layer of a printed wiring board). In addition, the resin composition of the present invention can also be well used as: a resin composition for embedding semiconductor components in semiconductor packaging or embedding components in a component-built-in circuit board (a resin composition for embedding components). The resin composition of the present invention can also be used in a wide range of applications that require resin compositions such as sheet-like laminated materials such as adhesive films and prepregs, solder resists, bottom fillers, chip welding materials, and hole-filling resins.

[0240] [Sheet-like laminated material]

[0241] The resin composition of the present invention can be used in a varnish state by coating, but is generally preferably used in the form of a sheet-like laminate containing the resin composition in industrial terms.

[0242] As the sheet-like laminated material, the adhesive films and prepregs shown below are preferred.

[0243] In one embodiment, the adhesive film includes 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.

[0244] From the viewpoint of thinning the printed wiring board, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, further preferably 60 μm or less or 50 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and can usually be 1 μm or more, 5 μm or more, etc.

[0245] Examples of the support include films formed of a plastic material, metal foil and release paper, and films formed of a plastic material and metal foil are preferred.

[0246] When a film formed of a plastic material is used as a support, the plastic material includes, for example, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0247] When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, preferably copper foil. As the copper foil, a foil formed of a single metal of copper can be used, or a foil formed of an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

[0248] For the support, a matte treatment or a corona treatment may be applied to the surface of the side bonded to the resin composition layer. In addition, as the support, a support with a release layer having a release layer on the surface of the side bonded to the resin composition layer may be used. As a release agent for the release layer of the support with a release layer, for example, one or more release agents selected from alkyd resins, olefin resins, polyurethane resins and silicone resins may be cited. As commercially available products of the release agent, for example, "SK-1", "AL-5", "AL-7" etc. made by Lintec Co., Ltd. as an alkyd resin release agent may be cited.

[0249] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When the support is a support with a release layer, the thickness of the entire support with a release layer is preferably within the above range.

[0250] The adhesive film can be produced, for example, by preparing a resin varnish obtained by dissolving a resin composition in an organic solvent, applying the resin varnish on a support using a die coater or the like, and drying to form a resin composition layer.

[0251] Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone, acetates 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. The organic solvent may be used alone or in combination of two or more.

[0252] Drying can be carried out by known methods such as heating and hot air blowing. The drying conditions are not particularly limited, and the drying is carried out under the condition that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. It varies depending on the boiling point of the organic solvent in the resin varnish. For example, in the case of using a resin varnish containing 30% to 60% by mass of an organic solvent, the resin composition layer can be formed by drying at 50° C. to 150° C. for 3 minutes to 10 minutes.

[0253] In the adhesive film, a protective film selected according to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (i.e., the surface on the side opposite to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent garbage from adhering to the surface of the resin composition layer or causing damage. The adhesive film can be rolled up and stored. In the case where the adhesive film has a protective film, it can be used by peeling off the protective film.

[0254] In one embodiment, the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.

[0255] The sheet-like fiber substrate used for the prepreg is not particularly limited, and materials commonly used as prepreg substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, and further preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber substrate is not particularly limited, and is usually 10 μm or more.

[0256] The prepreg can be produced by a known method such as a hot melt method or a solvent method.

[0257] The thickness of the prepreg can be set to the same range as that of the resin composition layer in the adhesive film described above.

[0258] In the sheet-like laminated material, the optimum value of the minimum melt viscosity of the resin composition layer for realizing good circuit embedding, component embedding is different according to the specific design (circuit thickness of inner substrate, line width / line spacing ratio, manufacturing component built-in circuit board for accommodating the cavity size of components, etc.) of printed wiring board. Therefore, when manufacturing the sheet-like laminated material, the condition of the desired minimum melt viscosity is designed according to the resin composition layer. However, about the sheet-like laminated material of the resin composition in the past using a curing accelerator, sometimes the solidification of the resin composition is gradually carried out when storing and viscosity increases, and sometimes the minimum melt viscosity significantly higher than the desired value is shown when used to manufacture the printed wiring board.

[0259] In contrast, the resin composition of the present invention in which the (C) component and the (D) component are combined can not only realize a cured product with low dielectric loss tangent, good coating adhesion and substrate adhesion, but also the curing process of the resin composition during storage is suppressed, and the desired minimum melt viscosity can be advantageously maintained. In one embodiment, the sheet-like laminated material of the present invention, when the minimum melt viscosity of the resin composition layer just after it is made is set to V1 (poise), and the minimum melt viscosity of the resin composition layer after being stored at room temperature (25°C) for 24 hours is set to V2 (poise), the ratio of V2 / V1 (hereinafter also referred to as "viscosity increase ratio") is preferably 2 or less, more preferably 1.8 or less, further preferably 1.6 or less, further preferably 1.5 or less, particularly preferably 1.4 or less, 1.3 or less, 1.2 or less or 1.1 or less. The lower limit of the viscosity increase ratio is preferably 1.

[0260] Here, the "minimum melt viscosity" of the resin composition layer refers to the minimum viscosity of the resin composition layer when the resin of the resin composition layer is melted. In detail, if the resin composition layer is heated at a certain heating rate to melt the resin, the melt viscosity decreases as the temperature rises in the initial stage, and then the melt viscosity increases as the temperature rises after exceeding a certain temperature. "Minimum melt viscosity" refers to the melt viscosity of the above-mentioned minimum point. The minimum melt viscosity of the resin composition layer can be measured by the method described in the <Determination of Minimum Melt Viscosity> described later. Specifically, the minimum melt viscosity of the resin composition layer can be obtained by performing a dynamic viscoelasticity measurement under the conditions of a measurement starting temperature of 60°C, a heating rate of 5°C / min, a vibration frequency of 1Hz, and a strain of 1deg. As a dynamic viscoelasticity measuring device, for example, "Rheosol-G3000" manufactured by UBM Co., Ltd. can be cited.

[0261] [Printed wiring board]

[0262] The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.

[0263] In one embodiment, the printed wiring board of the present invention can be produced by a method including the following steps (I) and (II) using the above-mentioned adhesive film.

[0264] (I) A step of laminating an adhesive film on the inner substrate so that the resin composition layer of the adhesive film is bonded to the inner substrate

[0265] (II) Step of thermally curing the resin composition layer to form an insulating layer

[0266] The "inner layer substrate" used in step (I) mainly refers to 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 a circuit substrate having a patterned conductor layer (circuit) formed on one or both sides of the substrate. In addition, the inner layer circuit substrate of an intermediate product that needs to further form an insulating layer and / or a conductor layer when manufacturing a printed wiring board is also included in the "inner layer substrate" referred to in the present invention. In the case where the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components can be used.

[0267] The inner substrate and the adhesive film can be laminated, for example, by heat-pressing the adhesive film to the inner substrate from the support body side. As a component for heat-pressing the adhesive film to the inner substrate (hereinafter also referred to as a "heat-pressing component"), for example, a heated metal plate (SUS end plate (mirror plate) etc.) or a metal roller (SUS roller) etc. can be cited. It should be noted that it is better not to press the heat-pressing component directly on the adhesive film, but to press it through an elastic material such as heat-resistant rubber so that the adhesive film fully conforms to the surface unevenness of the inner substrate.

[0268] The lamination of the inner substrate and the adhesive film can be implemented by vacuum lamination. In the vacuum lamination, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heating and pressing pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably implemented under reduced pressure conditions of 26.7hPa or less.

[0269] Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Meiki Mfg. Co., Ltd. and a vacuum applicator manufactured by Nikko Materials Co., Ltd.

[0270] After lamination, the laminated adhesive film may be smoothed by, for example, pressing a heating and pressing member from the support body side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing treatment may be the same as the heating and pressing conditions for the above-mentioned lamination. The smoothing treatment may be performed by a commercially available laminator. It should be noted that the lamination and smoothing treatment may be performed continuously using the above-mentioned commercially available vacuum laminator.

[0271] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0272] In the step (II), the resin composition layer is thermally cured to form an insulating layer.

[0273] The heat curing conditions of the resin composition layer are not particularly limited, and conditions generally used when forming an insulating layer of a printed wiring board can be used.

[0274] For example, the thermal curing conditions of the resin composition layer vary depending on the type of resin composition, and for example, the curing temperature may be set within the range of 120°C to 240°C (preferably within the range of 150°C to 220°C, and more preferably within the range of 170°C to 200°C), and the curing time may be set within the range of 5 minutes to 120 minutes (preferably within the range of 10 minutes to 100 minutes, and more preferably within the range of 15 minutes to 90 minutes).

[0275] The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, the resin composition layer may be preheated at a temperature of 50° C. or higher and lower than 120° C. (preferably 60° C. or higher and 110° C. or lower, and more preferably 70° C. or higher and 100° C. or lower) for 5 minutes or more (preferably 5 minutes to 150 minutes, and more preferably 15 minutes to 120 minutes) before the resin composition layer is thermally cured.

[0276] When manufacturing a printed wiring board, it is also possible to implement a step (III) of opening holes in the insulating layer, a step (IV) of roughening the insulating layer, and a step (V) of forming a conductor layer on the surface of the insulating layer. These steps (III) to (V) can be implemented according to various methods known to those skilled in the art used in the manufacture of printed wiring boards. It should be noted that when the support is removed after step (II), the removal of the support can be implemented between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V).

[0277] In other embodiments, the printed wiring board of the present invention can be produced using the above-mentioned prepreg. The production method is basically the same as that in the case of using an adhesive film.

[0278] Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as through holes and vias in the insulating layer. Step (III) can be implemented using, for example, a drill, a laser, or a plasma, depending on the composition of the resin composition used to form the insulating layer. The size and shape of the hole can be appropriately determined according to the design of the printed wiring board.

[0279] Step (IV) is a step of roughening the insulating layer. The steps and conditions of the roughening treatment are not particularly limited, and the known steps and conditions commonly used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by sequentially carrying out swelling treatment using a swelling liquid, roughening treatment using an oxidizing agent, and neutralization treatment using a neutralizing liquid. As the swelling liquid, there is no particular limitation, and alkali solutions, surfactant solutions, etc. can be cited, preferably alkali solutions, and as the alkali solution, sodium hydroxide solutions and potassium hydroxide solutions are more preferred. As commercially available swelling liquids, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan Co., Ltd. can be cited. The swelling treatment using a swelling liquid is not particularly limited, and for example, it can be carried out by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of controlling the swelling of the resin of the insulating layer to an appropriate level, it is preferred to immerse the cured body in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes. As an oxidant, there is no particular limitation, and examples thereof include alkaline permanganate solutions obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidant such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidant solution heated to 60°C to 80°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. As commercially available oxidants, alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing solution Securiganth P" manufactured by Atotech Japan Co., Ltd. can be cited. In addition, as a neutralizing solution, an acidic aqueous solution is preferred, and as a commercially available product, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd. can be cited. The treatment with a neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with an oxidizing agent in a neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of operability, etc., a method in which the object subjected to the roughening treatment with an oxidizing agent is immersed in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferred.

[0280] Step (V) is a step of forming a conductor layer.

[0281] The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductor layer can be a single metal layer or an alloy layer. As the alloy layer, for example, a layer formed by an alloy of two or more metals selected from the above metals (such as nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) can be listed. Among them, from the viewpoints of versatility, cost, and ease of pattern formation of the conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferred, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy is more preferred, and a single metal layer of copper is more preferred.

[0282] The conductor layer may be a single layer structure, or a multilayer structure in which two or more single metal layers or alloy layers formed of different types of metals or alloys are stacked. When the conductor layer is 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.

[0283] The thickness of the conductor layer varies depending on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0284] In one embodiment, the conductor layer can be formed by plating. For example, the conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method.

[0285] In other embodiments, the conductor layer can be formed using a metal foil. When a metal foil is used to form a conductor layer, step (V) is preferably implemented between step (I) and step (II). For example, after step (I), the support is removed and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil can be implemented by a vacuum lamination method. The lamination conditions can be the same as those described for step (I). Next, step (II) is implemented to form an insulating layer. Then, the metal foil on the insulating layer can be used to form a conductor layer with a desired wiring pattern by currently known techniques such as a subtractive method and an improved semi-additive method.

[0286] The metal foil can be produced by a known method such as electrolysis or rolling. Commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Co., Ltd.

[0287] When a printed wiring board is produced using the resin composition of the present invention containing the specific (C) component and (D) component in combination, an insulating layer having a low dielectric loss tangent and good plating adhesion and base adhesion can be realized.

[0288] [Semiconductor packaging]

[0289] The semiconductor package of the present invention comprises a circuit substrate, a semiconductor component mounted on the circuit substrate, and a sealing material for embedding (sealing) the semiconductor component. The semiconductor package of the present invention is characterized in that the sealing material is formed by a cured product of the resin composition of the present invention. Here, the structure and type of the circuit substrate and semiconductor component constituting the semiconductor package of the present invention are not particularly limited, and any circuit substrate and semiconductor component commonly used when forming a semiconductor package can be used.

[0290] The semiconductor package of the present invention can be produced by embedding (sealing) a semiconductor component with the resin composition of the present invention. The conditions for sealing the semiconductor are not particularly limited, and any sealing conditions generally used in the production of semiconductor packages can be used.

[0291] [Semiconductor devices]

[0292] The semiconductor device of the present invention includes a cured product of the resin composition of the present invention. The semiconductor device of the present invention can be produced using the printed wiring board or the semiconductor package of the present invention.

[0293] Examples of the semiconductor device include various semiconductor devices used in electrical products (eg, computers, mobile phones, digital cameras, and televisions) and vehicles (eg, motorcycles, cars, trains, ships, and aircraft).

[0294] Example

[0295] The present invention will be described in detail below with reference to the following examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" indicating amounts represent "parts by mass" and "% by mass" respectively, unless otherwise expressly stated.

[0296] First, the measurement method and evaluation method of physical property evaluation in this specification are described.

[0297] <Preparation of samples for evaluation of cured properties>

[0298] The adhesive films obtained in Examples and Comparative Examples were thermally cured at 200° C. for 90 minutes, and the support was peeled off to prepare sheet-shaped samples for evaluating cured physical properties.

[0299] <Measurement of dielectric loss tangent>

[0300] A test piece with a width of 2 mm and a length of 80 mm was cut from the sample for curing property evaluation. For the cut test piece, the measuring device "HP8362B" made by Agilent Technologies was used to measure the dielectric loss tangent by the resonant cavity perturbation method at a measuring frequency of 5.8 GHz and a measuring temperature of 23°C. The case where the dielectric loss tangent is 0.0035 or less is evaluated as "○" (good), the case where it is greater than 0.0035 and less than 0.0040 is evaluated as "△" (qualified), and the case where it exceeds 0.0040 is evaluated as "×" (bad).

[0301] <Preparation of evaluation substrate>

[0302] (1) Base treatment of inner layer circuit board

[0303] Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.8 mm, "R1515A" manufactured by Panasonic Corporation) with an inner layer circuit formed thereon were immersed in a microetchant ("CZ-8101" manufactured by Mag Co., Ltd.) and etched 1 μm to roughen the copper surface.

[0304] (2) Lamination of adhesive films

[0305] The adhesive films prepared in the examples and comparative examples were laminated on both sides of the inner layer circuit substrate using a batch vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.) in such a manner that the resin composition layer was bonded to the inner layer circuit substrate. The lamination was performed as follows: after reducing the pressure for 30 seconds to a pressure of 13 hPa or less, the pressure was pressed for 30 seconds at 100° C. and a pressure of 0.74 MPa.

[0306] (3) Curing of the resin composition layer

[0307] The laminated adhesive film was thermally cured at 200° C. for 90 minutes to form a cured product (insulating layer) on both surfaces of the inner layer circuit board. Then, the support was peeled off from the adhesive film.

[0308] (4) Roughening treatment

[0309] The inner layer circuit board with the insulating layer formed was immersed in a swelling solution ("Swelling Dip Securiganth P" manufactured by Atotech Japan Co., Ltd., an aqueous sodium hydroxide solution containing diethylene glycol monobutyl ether) at 60°C for 10 minutes, then immersed in a roughening solution ("Concentrate Compact P" manufactured by Atotech Japan Co., Ltd., an aqueous solution with a potassium permanganate concentration of 60g / L and a sodium hydroxide concentration of 40g / L) at 80°C for 20 minutes, and finally immersed in a neutralizing solution ("Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd., an aqueous solution of hydroxylamine sulfate) at 40°C for 5 minutes. Then, it was dried at 80°C for 30 minutes. The resulting substrate is called "evaluation substrate A".

[0310] (5) Formation of plated conductor layer

[0311] According to the semi-additive method, a plated conductor layer (second conductor layer) is formed on the surface of the evaluation substrate A. Specifically, the evaluation substrate A is immersed in an electroless plating solution containing PdCl2 at 40°C for 5 minutes, and then immersed in an electroless copper plating solution at 25°C for 20 minutes. After the obtained evaluation substrate A is heated at 150°C for 30 minutes for annealing, copper sulfate electrolytic plating is performed to form a plated conductor layer with a thickness of 30μm. The evaluation substrate A formed with the plated conductor layer is annealed at 190°C for 60 minutes. The obtained substrate is referred to as "evaluation substrate B".

[0312] <Measurement of coating adhesion>

[0313] A 10 mm wide and 100 mm long incision was formed in the plated conductor layer (second conductor layer) of the evaluation substrate B, one end of which was peeled off and clamped with a clamp, and the load (kgf / cm (N / cm)) when peeling 35 mm in the vertical direction at a speed of 50 mm / min at room temperature (25°C) was measured. A tensile tester ("AC-50C-SL" manufactured by TSE Co., Ltd.) was used for the measurement. The case where the load was greater than 0.4 kgf / cm was evaluated as "○" (good), and the case where the load was less than 0.4 kgf / cm was evaluated as "×" (bad).

[0314] <Measurement of substrate adhesion>

[0315] (1) Base treatment of copper foil

[0316] The shiny surface of "3EC-III" (electrolytic copper foil, 35 μm) manufactured by Mitsui Mining and Co., Ltd. was immersed in a microetchant ("CZ8101" manufactured by Mag Co., Ltd.) to roughen the copper surface (Ra value = 1 μm), and then subjected to rust prevention treatment (CL8300). This copper foil is called CZ copper foil. Furthermore, it was heated in an oven at 130°C for 30 minutes.

[0317] (2) Copper foil lamination and insulation layer formation

[0318] The same operation as in "(2) Lamination of adhesive film" in the above <Preparation of evaluation substrate> was performed to prepare a substrate from which the support body was peeled off. The treated surface of the CZ copper foil of "3EC-III" was laminated on the resin composition layer under the same conditions as in "(2) Lamination of adhesive film" in the above <Preparation of evaluation substrate>. Then, the resin composition layer was cured under the curing conditions of 190°C and 90 minutes to form an insulating layer, thereby preparing a sample.

[0319] (3) Measurement of copper foil peel strength (base adhesion)

[0320] The prepared sample was cut into small pieces of 150×30 mm. A cutter was used to cut a 10 mm wide and 100 mm long portion of the copper foil portion of the small piece, and one end of the copper foil was peeled off and clamped with a clamp ("AC-50C-SL" manufactured by TSE Co., Ltd.), and the load when peeling 35 mm in the vertical direction at a speed of 50 mm / min at room temperature was measured using an Instron universal testing machine in accordance with JIS C6481. The case where the load was greater than 0.5 kgf / cm was evaluated as "○" (good), and the case where the load was less than 0.5 kgf / cm was evaluated as "×" (bad).

[0321] <Determination of minimum melt viscosity>

[0322] The resin composition layer of the adhesive film prepared in the examples and comparative examples was compressed by a mold to prepare particles for measurement (diameter 18 mm, 1.2-1.3 g). The melt viscosity of the obtained particles for measurement was measured using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM Co., Ltd.). For the particles for measurement, a parallel plate with a diameter of 18 mm was used to increase the temperature from a starting temperature of 60°C to 200°C at a heating rate of 5°C / min. The dynamic viscoelastic coefficient was measured under the measurement conditions of a measurement temperature interval of 2.5°C, a vibration frequency of 1Hz, and a strain of 1deg, and the minimum melt viscosity (poise) was calculated. For each resin composition layer, the initial minimum melt viscosity V1 (poise) just after the adhesive film was made and the minimum melt viscosity V2 (poise) after being stored at room temperature (25°C) for 24 hours were determined, and the viscosity increase ratio (V2 / V1) was calculated.

[0323] The case where the viscosity increase ratio was greater than 2 was evaluated as “△”, and the case where it was 2 or less was evaluated as “○”.

[0324] <Example 1>

[0325] 30 parts of bimethylol epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight about 185) were heated and dissolved in 30 parts of solvent naphtha while stirring, and then cooled to room temperature. 250 parts of spherical silica ("SO-C2" manufactured by Yaduma Co., Ltd., average particle size 0.5 μm, carbon content per unit surface area 0.38 mg / m2) surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed. 2 ), and kneaded and dispersed using a three-roll mill. Thereto were mixed 53.8 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC Corporation, a toluene solution containing 65% of nonvolatile components having an active group equivalent of about 223), 20 parts of a resin having an acrylic group (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.), 10 parts of a resin having a styrene group (“OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution containing 60% of nonvolatile components), 5 parts of a coumarone-indene resin (“H-100” manufactured by Nippon Paint Chemical Co., Ltd.), 2 parts of a 5% MEK solution of 4-dimethylaminopyridine (DMAP) as a curing accelerator, 0.13 parts of dicumyl peroxide (“PERCUMYLD” manufactured by NOF Corporation), and 1 part of 1,3-bis(diphenylphosphino)propane (“DPPP” manufactured by Hokko Chemical Co., Ltd.), and the mixture was uniformly dispersed using a rotary mixer to prepare a resin varnish 1.

[0326] Next, using a die coater, the resin varnish 1 was evenly applied on the release layer of a PET film with an alkyd resin release layer ("AL-5" manufactured by Lintec, with a thickness of 38 μm) so that the thickness of the dried resin composition layer reached 40 μm, and dried at 80 to 110° C. (95° C. on average) for 5 minutes to form an adhesive film 1.

[0327] <Example 2>

[0328] Resin varnish 2 and adhesive film 2 were prepared in the same manner as in Example 1 except that the amount of 1,3-bis(diphenylphosphino)propane ("DPPP" manufactured by Hokuko Chemical Co., Ltd.) added was changed from 1 part to 0.5 parts.

[0329] <Example 3>

[0330] Resin varnish 3 and adhesive film 3 were prepared in the same manner as in Example 1 except that the amount of 1,3-bis(diphenylphosphino)propane ("DPPP" manufactured by Hokuko Chemical Co., Ltd.) added was changed from 1 part to 0.01 part.

[0331] <Example 4>

[0332] Resin varnish 4 and adhesive film 4 were prepared in the same manner as in Example 1 except that the amount of 1,3-bis(diphenylphosphino)propane ("DPPP" manufactured by Hokuko Chemical Co., Ltd.) added was changed from 1 part to 10 parts.

[0333] <Example 5>

[0334] Resin varnish 5 and adhesive film 5 were prepared in the same manner as in Example 1 except that 1 part of 1,3-bis(diphenylphosphino)propane ("DPPP" manufactured by Hokko Chemical Co., Ltd.) was replaced with 1 part of diphenylcyclohexylphosphine ("DPCP" manufactured by Hokko Chemical Co., Ltd.).

[0335] <Example 6>

[0336] Resin varnish 6 and adhesive film 6 were prepared in the same manner as in Example 1 except that 1 part of 1,3-bis(diphenylphosphino)propane ("DPPP" manufactured by Hokko Chemical Co., Ltd.) was replaced with 1 part of 1,3-bis(diphenylphosphino)butane ("DPBP" manufactured by Hokko Chemical Co., Ltd.).

[0337] <Example 7>

[0338] Resin varnish 7 and adhesive film 7 were prepared in the same manner as in Example 1 except that 1 part of 1,3-bis(diphenylphosphino)propane ("DPPP" manufactured by Hokko Chemical Co., Ltd.) was replaced with 1 part of [4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine ("Amphos" manufactured by Hokko Chemical Co., Ltd.).

[0339] <Example 8>

[0340] Resin varnish 8 and adhesive film 8 were prepared in the same manner as in Example 1 except that the amount of 1,3-bis(diphenylphosphino)propane ("DPPP" manufactured by Hokuko Chemical Co., Ltd.) added was changed from 1 part to 15 parts.

[0341] <Comparative Example 1>

[0342] Resin varnish 9 and adhesive film 9 were prepared in the same manner as in Example 1 except that 1,3-bis(diphenylphosphino)propane ("DPPP" manufactured by Hokuko Chemical Co., Ltd.) was not added.

[0343] <Comparative Example 2>

[0344] A resin varnish 10 and an adhesive film 10 were prepared in the same manner as in Example 1 except that 1 part of 1,3-bis(diphenylphosphino)propane (“DPPP” manufactured by Hokko Chemical Co., Ltd.) was replaced with 1 part of triphenylphosphine (“TPPP” manufactured by Hokko Chemical Co., Ltd.).

[0345] <Comparative Example 3>

[0346] Resin varnish 11 and adhesive film 11 were prepared in the same manner as in Example 1 except that 20 parts of a resin having an acrylic group ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd.) and 10 parts of a resin having a styrene group ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution containing 60% nonvolatile matter) were not added.

[0347] Table 1 shows the evaluation results of Examples and Comparative Examples.

[0348] [Table 1]

[0349]

[0350] Regarding the cases where spherical silica "SO-C2" was not added, the cases where a curing accelerator (dimethylaminopyridine (DMAP) and "PERCUMYL D") was not added, and the cases where coumarone-indene resin "H-100" was not added, it was confirmed that although there were differences in degree, they all resulted in the same results as the above-mentioned embodiments.

Claims

1. A resin composition, wherein The invention comprises: (A) an epoxy resin, (B) a curing agent, (C) a resin having a free radical polymerizable unsaturated group, (D) an aliphatic phosphine compound, and (E) an inorganic filler material. Component (A) comprises a biphenyl type epoxy resin, Component (B) comprises an active ester curing agent, The component (C) has, as a radical polymerizable unsaturated group, at least one group selected from the group consisting of an acryloyl group, a methacryloyl group, a styryl group, an alkenyl group, and a maleimide group, The component (D) contains phosphorus atoms directly bonded to both aliphatic carbon atoms and aromatic carbon atoms, When the total amount of nonvolatile components in the resin composition is 100% by mass, the content of the component (C) is 1% by mass to 20% by mass. When the total amount of the resin components in the resin composition is 100% by mass, the content of the component (D) is 0.001% by mass to 10% by mass. When the nonvolatile component in the resin composition is 100 mass %, the content of the (E) inorganic filler is 50 mass % or more.

2. The resin composition according to claim 1, wherein The component (D) has 1 to 4 phosphorus atoms directly bonded to an aliphatic carbon atom in one molecule.

3. The resin composition according to claim 1, wherein The component (D) has one or two phosphorus atoms directly bonded to an aliphatic carbon atom in one molecule.

4. The resin composition according to claim 1, wherein The component (D) has 2 to 40 aliphatic carbon atoms in one molecule.

5. The resin composition according to claim 4, wherein The component (D) has three or more aliphatic carbon atoms in one molecule.

6. The resin composition according to claim 4, wherein The component (D) has 20 or less aliphatic carbon atoms in one molecule.

7. The resin composition according to claim 4, wherein The component (D) has 12 or less aliphatic carbon atoms in one molecule.

8. The resin composition according to claim 1, wherein Component (D) is a compound represented by formula (D1) or formula (D2), In formula (D1), R d1 and R d2 Each independently represents a hydrogen atom or is of the formula: -(RO) l - a monovalent group represented by R', wherein l represents an integer of 0 to 5, R represents a divalent aromatic group which may have a substituent, or a divalent aliphatic group which may have a substituent, and R' represents a monovalent aromatic group which may have a substituent, or a monovalent aliphatic group which may have a substituent, and when there are multiple R's, they may be the same or different from each other; R d1 and R d2 At least one of them is represented by the formula: -(RO) l -R' represents a monovalent group, R (l = 1 to 5) directly bonded to the phosphorus atom and R' (l = 0) represent a divalent aromatic group which may have a substituent and a monovalent aromatic group which may have a substituent, respectively, R d3 Represented by the formula: -(R"-O) m -R"' represents a monovalent group, wherein m represents an integer of 0 to 5, R" represents a divalent aliphatic group which may have a substituent, R"' represents a monovalent aliphatic group which may have a substituent, and when there are multiple R", they may be the same or different from each other, In formula (D2), R d1 and R d2 Synonymous with above; L represents the formula: -(R"-O) n -R"- represents a divalent group, wherein n represents an integer of 0 to 5, R" has the same meaning as above, and when there are multiple R", they may be the same as or different from each other; R d4 and R d5 Each independently represents a hydrogen atom, with the formula: -(RO) l -R' represents a monovalent group, or a monovalent group represented by the formula: -LP(-R d1 )(-R d2 ) represents a monovalent group, where l, R, R', L, R d1 and R d2 Synonymous with above.

9. The resin composition according to claim 8, wherein l is an integer from 0 to 2.

10. The resin composition according to claim 8, wherein m is an integer from 0 to 2.

11. The resin composition according to claim 8, wherein n is an integer from 0 to 2.

12. The resin composition according to claim 8, wherein In formula (D1), i)R d1 and R d2 All are expressed in the formula: -(RO) l - a monovalent group represented by R', l is 0, and R' is an aromatic group which may have a substituent; ii) R d3 Expressed in the formula: -(R"-O) m -R"' represents a monovalent group, m is an integer of 0 to 2, R" is an alkylene group which may have a substituent or a cycloalkylene group which may have a substituent, and R"' is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a cycloalkyl group which may have a substituent.

13. The resin composition according to claim 8, wherein In formula (D1), i)R d1 and R d2 All are expressed in the formula: -(RO) l -R' represents a monovalent group, l is 0, and R' is a phenyl group which may have a substituent; ii) R d3 Expressed in the formula: -(R"-O) m -R'" represents a monovalent group, m is 0, and R'" is a cycloalkyl group which may have a substituent.

14. The resin composition according to claim 8, wherein In formula (D1), i)R d1 Expressed in the formula: -(RO) l - a monovalent group represented by R', l is 0, and R' is an aromatic group which may have a substituent; ii) R d2 Expressed in the formula: -(RO) l - a monovalent group represented by R', l is 0, and R' is an alkyl group which may have a substituent or an alkenyl group which may have a substituent; iii) R d3 Expressed in the formula: -(R"-O) m -R"' represents a monovalent group, m is an integer of 0 to 2, R" is an alkylene group which may have a substituent or a cycloalkylene group which may have a substituent, and R"' is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a cycloalkyl group which may have a substituent.

15. The resin composition according to claim 8, wherein In formula (D1), i)R d1 Expressed in the formula: -(RO) l -R' represents a monovalent group, l is 0, and R' is a phenyl group which may have a substituent; ii) R d1 Expressed in the formula: -(RO) l -R' represents a monovalent group, l is 0, and R' is an alkyl group which may have a substituent; iii) R d3 Expressed in the formula: -(R"-O) m -R'" represents a monovalent group, m is 0, and R'" is an alkyl group which may have a substituent.

16. The resin composition according to claim 8, wherein In formula (D2), i)R d1 and R d2 All are expressed in the formula: -(RO) l - a monovalent group represented by R', l is 0, and R' is an aromatic group which may have a substituent; ii) L represents the formula: -(R"-O) n -R"- represents a divalent group, n is an integer of 0 to 2, and R" is an alkylene group which may have a substituent or a cycloalkylene group which may have a substituent; iii) R d4 and R d5 All are expressed in the formula: -(RO) l -R' represents a monovalent group, l is 0, and R' is an aryl group which may have a substituent.

17. The resin composition according to claim 8, wherein In formula (D2), i)R d1 and R d2 All are expressed in the formula: -(RO) l -R' represents a monovalent group, l is 0, and R' is a phenyl group which may have a substituent; ii) L represents the formula: -(R"-O) n -R"- represents a divalent group, n is 0, and R" is an alkylene group which may have a substituent; iii) R d4 and R d5 All are expressed in the formula: -(RO) l -R' represents a monovalent group, l is 0, and R' is a phenyl group which may have a substituent.

18. The resin composition according to claim 1, wherein The component (D) includes a compound represented by any of the following formulae, 19. The resin composition according to claim 1, wherein The content of the component (D) is 0.01% by mass or more.

20. The resin composition according to claim 1, wherein The content of the component (D) is 0.1% by mass or more.

21. The resin composition according to claim 1, wherein The content of the component (D) is 0.2% by mass or more.

22. The resin composition according to claim 1, wherein The content of the component (D) is 0.5% by mass or more.

23. The resin composition according to claim 1, wherein The content of the component (D) is 8% by mass or less.

24. The resin composition according to claim 1, wherein The content of the component (D) is 6 mass % or less.

25. The resin composition according to claim 1, wherein The content of the component (D) is 3% by mass or less.

26. The resin composition according to claim 1, wherein When the total amount of nonvolatile components in the resin composition is 100% by mass, the content of the component (A) is 3% by mass to 70% by mass.

27. The resin composition according to claim 26, wherein The content of the component (A) is 5% by mass or more.

28. The resin composition according to claim 26, wherein The content of the component (A) is 8% by mass or more.

29. The resin composition according to claim 26, wherein The content of the component (A) is 50% by mass or less.

30. The resin composition according to claim 26, wherein The content of the component (A) is 20% by mass or less.

31. The resin composition according to claim 1, wherein The amount ratio of the epoxy resin (A) to the curing agent (B) is 1:0.4 to 1:1.2 in terms of the ratio of [the total number of epoxy groups of the epoxy resin]:[the total number of reactive groups of the curing agent].

32. The resin composition according to claim 1, wherein (C) Component has one or more groups selected from the group consisting of an acryloyl group, a methacryloyl group, a styryl group, an allyl group, a vinyl group, a propenyl group, and a maleimide group.

33. The resin composition according to claim 1, wherein The component (C) is a resin having a cyclic ether structure having 5 or more members.

34. The resin composition according to claim 33, wherein The cyclic ether structure having 5 or more members is a dioxane structure.

35. The resin composition according to claim 1, wherein (C) component is selected from the group consisting of a compound represented by the following formula (C1), a compound represented by the following formula (C6), a compound represented by the following formula (C7), a compound represented by the following formula (C9), a compound represented by the following formula (C10), and a benzocyclobutene resin; In formula (C1), R 1 ~R 6 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; A represents a divalent group represented by the following formula (C2) or the following formula (C3); -CH2-OBO-CH2- (C2) In formula (C2), B represents a divalent group represented by the following formula (C2-1), (C2-2) or (C2-3); In formula (C2-1), R 15 ~R 18 Each independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group; In formula (C2-2), R 19 ~R 26 Each independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group; In formula (C2-3), R 27 ~R 34 Each independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and E represents a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms; In formula (C3), D represents a divalent group represented by the following formula (C4); In formula (C4), R 7 ~R 14 Each independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group; a and b are integers greater than or equal to 0 and less than or equal to 100, at least one of which is not 0; B represents a divalent group represented by the above formula (C2-1), (C2-2) or (C2-3); In formula (C7), ring F represents a divalent group having a cyclic ether structure of 5 or more members; 1 and B 2 Each independently represents a single bond or a divalent linking group; C 1 and C 2 Each independently represents a functional group; In the formula (C10), n represents 1 to 5.

36. The resin composition according to claim 35, wherein The compound represented by formula (C1) is a compound represented by the following formula (C5), In formula (C5), R 1 ~R 6 and R in the formula (C1) 1 ~R 6 B has the same meaning as B in the formula (C2), and a and b have the same meaning as a and b in the formula (C4).

37. The resin composition according to claim 35, wherein The compound represented by formula (C7) is a compound represented by the following formula (C8), 38. The resin composition according to claim 1, wherein The number average molecular weight of the component (C) is 100 to 10,000.

39. The resin composition according to claim 38, wherein The number average molecular weight of the component (C) is 200 or more.

40. The resin composition according to claim 38, wherein The number average molecular weight of the component (C) is 3,000 or less.

41. The resin composition according to claim 1, wherein The content of the component (C) is 3% by mass or more.

42. The resin composition according to claim 1, wherein The content of the component (C) is 5% by mass or more.

43. The resin composition according to claim 1, wherein The content of the component (C) is 10% by mass or less.

44. The resin composition according to claim 1, wherein The resin composition is used for forming an insulating layer of a conductor layer.

45. A sheet-like laminated material, wherein: A resin composition comprising the resin composition according to any one of claims 1 to 44.

46. ​​A printed wiring board, wherein: An insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 44.

47. A semiconductor device, wherein: A cured product comprising the resin composition according to any one of claims 1 to 44.

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