JP5915610B2 - Resin composition - Google Patents

Description

  The present invention relates to a resin composition.

  As a manufacturing technique of a multilayer printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the manufacturing method by the build-up method, the insulating layer is generally formed by thermosetting a resin composition.

  For example, Patent Document 1 discloses a technique for forming an insulating layer by thermally curing a resin composition containing an epoxy resin, an active ester compound, and a curing accelerator containing 4-dimethylaminopyridine. . Patent Document 2 discloses a technique for thermally curing a resin composition containing an epoxy resin and an active ester compound to form an insulating layer, and 1-benzyl-2-phenylimidazole is used as a curing accelerator. The resin composition containing is specifically disclosed (Example).

JP 2011-178857 A International Publication No. 2013/027732

  In the production of a multilayer printed wiring board, the resin composition for forming an insulating layer is desired to be quickly cured at the time of thermal curing, and a curing accelerator is preferably used. However, with regard to conventional resin compositions containing a curing accelerator, the curing may gradually progress and the viscosity may increase during storage of the resin composition. The present inventors have found that it may be difficult to achieve sex and the like.

  An object of the present invention is to provide a resin composition having excellent curing potential, which can suppress the progress of curing during storage and can be quickly cured during thermal curing to provide an insulating layer.

  As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by using a curing accelerator containing a specific compound, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition comprising (A) an epoxy resin, (B) an active ester curing agent, and (C) a curing accelerator,
(C) The resin composition containing 1 or more types selected from the group which a component consists of a pyridine compound which has an electron withdrawing group in 4-position, and an imidazole compound which has an electron withdrawing group in 1-position.
[2] The resin composition according to [1], wherein the electron withdrawing group is a group having a Hammett's substituent constant σ _m value larger than 0.
[3] A pyridine compound having an electron withdrawing group at the 4-position has a halogen atom, a cyano group, a nitro group, a phenyl group optionally having a substituent at the 4-position, a carbonyl group, a thiocarbonyl group, a sulfonyl group, Alternatively, the resin composition according to [1] or [2], which is a pyridine compound having a phosphoryl group.
[4] An imidazole compound having an electron withdrawing group at the 1-position has a cyano group, a phenyl group which may have a substituent, a vinyl group which may have a substituent, and a substituent at the 1-position. Any of [1] to [3] which is an imidazole compound having a carboxymethylene group which may be substituted, a cyanoalkylene group having 2 or 3 carbon atoms which may have a substituent, a carbonyl group or a sulfonyl group A resin composition according to claim 1.
[5] The resin composition according to any one of [1] to [4], wherein the pyridine compound having an electron withdrawing group at the 4-position is a pyridine compound having a cyano group or a carbonyl group at the 4-position.
[6] The imidazole compound having an electron withdrawing group at the 1-position is an imidazole compound having a phenyl group, a carbonyl group, or a sulfonyl group that may have a substituent at the 1-position [1] to [5]. The resin composition in any one of.
[7] Component (C) is 4-benzoylpyridine, 4-cyanopyridine, ethyl isonicotinate, 1,1′-carbonyldiimidazole, 1,1′-sulfonyldiimidazole, 1- (4-cyanophenyl) The resin composition according to any one of [1] to [6], comprising at least one selected from the group consisting of imidazole and 1- (4-nitrophenyl) -1H-imidazole.
[8] Any of [1] to [7], wherein the ratio of the total number of epoxy groups in component (A) to the total number of reactive groups in component (B) is 1: 0.2 to 1: 2. The resin composition described in 1.
[9] The resin composition according to any one of [1] to [8], further including (D) an inorganic filler.
[10] The resin composition according to [9], in which the content of the component (D) is 30 to 90% by mass when the nonvolatile component in the resin composition is 100% by mass.
[11] The resin composition according to [9], wherein the content of the component (D) is 50 to 90% by mass when the nonvolatile component in the resin composition is 100% by mass.
[12] The resin composition according to any one of [9] to [11], wherein the average particle diameter of the component (D) is 0.01 to 5 μm.
[13] The component (A) is selected from the group consisting of bisphenol A type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin, and dicyclopentadiene type epoxy resin. The resin composition in any one of [1]-[12] containing 1 or more types.
[14] The resin composition according to any one of [1] to [13], further comprising (E) a thermoplastic resin.
[15] The resin composition according to any one of [1] to [14], which is a resin composition for an insulating layer of a multilayer printed wiring board.
[16] The resin composition according to any one of [1] to [15], which is a resin composition for a buildup insulating layer of a multilayer printed wiring board.
[17] A sheet-shaped laminated material including a layer of the resin composition according to any one of [1] to [16].
[18] A cured product obtained by thermosetting the resin composition according to any one of [1] to [16].
[19] The cured product according to [18], which has a glass transition temperature (Tg) of 100 to 250 ° C.
[20] When the conductor layer is formed by plating on the surface of the cured product after the roughening treatment, the peel strength between the surface of the cured product and the conductor layer is 0.25 to 0.8 kgf / cm [18] or Hardened | cured material as described in [19].
[21] A multilayer printed wiring board including an insulating layer formed of the cured product according to any one of [18] to [20].
[22] A semiconductor device including the multilayer printed wiring board according to [21].

  ADVANTAGE OF THE INVENTION According to this invention, the progress of hardening can be suppressed at the time of storage, and it can provide the resin composition excellent in the cure latency which can harden | cure rapidly at the time of thermosetting, and can provide an insulating layer.

  A cured product obtained by thermosetting the resin composition of the present invention exhibits a high glass transition temperature (Tg) and a low linear thermal expansion coefficient. That is, the resin composition of the present invention can provide excellent curing characteristics during thermosetting.

<Explanation of terms>
In the present specification, the term “pyridine compound having an electron withdrawing group at the 4-position” is substituted at the 4-position with an electron-withdrawing group, and the 2-position, 3-position, 5-position and 6-position are unsubstituted. It means both a certain pyridine and a pyridine in which the 4-position is substituted with an electron-attracting group and one or more positions of the 2-position, 3-position, 5-position and 6-position are substituted with a substituent.

  In the present specification, the term “imidazole compound having an electron withdrawing group at the 1-position” refers to an imidazole substituted at the 1-position with an electron-withdrawing group and unsubstituted at the 2-position, 4-position and 5-position. It means both imidazole substituted at the 1-position with an electron withdrawing group and at least one position at the 2-position, 4-position and 5-position with a substituent.

  In this specification, the term “optionally substituted” for a compound or group refers to the case where the hydrogen atom of the compound or group is not substituted with a substituent, and the hydrogen of the compound or group. It means both when a part or all of the atoms are substituted with a substituent.

  In this specification, 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, unless otherwise specified. Group, monovalent heterocyclic group, amino group, silyl group, acyl group, acyloxy group, carboxy group, aldehyde group, sulfo group, cyano group, nitro group, hydroxy group, mercapto group and oxo group.

  As a halogen atom used as a substituent, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

  The alkyl group used as a substituent may be either linear or branched. The number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-14, still more preferably 1-12, even more preferably 1-6, and particularly preferably 1-3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. , Decyl, and undecyl groups. As will be described later, the alkyl group used as a substituent may further have a substituent (“secondary substituent”). Examples of such an alkyl group having a secondary substituent include an alkyl group substituted with a halogen atom, specifically, a trifluoromethyl group, a trichloromethyl group, a tetrafluoroethyl group, a tetrachloroethyl group, and the like. Is mentioned.

  The number of carbon atoms of the cycloalkyl group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 6. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

  The alkoxy group used as a substituent may be either linear or branched. The number of carbon atoms of the alkoxy group is preferably 1-20, more preferably 1-12, still more preferably 1-6. Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, Examples include octyloxy group, nonyloxy group, and decyloxy group.

  The number of carbon atoms of the cycloalkyloxy group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 6. Examples of the cycloalkyloxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

  The aryl group used as a substituent is a group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon. The number of carbon atoms of the aryl group used as a substituent is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and even more preferably 6 to 10. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.

  The number of carbon atoms of the aryloxy group used as a substituent is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and even more preferably 6 to 10. Examples of the aryloxy group used as a substituent include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group.

The number of carbon atoms of the arylalkyl group used as a substituent is preferably 7 to 25, more preferably 7 to 19, still more preferably 7 to 15, and even more preferably 7 to 11. Examples of the arylalkyl group include a phenyl-C ₁ -C ₁₂ alkyl group, a naphthyl-C ₁ -C ₁₂ alkyl group, and an anthracenyl-C ₁ -C ₁₂ alkyl group.

The number of carbon atoms of the arylalkoxy group used as a substituent is preferably 7 to 25, more preferably 7 to 19, still more preferably 7 to 15, and even more preferably 7 to 11. Examples of the arylalkoxy group include a phenyl-C ₁ -C ₁₂ alkoxy group and a naphthyl-C ₁ -C ₁₂ alkoxy group.

  The monovalent heterocyclic group used as a substituent refers to a group obtained by removing one hydrogen atom from a heterocyclic ring of a heterocyclic compound. The number of carbon atoms of the monovalent heterocyclic group is preferably 3-21, more preferably 3-15, and still more preferably 3-9. The monovalent heterocyclic group includes a monovalent aromatic heterocyclic group (heteroaryl group). Examples of the monovalent heterocyclic ring include thienyl group, pyrrolyl group, furanyl group, furyl group, pyridyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, triazinyl group, pyrrolidyl group, piperidyl group, quinolyl group, and isoquinolyl group. Is mentioned.

  The acyl group used as a substituent refers to a group represented by the formula: —C (═O) —R (wherein R is an alkyl group or an aryl group). The alkyl group represented by R may be linear or branched. Examples of the aryl group represented by R include a phenyl group, a naphthyl group, and an anthracenyl group. The number of carbon atoms of the acyl group is preferably 2 to 20, more preferably 2 to 13, and further preferably 2 to 7. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, and a benzoyl group.

  The acyloxy group used as a substituent refers to a group represented by the formula: —O—C (═O) —R (wherein R is an alkyl group or an aryl group). The alkyl group represented by R may be linear or branched. Examples of the aryl group represented by R include a phenyl group, a naphthyl group, and an anthracenyl group. The number of carbon atoms of the acyloxy group is preferably 2 to 20, more preferably 2 to 13, and further preferably 2 to 7. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, and a benzoyloxy group.

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

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

[Resin composition]
The resin composition of the present invention comprises (A) an epoxy resin, (B) an active ester curing agent, and (C) a curing accelerator, and (C) a pyridine compound having an electron withdrawing group at the 4-position; It includes one or more selected from the group consisting of imidazole compounds having an electron withdrawing group at the 1-position.

  As described above, in a conventional resin composition containing a curing accelerator, curing may gradually progress during storage and the viscosity may increase. In a conventional resin composition system in which a part that is extremely reactive as curing progresses even at the time of storage and a part that exhibits appropriate reactivity such that curing proceeds only by heating associated with the thermosetting process are mixed. In addition to the poor curing potential, there was room for improvement in the properties of the cured product obtained by thermal curing. That is, in a resin composition in which such highly different portions are mixed, phase separation tends to occur and the phase separation structure tends to be coarsened. For example, the desired glass transition temperature (Tg) and the like can be obtained. There were cases where it was disadvantageous to obtain physical properties. On the other hand, the resin composition of the present invention is used by combining the specific components (A) to (C) described above, so that the progress of curing is suppressed during storage, and the cured product is rapidly cured during thermal curing. Can bring. Thus, in the resin composition of the present invention having no unevenness in reactivity, the entire resin composition can be cured almost simultaneously, and even when phase separation occurs, before the phase separation structure becomes coarse The curing reaction can be completed. Although mentioned later in detail, the resin composition of this invention brings about the hardened | cured material which is further excellent in characteristics, such as a glass transition temperature (Tg) and a linear thermal expansion coefficient. It has been confirmed that such an effect is particularly prominent when an active ester curing agent is used as a curing agent, and is synergistically expressed by a combination of the active ester curing agent and the specific curing accelerator. Is.

  Hereinafter, the components (A) to (C) will be described.

<(A) component>
The component (A) contained in the resin composition of the present invention is an epoxy resin.

  The epoxy resin is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, dicyclo Pentadiene type epoxy resin, anthracene type epoxy resin, fluorene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, trisphenol epoxy resin, phosphorus-containing epoxy resin, alicyclic epoxy resin, linear aliphatic epoxy resin, Phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, epoxy resin having butadiene structure, heterocyclic epoxy resin, containing spiro ring Poxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, diglycidyl etherified product of bisphenols, diglycidyl etherified product of naphthalenediol, glycidyl etherified product of phenols, and diglycidyl etherified product of alcohols, and these And alkyl-substituted products, halides, and hydrogenated products of epoxy resins. Among these, an epoxy resin selected from the group consisting of bisphenol A type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin, and dicyclopentadiene type epoxy resin is preferable. These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, two or more epoxy groups in one molecule and a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and two or more (preferably three or more) per molecule. And an epoxy group which is solid at a temperature of 20 ° C. (hereinafter referred to as “solid epoxy resin”). By using a liquid epoxy resin and a solid epoxy resin in combination as an epoxy resin, a resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the insulating layer formed by curing the resin composition is also improved.

  As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, or glycidyl ester type epoxy resin are preferable, bisphenol A type epoxy resin, naphthalene type epoxy resin, or A glycidyl ester type epoxy resin is more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, and “828US” (bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation). ), “JER828EL” (bisphenol A type epoxy resin), “jER807” (bisphenol F type epoxy resin), “jER152” (phenol novolac type epoxy resin), “ZX1059” (bisphenol A type) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Epoxy resin and bisphenol F type epoxy resin), “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, and the like. These may be used individually by 1 type, or may use 2 or more types together.

  Examples of solid epoxy resins include tetrafunctional naphthalene type epoxy resins, naphthol novolak epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, A cyclopentadiene type epoxy resin is preferable, a tetrafunctional naphthalene type epoxy resin, a naphthol novolak type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin or a dicyclopentadiene type epoxy resin is more preferable, and a naphthol novolak type epoxy resin, biphenyl. Type epoxy resin, naphthylene ether type epoxy resin or dicyclopentadiene type epoxy resin is more preferable. Specific examples of the solid epoxy resin include “HP-4700”, “HP-4710” (tetrafunctional naphthalene type epoxy resin), “N-690” (cresol novolac type epoxy resin) manufactured by DIC Corporation, “ N-695 "(cresol novolac type epoxy resin)," HP-7200 "(dicyclopentadiene type epoxy resin)," EXA7311 "," EXA7311-G3 "," HP6000 "," EXA7311-G4 "," EXA7311-G4S " ”(Naphthylene ether type epoxy resin),“ EPPN-502H ”(trisphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd.,“ NC7000L ”(naphthol novolac epoxy resin),“ NC3000H ”,“ NC3000 ”,“ NC3000L ” ”,“ NC3100 ”(biphenyl type XES resin), "ESN475V" (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "ESN485" (naphthol novolak type epoxy resin), "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation , “YX4000H”, “YX4000HK” (bixylenol type epoxy resin), “PG-100”, “CG-500” manufactured by Osaka Gas Chemical Co., Ltd., “YL7800” (fluorene type epoxy manufactured by Mitsubishi Chemical Corporation) Resin) and the like.

  When the liquid epoxy resin and the solid epoxy resin are used in combination as the epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1: 6 by mass ratio. preferable. By making the quantitative ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is obtained when used in the form of an adhesive film, ii) when used in the form of an adhesive film Sufficient flexibility and handleability are improved, and iii) an insulating layer having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii) above, the quantitative ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.3 to 1: 5 by mass ratio. Is more preferable, the range of 1: 0.6 to 1: 4.5 is more preferable, and the range of 1: 0.8 to 1: 4 is particularly preferable.

3-50 mass% is preferable, as for content of (A) component in a resin composition, 5-45 mass% is more preferable, 5-40 mass% is still more preferable, and 7-35 mass% is especially preferable.
In addition, in this invention, content of each component in a resin composition is a value when the sum total of the non-volatile component in a resin composition shall be 100 mass% unless there is separate description.

  The epoxy equivalent of the epoxy resin is preferably 50 to 3000, more preferably 80 to 2000, and still more preferably 110 to 1000. By being in this range, the crosslink density of the cured product is sufficient and an insulating layer having a low surface roughness is obtained. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

<(B) component>
The component (B) contained in the resin composition of the present invention is an active ester curing agent.

  Although there is no restriction | limiting in particular as an active ester hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are contained in 1 molecule. A compound having two or more is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Among these, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable.

  Examples of the carboxylic acid compound include an aliphatic carboxylic acid having 1 to 20 carbon atoms (preferably 2 to 10 and more preferably 2 to 8) and an aromatic having 7 to 20 carbon atoms (preferably 7 to 10). Carboxylic acid is mentioned. Suitable aliphatic carboxylic acids include, for example, acetic acid, malonic acid, succinic acid, maleic acid, itaconic acid and the like. Suitable examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like.

  Examples of the phenol compound include phenol compounds having 6 to 40 carbon atoms (preferably 6 to 30, more preferably 6 to 23, and further preferably 6 to 22). Specific examples include hydroquinone, Resorcin, bisphenol A, bisphenol F, bisphenol S, phenol phthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydroxybenzophenone, tri Examples thereof include hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol and the like. A phenol novolac may also be used as the phenol compound.

  Examples of the naphthol compound include naphthol compounds having 10 to 40 carbon atoms (preferably 10 to 30, more preferably 10 to 20), and specific examples include α-naphthol, β-naphthol, , 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like. A naphthol novolak may also be used as the naphthol compound.

  Preferable specific examples of the active ester curing agent include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolac. The active ester compound containing is mentioned, Among these, the active ester compound containing a naphthalene structure and the active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. In the present invention, the “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.

  Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene type diphenol structure. "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolac Examples of the active ester compound containing YLH1026 (manufactured by Mitsubishi Chemical Corporation).

  An active ester hardening | curing agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The quantity ratio of the component (A) and the component (B) in the resin composition is the ratio of the total number of epoxy groups in the component (A) and the total number of reactive groups in the component (B) ([(A) component The total number of epoxy groups]: [total number of reactive groups in component (B)]) is preferably in the range of 1: 0.2 to 1: 2, more preferably 1: 0.3 to 1: 1.5. Preferably, 1: 0.4 to 1: 1 is more preferable. Here, the total number of epoxy groups in the component (A) is a value obtained by totaling the values obtained by dividing the solid mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the reactive groups in the component (B). A total number is the value which totaled the value which remove | divided the solid content mass of each active ester hardening | curing agent by the reactive group equivalent about all the active ester hardening | curing agents.

<(C) component>
Component (C) contained in the resin composition of the present invention contains one or more selected from the group consisting of a pyridine compound having an electron withdrawing group at the 4-position and an imidazole compound having an electron-withdrawing group at the 1-position. It is a curing accelerator.

  In this invention, the resin composition which is excellent in hardening latency is implement | achieved by using such a specific hardening accelerator in combination with (A) component and (B) component.

In the pyridine compound having an electron withdrawing group at the 4-position and the imidazole compound having an electron withdrawing group at the 1-position, the electron-withdrawing group is not particularly limited as long as it exhibits an electron-withdrawing property with respect to the pyridine ring and the imidazole ring. A group having a Hammett's substituent constant σ _m value of greater than 0 is preferred.

Here, Hammett's substituent constant will be described. Hammett's rule is an empirical rule proposed by Hammett (1935) to quantitatively discuss the influence of substituents on the reaction or equilibrium of benzene derivatives. Substituent constants determined by Hammett's rule include σ _p values and σ _m values, and these values have been clarified for various groups. For example, Iwanami Rikagaku Dictionary 5th edition (1999), Chem. Rev. , Vol. 91, pp. In documents such as 165-195 (1991), the σ _p value and σ _m value of each group can be confirmed. a sigma _p value and sigma _m value both tend to exhibit strong electron-withdrawing greater the value. In the present invention, the σ _m value is focused. From the viewpoint of obtaining a resin composition having excellent curing latency in combination with the component (A) and the component (B), the electron withdrawing group is a Hammett substitution. The group constant σ _m value is more preferably 0.05 or more, still more preferably 0.1 or more, still more preferably 0.15 or more, particularly preferably 0.2 or more, 0.25 or more, 0.3 or more, Or it is 0.35 or more. The upper limit of the σ _m value is not particularly limited, but is usually 2 or less, preferably 1.8 or less, more preferably 1.6 or less, still more preferably 1.4 or less, even more preferably 1.2 or less, Particularly preferably, it is 1.1 or less or 1.0 or less.

Note that 4-dimethylaminopyridine used as a curing accelerator in the prior art is a pyridine compound having a dimethylamino group at the 4-position. The dimethylamino group is an electron donating group, and its σ _m value is −0.16. Similarly, 1-benzyl-2-phenylimidazole used as a curing accelerator in the prior art is an imidazole compound having a benzyl group at the 1-position. The benzyl group is an electron donating group, and the σ _m value is −0.08.

Examples of the group having Hammett's substituent constant σ _m value larger than 0 include, for example, a halogen atom (in the range of about 0.34 to 0.39 depending on the type), a cyano group (0.56), a nitro group (0. 71), an optionally substituted phenyl group (in the range of approximately 0.06 to 0.30 depending on the type), and an optionally substituted vinyl group (approximately 0.00. 02 to 0.77), a carboxymethylene group which may have a substituent (0.07 or more depending on the type), and a cyanoalkylene having 2 or 3 carbon atoms which may have a substituent A group (in the range of about 0.05 to 0.97 depending on the type), a carbonyl group (in the range of about 0.23 to 0.63 depending on the type of the group bonded to the other bond), a thiocarbonyl group ( Approximately 0.25 depending on the type of group attached to the other bond 0.30), a sulfonyl group (approximately 0.51-1.10 depending on the type of group bonded to the other bond), and a phosphoryl group (type of group bonded to the other bond) Depending on the case, about 0.13 to 0.81) may be mentioned. Values in parentheses indicate Hammett's substituent constant σ _m value.

From the viewpoint of obtaining a resin composition having excellent curing latency in combination with the component (A) and the component (B), a pyridine compound having an electron withdrawing group at the 4-position is
4-position halogen atom, cyano group, nitro group, phenyl group which may have a substituent, vinyl group which may have a substituent, carboxymethylene group which may have a substituent, substitution It is preferably a pyridine compound having a cyanoalkylene group having 2 or 3 carbon atoms which may have a group, a carbonyl group, a thiocarbonyl group, a sulfonyl group, or a phosphoryl group;
More preferably, it is a pyridine compound having a halogen atom, a cyano group, a nitro group, an optionally substituted phenyl group, a carbonyl group, a thiocarbonyl group, a sulfonyl group, or a phosphoryl group at the 4-position;
More preferably, it is a pyridine compound having a halogen atom, a cyano group, a nitro group, an optionally substituted phenyl group, a carbonyl group, a sulfonyl group, or a phosphoryl group at the 4-position;
Even more preferably, it is a pyridine compound having a cyano group or a carbonyl group at the 4-position;
A pyridine compound having a carbonyl group at the 4-position is particularly preferable.

From the viewpoint of obtaining a resin composition having excellent curing latency in combination with the component (A) and the component (B), an imidazole compound having an electron withdrawing group at the 1-position is
1-position halogen atom, cyano group, nitro group, phenyl group which may have a substituent, vinyl group which may have a substituent, carboxymethylene group which may have a substituent, substitution An imidazole compound having a cyanoalkylene group having 2 or 3 carbon atoms which may have a group, a carbonyl group, a thiocarbonyl group, a sulfonyl group, or a phosphoryl group;
1-position has a cyano group, a phenyl group which may have a substituent, a vinyl group which may have a substituent, a carboxymethylene group which may have a substituent, and a substituent. More preferably an imidazole compound having a cyanoalkylene group having 2 or 3 carbon atoms, a carbonyl group, or a sulfonyl group;
A 1-position cyano group, a phenyl group which may have a substituent, a vinyl group which may have a substituent, a cyanoalkylene group having 2 or 3 carbon atoms which may have a substituent, More preferably, it is an imidazole compound having a carbonyl group or a sulfonyl group;
Even more preferably, it is an imidazole compound having a phenyl group, a carbonyl group, or a sulfonyl group which may have a substituent at the 1-position;
Particularly preferred is an imidazole compound having a carbonyl group at the 1-position.

  When the component (C) includes a pyridine compound having a phenyl group optionally having a substituent at the 4-position or a pyridine compound having a phenyl group optionally having a substituent at the 1-position, the phenyl group is present. Examples of the substituent that may be used are as described above. When the phenyl group has a plurality of substituents, they may be the same or different. Among these, as the substituent that the phenyl group may have, one or more groups selected from the group consisting of a halogen atom, an alkyl group, a cyano group, a nitro group, and an aldehyde group are preferable, and a halogen atom, a cyano group, More preferred is one or more groups selected from the group consisting of nitro groups and aldehyde groups. These substituents may have a secondary substituent. Accordingly, a fluoroalkyl group such as a trifluoromethyl group is naturally included in the substituent of the present application.

  When the component (C) includes a pyridine compound having a vinyl group which may have a substituent at the 4-position or a pyridine compound having a vinyl group which may have a substituent at the 1-position, the vinyl group is present. Examples of the substituent that may be used are as described above. When the vinyl group has a plurality of substituents, they may be the same or different. Among them, the substituent that the vinyl group may have is preferably one or more groups selected from the group consisting of a halogen atom, an alkyl group, a cyano group, a nitro group, and an aldehyde group, a halogen atom, a cyano group, More preferred is one or more groups selected from the group consisting of nitro groups and aldehyde groups. These substituents may have a secondary substituent. Accordingly, a fluoroalkyl group such as a trifluoromethyl group is naturally included in the substituent of the present application.

  When the component (C) includes a pyridine compound having a carboxymethylene group optionally having a substituent at the 4-position or an imidazole compound having a carboxymethylene group optionally having a substituent at the 1-position, the carboxymethylene Examples of the substituent that the group may have are as described above. When the carboxymethylene group has a plurality of substituents, they may be the same or different. Especially, as a substituent which a carboxymethylene group may have, 1 or more groups selected from the group which consists of a halogen atom, a cyano group, and a nitro group are preferable.

  (C) A pyridine compound having a cyanoalkylene group having 2 or 3 carbon atoms which may have a substituent at the 4-position, or 2 or 3 carbon atoms which may have a substituent at the 1-position When the imidazole compound having a cyanoalkylene group is included, examples of the substituent that the cyanoalkylene group having 2 or 3 carbon atoms may have are as described above. When the cyanoalkylene group having 2 or 3 carbon atoms has a plurality of substituents, they may be the same or different. The cyanoalkylene group having 2 or 3 carbon atoms means a cyanomethylene group or a cyanoethylene group, and the number of carbon atoms of the substituent is not included in the number of carbon atoms. The substituent which the cyanoalkylene group having 2 or 3 carbon atoms may have is preferably one or more groups selected from the group consisting of a halogen atom, a cyano group and a nitro group.

  When the component (C) includes a pyridine compound having a carbonyl group at the 4-position or an imidazole compound having a carbonyl group at the 1-position, the other bond of the carbonyl group (that is, opposite to the 4-position of pyridine or the 1-position of imidazole) Group (hereinafter also referred to as “monovalent group bonded to a carbonyl group”) is not particularly limited, but is preferably a hydrogen atom, a hydroxy group, or an alkyl group which may have a substituent. , An alkoxy group which may have a substituent, an aryl group which may have a substituent, an aryloxy group which may have a substituent, a monovalent which may have a substituent A heterocyclic group, a heterocyclic oxy group which may have a substituent, an amino group which may have a substituent, an alkylcarbonyl group which may have a substituent, and a substituent; Arylca A carbonyl group, a heterocyclic carbonyl group which may have a substituent, an alkyldithio group which may have a substituent, an aryldithio group which may have a substituent, or a substituent. It may be a heterocyclic dithio group.

  In the monovalent group bonded to the carbonyl group, the number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-15, still more preferably 1-12, even more preferably 1-9, particularly preferably. 1-6, 1-4, or 1-3. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, and a tetradecyl group. , Pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and icosyl group.

  In the monovalent group bonded to the carbonyl group, the number of carbon atoms of the alkoxy group is preferably 1-20, more preferably 1-15, still more preferably 1-12, even more preferably 1-9, particularly preferably. 1-6, 1-4, or 1-3. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, and a dodecyloxy group. , Tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group and icosyloxy group.

  In the monovalent group bonded to the carbonyl group, the number of carbon atoms of the aryl group is preferably 6 to 18, more preferably 6 to 14, still more preferably 6 to 12, and still more preferably 6 to 10. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group, and among them, a phenyl group is preferable.

  In the monovalent group bonded to the carbonyl group, the number of carbon atoms of the aryloxy group is preferably 6 to 18, more preferably 6 to 14, still more preferably 6 to 12, and still more preferably 6 to 10. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the aryloxy group include a phenoxy group, a naphthyloxy group, and an anthracenyloxy group, and among them, a phenoxy group is preferable.

  In the monovalent group bonded to the carbonyl group, the number of carbon atoms of the monovalent heterocyclic group is preferably 3 to 21, more preferably 3 to 15, still more preferably 3 to 9, and even more preferably 3 to 5. It is. The monovalent heterocyclic group includes a monovalent aromatic heterocyclic group (heteroaryl group). Examples of the monovalent heterocyclic group include thienyl group, pyrrolyl group, furanyl group, imidazolyl group, furyl group, pyridyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, triazinyl group, pyrrolidyl group, piperidyl group, quinolyl group. And an isoquinolyl group, among which an imidazolyl group and a pyridyl group are preferable.

  In the monovalent group bonded to the carbonyl group, the number of carbon atoms of the heterocyclic oxy group is preferably 3 to 21, more preferably 3 to 15, still more preferably 3 to 9, and even more preferably 3 to 5. . The heterocyclic oxy group also includes an aromatic heterocyclic oxy group (heteroaryloxy group). Examples of the heterocyclic oxy group include thienyloxy group, pyrrolyloxy group, furanyloxy group, imidazolyloxy group, furyloxy group, pyridyloxy group, pyridazinyloxy group, pyrimidyloxy group, pyrazinyloxy group, and triazinyloxy group. Pyrrolidyloxy group, piperidyloxy group, quinolyloxy group and isoquinolyloxy group, among which imidazolyloxy group and pyridyloxy group are preferable.

  In the monovalent group bonded to the carbonyl group, the number of carbon atoms of the alkylcarbonyl group is preferably 2 to 21, more preferably 2 to 16, still more preferably 2 to 13, even more preferably 2 to 10, and particularly preferably. Is 2-7, 2-5, or 2-4. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the alkylcarbonyl group include a methylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, a butylcarbonyl group, a pentylcarbonyl group, a hexylcarbonyl group, a heptylcarbonyl group, an octylcarbonyl group, a nonylcarbonyl group, and a decylcarbonyl group. Is mentioned.

  In the monovalent group bonded to the carbonyl group, the number of carbon atoms of the arylcarbonyl group is preferably 7-19, more preferably 7-15, still more preferably 7-13, and even more preferably 7-11. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the arylcarbonyl group include a phenylcarbonyl group, a naphthylcarbonyl group, and an anthracenylcarbonyl group.

  In the monovalent group bonded to the carbonyl group, the number of carbon atoms of the heterocyclic carbonyl group is preferably 4 to 22, more preferably 4 to 16, still more preferably 4 to 10, and even more preferably 4 to 6. . The number of carbon atoms of the substituent is not included in the number of carbon atoms. The heterocyclic carbonyl group also includes an aromatic heterocyclic carbonyl group (heteroarylcarbonyl group). Examples of the heterocyclic carbonyl group include thienylcarbonyl group, pyrrolylcarbonyl group, furanylcarbonyl group, imidazolylcarbonyl group, furylcarbonyl group, pyridylcarbonyl group, pyridazinylcarbonyl group, pyrimidylcarbonyl group, Examples include a radinylcarbonyl group, a triazinylcarbonyl group, a pyrrolidylcarbonyl group, a piperidylcarbonyl group, a quinolylcarbonyl group, and an isoquinolylcarbonyl group, and among them, an imidazolylcarbonyl group and a pyridylcarbonyl group are preferable.

  In the monovalent group bonded to the carbonyl group, the alkyldithio group preferably has 1 to 20, more preferably 1 to 15, still more preferably 1 to 12, still more preferably 1 to 9, and particularly preferably. Is 1-6, 1-4, or 1-3. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the alkyldithio group include a methyldithio group, an ethyldithio group, a propyldithio group, a butyldithio group, a pentyldithio group, a hexyldithio group, a heptyldithio group, an octyldithio group, a nonyldithio group, and a decyldithio group.

  In the monovalent group bonded to the carbonyl group, the number of carbon atoms of the aryldithio group is preferably 6 to 18, more preferably 6 to 14, still more preferably 6 to 12, and still more preferably 6 to 10. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the aryldithio group include a phenyldithio group, a naphthyldithio group, and an anthracenyldithio group.

  In the monovalent group bonded to the carbonyl group, the number of carbon atoms of the heterocyclic dithio group is preferably 3 to 21, more preferably 3 to 15, still more preferably 3 to 9, and even more preferably 3 to 5. . The heterocyclic dithio group also includes an aromatic heterocyclic dithio group (heteroaryl dithio group). Examples of the heterocyclic dithio group include thienyl dithio group, pyrrolyl dithio group, furanyl dithio group, imidazolyl dithio group, furyl dithio group, pyridyl dithio group, pyridazinyl dithio group, pyrimidyl dithio group, pyrazinyl dithio group, triazinyl dithio group, pyrrole Examples thereof include a dildithio group, a piperidyldithio group, a quinolyldithio group, and an isoquinolyldithio group.

  Examples of the substituent that the monovalent group bonded to the carbonyl group may have are as described above. When the monovalent group bonded to the carbonyl group has a plurality of substituents, they may be the same or different. Especially, as a substituent which the monovalent group couple | bonded with a carbonyl group may have, 1 or more types of groups selected from the group which consists of a halogen atom, an amino group, and an aryl group are preferable. Among these, in the case of an aryl group, an aryl group having 6 to 14 carbon atoms is preferable, a phenyl group, a naphthyl group, and an anthracenyl group are more preferable, and an anthracenyl group is further preferable. These substituents may have a secondary substituent. Accordingly, an oxyaryl group such as an anthraquinolyl group is naturally included in the substituent of the present application.

  When the component (C) includes a pyridine compound having a thiocarbonyl group at the 4-position or an imidazole compound having a thiocarbonyl group at the 1-position, the other bond of the thiocarbonyl group (that is, pyridine 4-position or imidazole 1-position is The group (hereinafter also referred to as “monovalent group bonded to the thiocarbonyl group”) bonded to the other side bond is not particularly limited, but preferably has a hydrogen atom, a mercapto group, or a substituent. An alkyl group which may have a substituent, an aryl group which may have a substituent, a monovalent heterocyclic group which may have a substituent, or an amino group which may have a substituent.

  In the monovalent group bonded to the thiocarbonyl group, the alkyl group, aryl group, and heterocyclic group are as described for the monovalent group bonded to the carbonyl group.

  Examples of the substituent that the monovalent group bonded to the thiocarbonyl group may have are as described for the monovalent group bonded to the carbonyl group.

  When the component (C) includes a pyridine compound having a sulfonyl group at the 4-position or an imidazole compound having a sulfonyl group at the 1-position, the other bond of the sulfonyl group (that is, opposite to the 4-position of pyridine or the 1-position of imidazole) Group (hereinafter also referred to as “monovalent group bonded to a sulfonyl group”) is not particularly limited, but preferably has an alkyl group which may have a substituent, or a substituent. An aryl group which may be substituted, a monovalent heterocyclic group which may have a substituent, or an amino group which may have a substituent.

  In the monovalent group bonded to the sulfonyl group, the alkyl group, aryl group, and heterocyclic group are as described for the monovalent group bonded to the carbonyl group.

  Examples of the substituent that the monovalent group bonded to the sulfonyl group may have are as described for the monovalent group bonded to the carbonyl group.

  When the component (C) includes a pyridine compound having a phosphoryl group at the 4-position or an imidazole compound having a phosphoryl group at the 1-position, the other two bonds of the phosphoryl group (ie, bonded to the 4-position of pyridine or the 1-position of imidazole) Group (hereinafter also referred to as “monovalent group bonded to a phosphoryl group”) is not particularly limited, but preferably each independently a hydrogen atom, a hydroxy group, or a substituent. An alkyl group which may have a substituent, an aryl group which may have a substituent, a monovalent heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, An aryloxy group which may have a substituent, or a heterocyclic oxy group which may have a substituent.

  In the monovalent group bonded to the phosphoryl group, the alkyl group, aryl group, monovalent heterocyclic group, alkoxy group, aryloxy group, and heterocyclic oxy group are as described for the monovalent group bonded to the carbonyl group. It is.

  The example of the substituent which the monovalent group couple | bonded with a phosphoryl group may have is as having demonstrated the monovalent group couple | bonded with a carbonyl group.

  The imidazole compound having an electron withdrawing group at the 1-position used for the component (C) may be in the form of an acid salt. Examples of the acid used for forming the acid salt include organic acids. Suitable organic acids include, for example, monovalent or polyvalent carboxylic acids having 1 to 10 carbon atoms (for example, glycolic acid, citric acid, trimellitic acid, etc.), methyl sulfuric acid, ethyl sulfuric acid, p-toluenesulfonic acid. Is mentioned. When the imidazole compound having an electron withdrawing group at the 1-position is in the form of an acid salt, it is preferably a salt of a monovalent or polyvalent carboxylic acid having 1 to 10 carbon atoms, and especially a trimellitic acid salt. It is preferable.

  As described above, the pyridine compound having an electron withdrawing group at the 4-position used for the component (C) has a substituent at a position other than the 4-position (that is, the 2-position, 3-position, 5-position, and 6-position). You may do it. Further, the imidazole compound having an electron withdrawing group at the 1-position used for the component (C) may have a substituent at positions other than the 1-position (that is, the 2-position, 4-position, and 5-position). . These substituents are as described above. Among them, one or more groups selected from the group consisting of an alkyl group and an aryl group are preferable. Among these, in the case of an alkyl group, a C1-C12 alkyl group is preferable. In the case of an aryl group, an aryl group having 6 to 12 carbon atoms is preferable, a phenyl group, a naphthyl group, and an anthracenyl group are preferable, and a phenyl group is more preferable. These substituents may have a secondary substituent. For example, a fluoroalkyl group such as a trifluoromethyl group and a fluoroaryl group such as a perfluorophenyl group are naturally included in the substituent of the present application.

  In one embodiment, the pyridine compound having an electron withdrawing group at the 4-position and the imidazole compound having an electron withdrawing group at the 1-position used for the component (C) are represented by the following formulas (1) and (2), respectively. Is done.

〔式（１）中、Ｘ^１は電子求引基を表し、Ｒ^１は置換基を表し、ｍ１は０〜４の整数を表す。〕

[In ^the formula (1), ^{X 1} represents an electron withdrawing group, ^{R 1} represents a substituent, m1 represents an integer of 0-4. ]

〔式（２）中、Ｘ^２は電子求引基を表し、Ｒ^２は置換基を表し、ｍ２は０〜３の整数を表す。〕

Wherein ^{(2), X} 2 represents an electron withdrawing group, ^{R 2} represents a substituent, m2 represents an integer of 0 to 3. ]

In Formula (1) and Formula (2), X ¹ and X ² represent an electron withdrawing group, and a Hammett's substituent constant σm value is preferably larger than 0. From the viewpoint of obtaining a resin composition having excellent curing latency in combination with the component (A) and the component (B), the Hammett substituent constant σ _m value of X ¹ and X ² is more preferably 0.05. Above, more preferably 0.1 or more, still more preferably 0.15 or more, particularly preferably 0.2 or more, 0.25 or more, 0.3 or more, or 0.35 or more. The upper limit of the σ _m value is not particularly limited, but is usually 2 or less, preferably 1.8 or less, more preferably 1.6 or less, still more preferably 1.4 or less, even more preferably 1.2 or less, Particularly preferably, it is 1.1 or less or 1.0 or less.

In formula (1), as X ¹ ,
Halogen atom, cyano group, nitro group, phenyl group which may have a substituent, vinyl group which may have a substituent, carboxymethylene group which may have a substituent, An optionally substituted cyanoalkylene group having 2 or 3 carbon atoms, a group represented by the formula: —C (═O) —R ³ , a group represented by the formula: —C (═S) —R ⁴ ; A group represented by the formula: —S (═O) ₂ —R ⁵ or a group represented by the formula: —P (═O) (— R ⁶ ) ₂ is preferable;
Halogen atom, a cyano group, a nitro group, which may have a substituent phenyl group of the formula: -C (= O) group represented by -R ^3, wherein: at -C (= S) -R ⁴ A group represented by the formula: —S (═O) ₂ —R ⁵ , or a group represented by the formula: —P (═O) (— R ⁶ ) ₂ is more preferable;
A halogen atom, a cyano group, a nitro group, an optionally substituted phenyl group, a group represented by the formula: —C (═O) —R ³ , a formula: —S (═O) ₂ —R ⁵ Or a group represented by the formula: —P (═O) (— R ⁶ ) ₂ is more preferable;
A cyano group or a group represented by the formula: —C (═O) —R ³ is even more preferred;
A group represented by the formula: —C (═O) —R ³ is particularly preferred.
Here, R ³ is as described above for the “monovalent group bonded to the carbonyl group”, R ⁴ is as described for the above “monovalent group bonded to the thiocarbonyl group”, and R ⁵ Is as described for the “monovalent group bonded to the sulfonyl group”, and R ⁶ is as described for the “monovalent group bonded to the phosphoryl group”.

In formula (2), as X ² ,
Halogen atom, cyano group, nitro group, phenyl group which may have a substituent, vinyl group which may have a substituent, carboxymethylene group which may have a substituent, An optionally substituted cyanoalkylene group having 2 or 3 carbon atoms, a group represented by the formula: —C (═O) —R ³ , a group represented by the formula: —C (═S) —R ⁴ ; A group represented by the formula: —S (═O) ₂ —R ⁵ or a group represented by the formula: —P (═O) (— R ⁶ ) ₂ is preferable;
A cyano group, an optionally substituted phenyl group, an optionally substituted vinyl group, an optionally substituted carboxymethylene group, and an optionally substituted carbon A cyanoalkylene group having 2 or 3 atoms, a group represented by the formula: —C (═O) —R ³ , or a group represented by the formula: —S (═O) ₂ —R ⁵ is more preferable;
A cyano group, a phenyl group which may have a substituent, a vinyl group which may have a substituent, a cyanoalkylene group having 2 or 3 carbon atoms which may have a substituent, a formula:- More preferably a group represented by C (═O) —R ³ or a group represented by the formula: —S (═O) ₂ —R ⁵ ;
A phenyl group which may have a substituent, a group represented by the formula: —C (═O) —R ³ , or a group represented by the formula: —S (═O) ₂ —R ⁵ is even more. Preferably;
A group represented by the formula: —C (═O) —R ³ is particularly preferred.
Here, R ³ , R ⁴ , R ⁵ and R ⁶ are as described above.

In Formula (1) and Formula (2), R ¹ and R ² represent a substituent, and a group selected from the group consisting of an alkyl group and an aryl group is preferable. Among these, in the case of an alkyl group, a C1-C12 alkyl group is preferable. In the case of an aryl group, an aryl group having 6 to 12 carbon atoms is preferable, a phenyl group, a naphthyl group, and an anthracenyl group are more preferable, and a phenyl group is further preferable.

  In formula (1), m1 represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and still more preferably 0 or 1.

  In formula (2), m2 represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1.

  In the component (C), the pyridine compound having an electron withdrawing group at the 4-position may be used alone or in combination of two or more.

  In the component (C), the imidazole compound having an electron withdrawing group at the 1-position may be used alone or in combination of two or more.

  Specific examples of the pyridine compound having an electron withdrawing group at the 4-position that can be suitably used as the component (C) include 4-nitropyridine, 4-cyanopyridine, 4-fluoropyridine, isoniazid, isonicotinic acid, 4- Pyridine carboxaldehyde, thioisonicotinamide, 4-acetylpyridine, ethyl-4-pyridyl ketone, di (4-pyridyl) -ketone, methyl isonicotinate, dodecyl isonicotinate, phenyl isonicotinate, isonicotinic acid amide, N-ethylisonicotinamide, 4-methylsulfonylpyridine, 4-phenylsulfonylpyridine, 4-tosylpyridine, 4-mesylpyridine, 4-pyridinesulfonamide, 4-phenylpyridine, 4- (p-tolyl) -pyridine And diphenyl (4-pyridinyl) phosphineoxy And the like.

Specific examples of the imidazole compound having an electron withdrawing group at the 1-position that can be suitably used for the component (C) include 1-acetylimidazole, 1-vinylimidazole, 1-imidazoleacetic acid, N-tert-butoxycarbonylimidazole, 1- (4-formylphenyl) imidazole, 1,1′-oxalyldiimidazole, 1- (4-cyanophenyl) imidazole , 1-cyanoimidazole, 1,1′-thiocarbonylbis-1H-imidazole, 1- ( Methyldithiocarbonyl) imidazole, 1,1′-sulfonyldiimidazole, N-methanesulfonylimidazole, 1- (p-toluenesulfonyl) imidazole, 1- (2,4,6-trimethylbenzenesulfonyl) imidazole, 1- (2 , 4,6-Triisopropylbenzenesulfonyl ) Imidazole, 1- (trifluoromethanesulfonyl) imidazole , 1- (2-trifluoromethylphenyl) imidazole, 1- (3-trifluoromethylphenyl) imidazole, 1- (4-trifluoromethylphenyl) imidazole, and 1 - (4-nitrophenyl)-1H-imidazole.

Among these, from the viewpoint of obtaining a resin composition having particularly excellent curing latency in combination with the component (A) and the component (B), the component (C) includes 4-benzoylpyridine, 4-cyanopyridine, and isonicotinic acid. It preferably contains one or more selected from the group consisting of ethyl , 1,1′-sulfonyldiimidazole, 1- (4-cyanophenyl) imidazole, and 1- (4-nitrophenyl) -1H-imidazole, More preferably, it contains at least one selected from the group consisting of 4-benzoylpyridine and ethyl isonicotinate .

  The content of the component (C) in the resin composition is preferably in the range of 0.05 to 3% by mass, more preferably 100% by mass when the total amount of the non-volatile components of the component (A) and the component (B) is 100% by mass. Is preferably used in the range of 0.1 to 2% by mass.

<(D) component>
The resin composition of the present invention may further contain (D) an inorganic filler as necessary.

  Examples of inorganic fillers include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, and nitride. Boron, aluminum nitride, manganese nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, zirconium phosphate, and phosphoric acid Examples thereof include zirconium tungstate. Among these, silica such as amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica is particularly suitable. Moreover, spherical silica is preferable as the silica. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type. Examples of commercially available spherical fused silica include “SOC2” and “SOC1” manufactured by Admatechs.

  The average particle size of the inorganic filler is preferably in the range of 0.01 μm to 5 μm, preferably in the range of 0.05 μm to 2 μm, from the viewpoint of increasing the fluidity of the resin composition and realizing sufficient circuit embedding property and component embedding property. Is more preferable, the range of 0.1 μm to 1 μm is still more preferable, and 0.3 μm to 0.8 μm is even more preferable. The average particle diameter 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 prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-500 manufactured by Horiba, Ltd. can be used.

  Inorganic fillers are aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents from the viewpoint of improving moisture resistance and dispersibility. It is preferable that it is processed with 1 or more types of surface treating agents. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” (3-mercaptopropyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd.). Silane), Shin-Etsu Chemical "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical "SZ-31" (Hexamethyldisilazane) manufactured by Co., Ltd.

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

  The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.

  The content of the component (D) in the resin composition is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, from the viewpoint of obtaining an insulating layer having a low linear thermal expansion coefficient. Still more preferably, it is 60 mass% or more, Most preferably, it is 70 mass% or more. The upper limit of the content of the component (D) is preferably 90% by mass or less, more preferably 85% by mass or less, from the viewpoint of mechanical strength of the obtained insulating layer. Therefore, in one embodiment, content of (D) component in a resin composition becomes like this. Preferably it is 30-90 mass%, More preferably, it is 40-90 mass%, More preferably, it is 50-90 mass%.

  In one Embodiment, the resin composition of this invention contains the above-mentioned (A) component, (B) component, (C) component, and (D) component. The resin composition is selected from the group consisting of bisphenol A type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin, and dicyclopentadiene type epoxy resin as component (A). It is preferable that one or more selected components each contain silica as component (D). From the standpoint of realizing particularly excellent curing potential, the resin composition of the present invention comprises bisphenol A type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidyl ester type epoxy resin, biphenyl as component (A). An active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound as a component (B), using at least one selected from the group consisting of a type epoxy resin and a dicyclopentadiene type epoxy resin ( (C) a curing accelerator containing a pyridine having a cyano group or a carbonyl group at the 4-position and / or an imidazole having a phenyl group, a carbonyl group or a sulfonyl group optionally having a substituent at the 1-position (D) It is preferable that silica is included as a component.

<(E) component>
The resin composition of the present invention may further contain (E) a thermoplastic resin, if necessary.

  Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyethersulfone resin, polyphenylene ether resin, and polysulfone resin. A thermoplastic resin may be used individually by 1 type, or may use 2 or more types together.

  The weight average molecular weight in terms of polystyrene of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, or may use 2 or more types together. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). In addition, “FX280” and “FX293” manufactured by Toto Kasei Co., Ltd., “YL7553”, “YL6794”, “YL7213” manufactured by Mitsubishi Chemical Corporation, YL7290 "," YL7482 ", etc. are mentioned.

  Specific examples of the polyvinyl acetal resin include: Electric Butyral 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., S-Lec BH Series, BX Series manufactured by Sekisui Chemical Co., Ltd. KS series, BL series, BM series, etc. are mentioned.

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (described in JP-A No. 2002-12667 and JP-A No. 2000-319386).

  Specific examples of the polyamide-imide resin include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd.

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.

  Content of (E) component in a resin composition becomes like this. Preferably it is 0.1-20 mass%, More preferably, it is 0.5-10 mass%.

<Other ingredients>
The resin composition of the present invention may further contain additives such as (F) a curing agent other than the active ester curing agent, (G) a flame retardant, and (H) rubber particles, if necessary.

-(F) Curing agents other than active ester curing agents-
The curing agent other than the active ester curing agent is not particularly limited as long as it has a function of curing the epoxy resin. For example, a phenol-based curing agent, a naphthol-based curing agent, a benzoxazine-based curing agent, and a cyanate ester-based curing agent are included. Can be mentioned. Such a hardening | curing agent may be used individually by 1 type, or may be used in combination of 2 or more type.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Moreover, from a viewpoint of adhesiveness with a conductor layer (circuit wiring), a nitrogen-containing phenol type hardening | curing agent is preferable and a triazine frame | skeleton containing phenol type hardening | curing agent is more preferable. Among these, a triazine skeleton-containing phenol novolak resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesiveness (peel strength) to the conductor layer.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN375”, “SN395” manufactured by Toto Kasei Co., Ltd. "LA7052", "LA7054", "LA3018", etc. manufactured by DIC Corporation.

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Examples of cyanate ester-based curing agents include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Novolac and K Examples include polyfunctional cyanate resins derived from sol novolac, prepolymers in which these cyanate resins are partly triazines, etc. Specific examples of cyanate ester curing agents include “PT30” manufactured by Lonza Japan Co., Ltd. “PT60” (both phenol novolac-type polyfunctional cyanate ester resins), “BA230” (prepolymer in which a part or all of bisphenol A dicyanate is triazine-modified), and the like.

  When the resin composition of the present invention contains the component (F), the ratio of the total number of reactive groups in the component (F) to the total number of reactive groups in the component (B) ([ (F) Total number of reactive groups in component] / [Total number of reactive groups in component (B)]) is preferably 1 or less, more preferably 0.8 or less, even more preferably 0.6 or less, and even more. Preferably it is 0.5 or less, particularly preferably 0.4 or less.

-(G) Flame retardant-
Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. A flame retardant may be used individually by 1 type and may be used in combination of 2 or more type. Although content of (G) component in a resin composition layer is not specifically limited, 0.5-10 mass% is preferable and 1-9 mass% is more preferable.

-(H) Rubber particles-
As the rubber particles, for example, those that do not dissolve in the organic solvent described later, and are incompatible with the above-described components (A) and (B) (when included, the components (E) and (F)) are used. The Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which it does not dissolve in an organic solvent or resin and making it into particles.

  Examples of the rubber particles include core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, a two-layer structure in which an outer shell layer is made of a glassy polymer and an inner core layer is made of a rubbery polymer, or Examples include a three-layer structure in which the outer shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer. The glassy polymer layer is made of, for example, methyl methacrylate polymer, and the rubbery polymer layer is made of, for example, butyl acrylate polymer (butyl rubber). A rubber particle may be used individually by 1 type, or may use 2 or more types together.

  The average particle size of the rubber particles is preferably in the range of 0.005 μm to 1 μm, more preferably in the range of 0.2 μm to 0.6 μm. The average particle diameter of the rubber particles can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and a particle size distribution of rubber particles is created on a mass basis using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). And it can measure by making the median diameter into an average particle diameter.

  The content of the component (H) in the resin composition is preferably 1 to 10% by mass, more preferably 2 to 5% by mass.

  The resin composition of the present invention may contain other additives as necessary. Examples of such other additives include organic metals such as organic copper compounds, organic zinc compounds, and organic cobalt compounds. Examples include compounds and resin additives such as organic fillers, thickeners, antifoaming agents, leveling agents, adhesion-imparting agents, and coloring agents.

  The resin composition of the present invention can be suitably used as a resin composition (resin composition for an insulating layer of a multilayer printed wiring board) for forming an insulating layer of a multilayer printed wiring board. Since the resin composition of the present invention is excellent in curing latency, the desired circuit embedding property can be realized in the production of a multilayer printed wiring board. Among them, in the production of multilayer printed wiring boards by the build-up method, it can be suitably used as a resin composition for forming an insulating layer (resin composition for build-up insulating layers of multilayer printed wiring boards). It can be more suitably used as a resin composition for forming an insulating layer in which a conductor layer is formed by plating (a resin composition for a build-up insulating layer of a multilayer printed wiring board in which a conductor layer is formed by plating). . In addition, since the resin composition of the present invention can realize the desired fluidity and component embedding property, it can be suitably used even when the multilayer printed wiring board is a component built-in circuit board. That is, the resin composition of the present invention can be suitably used as a resin composition for embedding components on a component-embedded circuit board (resin composition for embedding components).

[Sheet laminated material]
The resin composition of the present invention can be applied in a varnish state and used for various applications, but industrially, it is generally preferable to use it in the form of a sheet-like laminated material including a layer of the resin composition. is there.

  As the sheet-like laminated material, the following adhesive films and prepregs are preferable.

  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 the resin composition of the present invention. Formed from.

  The thickness of the resin composition layer varies depending on the use, but when used as an insulating layer of a multilayer printed wiring board, it is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and even more preferably 50 μm or less. It is. Although the minimum of the thickness of a resin composition layer changes with uses, when using as an insulating layer of a multilayer printed wiring board, it is 10 micrometers or more normally.

  A film made of a plastic material is preferably used as the support. Examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”), polycarbonate (hereinafter referred to as “PET”). PC ”), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable. In a preferred embodiment, the support is a polyethylene terephthalate film.

  The support may be subjected to a mat treatment or a corona treatment on the surface to be joined to the resin composition layer. Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used.

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

  The adhesive film is prepared, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish on a support using a die coater, and drying the organic solvent. Can be produced.

  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, cellosolve and butyl carbitol, etc. Carbitols, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

  Drying may be performed by a known method such as heating or hot air blowing. The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of the organic solvent is used, the resin composition layer is dried at 50 to 150 ° C. for 3 to 10 minutes. Can be formed.

  In the adhesive film, a protective film according to the support can be further laminated on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support). Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can be stored in a roll shape. When an adhesive film has a protective film, it can be used by peeling off the protective film.

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

  The sheet-like fiber base material used for a prepreg is not specifically limited, What is used normally as base materials for prepregs, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, can be used. When used for forming an insulating layer of a multilayer printed wiring board, a thin sheet-like fiber substrate having a thickness of 50 μm or less is preferably used, and particularly a sheet-like fiber substrate having a thickness of 10 μm to 40 μm is preferable. A sheet-like fiber substrate of 10 μm to 30 μm is more preferable, and a sheet-like fiber substrate of 10 to 20 μm is more preferable.

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

  The thickness of the prepreg can be in the same range as the resin composition layer in the adhesive film described above.

  In the sheet-like laminated material, the minimum melt viscosity of the resin composition layer is determined based on the specific design of the multilayer printed wiring board (the circuit thickness of the inner layer circuit board, the line / space ratio, The optimum values for achieving good circuit embeddability and component embeddability differ depending on the cavity size and the like. Therefore, when manufacturing a sheet-like laminated material, it designs so that a resin composition layer may show desired minimum melt viscosity. However, with regard to a sheet-like laminated material using a conventional resin composition containing a curing accelerator, the viscosity of the resin composition may gradually increase during storage, and the viscosity may increase. Sometimes had a minimum melt viscosity significantly higher than the expected value.

On the other hand, in the sheet-like laminated material including the resin composition layer of the present invention, the progress of curing of the resin composition during storage is suppressed, and the desired minimum melt viscosity can be advantageously maintained. In one embodiment, the sheet-shaped laminated material of the present invention is a resin composition after the minimum melt viscosity of the resin composition layer immediately after its manufacture is V ₁ (poise) and stored at room temperature (25 ° C.) for 7 days. When the minimum melt viscosity of the layer is V ₂ (poise), the ratio of V ₂ / V ₁ (hereinafter also referred to as “thickening ratio”) is preferably 2 or less, more preferably 1.8 or less, Preferably it is 1.6 or less, More preferably, it is 1.5 or less, Especially preferably, it is 1.4 or less, 1.3 or less or 1.2 or less. The lower limit of the thickening factor is preferably 1.

  Here, the “minimum melt viscosity” of the resin composition layer refers to the lowest viscosity exhibited by the resin composition layer when the resin of the resin composition layer is melted. Specifically, when the resin composition layer is heated at a constant temperature increase rate to melt the resin, the initial stage of the melt viscosity decreases with increasing temperature, and then, when the temperature exceeds a certain temperature, the melt viscosity decreases with increasing temperature. To rise. “Minimum melt viscosity” refers to the melt viscosity at such a minimum point. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelastic method. Specifically, the minimum melt viscosity of the resin composition layer can be obtained by performing dynamic viscoelasticity measurement under the conditions of a measurement start temperature of 60 ° C., a temperature increase rate of 5 ° C./min, a frequency of 1 Hz, and a strain of 1 deg. it can. Examples of the dynamic viscoelasticity measuring apparatus include “Rheosol-G3000” manufactured by UBM Co., Ltd.

[Cured product]
The cured product of the present invention is obtained by thermosetting the resin composition of the present invention.

  The thermosetting conditions for the resin composition are not particularly limited, and for example, the conditions normally employed when forming the insulating layer of the multilayer printed wiring board may be used.

  For example, although the thermosetting conditions of the resin composition vary depending on the composition of the resin composition, the curing temperature is in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 210 ° C, more preferably in the range of 170 ° C to 190 ° C. C.) and the curing time can be in the range of 5 minutes to 90 minutes (preferably 10 minutes to 75 minutes, more preferably 15 minutes to 60 minutes).

  Before the resin composition is thermally cured, the resin composition may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition, the resin composition is kept at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower) for 5 minutes. Preheating may be performed as described above (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

As described above, the resin composition of the present invention suppresses the progress of curing during storage, but quickly cures during thermal curing, resulting in a cured product having the desired characteristics. Specifically, the cured product of the present invention can exhibit a high glass transition temperature (Tg). For example, the cured product of the present invention is preferably 100 ° C or higher, more preferably 120 ° C or higher, still more preferably 140 ° C or higher, even more preferably 160 ° C or higher, particularly preferably 165 ° C or higher, 170 ° C or higher, 175 ° C. As described above, Tg of 180 ° C. or higher or 185 ° C. or higher can be shown. Although the upper limit of Tg of the hardened | cured material of this invention is not restrict | limited in particular, Usually, it is 250 degrees C or less. Therefore, in one Embodiment, Tg of the hardened | cured material of this invention is 100 to 250 degreeC.
The Tg of the cured product can be measured by a known method such as thermomechanical analysis. Examples of the thermomechanical analyzer include “Thermo Plus TMA8310” manufactured by Rigaku Corporation.

The cured product of the present invention can also exhibit a low coefficient of linear thermal expansion. For example, the cured product of the present invention is preferably 25 ppm or less, more preferably 20 ppm or less, even more preferably less than 20 ppm, even more preferably 18 ppm or less, particularly preferably 17 ppm or less, 16 ppm or less, 15 ppm or less, 14 ppm or less, or 13 ppm or less. The linear thermal expansion coefficient can be shown. Although the minimum of the linear thermal expansion coefficient of hardened | cured material is not restrict | limited in particular, Usually, it is 1 ppm or more.
The linear thermal expansion coefficient of the cured product can be measured by a known method such as thermomechanical analysis. Examples of the thermomechanical analyzer include “Thermo Plus TMA8310” manufactured by Rigaku Corporation. In this invention, the linear thermal expansion coefficient of hardened | cured material is a linear thermal expansion coefficient of 25-150 degreeC of a plane direction at the time of performing a thermomechanical analysis by the tension load method.

The hardened | cured material of this invention can form a conductor layer by plating, after roughening the surface. Regarding the cured product of the present invention, when a conductor layer is formed by plating on the surface of the cured product after the roughening treatment, the peel strength between the cured product surface and the conductor layer is preferably 0.25 kgf / cm or more. Preferably 0.3 kgf / cm or more, more preferably 0.35 kgf / cm or more, even more preferably 0.4 kgf / cm or more, particularly preferably 0.45 kgf / cm or more, 0.5 kgf / cm or more, 0.55 kgf / Cm or more or 0.6 kgf / cm or more. The upper limit of the peel strength is not particularly limited, but is usually 1.0 kgf / cm or less, 0.8 kgf / cm or less, and the like. Therefore, in one embodiment, when a conductor layer is formed by plating on the surface of the cured product after the roughening treatment, the peel strength between the surface of the cured product and the conductor layer is 0.25 to 0.8 kgf / cm. The peel strength between the cured product surface and the conductor layer refers to the peel strength (90-degree peel strength) when the conductor layer is peeled in the direction perpendicular to the cured product surface (90-degree direction). Can be determined by measuring the peel strength when peeled in the direction perpendicular to the surface of the cured product (90-degree direction) with a tensile tester. Examples of the tensile tester include “AC-50C-SL” manufactured by TSE Corporation.
Details of the roughening process and the conductor layer will be described later.

[Multilayer printed wiring board]
The multilayer printed wiring board of this invention contains the insulating layer formed with the hardened | cured material of this invention.

In one embodiment, the multilayer printed wiring board of the present invention can be produced by the method including the following steps (I) to (IV) using the above-mentioned adhesive film.
(I) Step of laminating an adhesive film on the inner circuit board so that the resin composition layer of the adhesive film is bonded to the substrate (II) Forming a cured product by thermosetting the resin composition layer of the adhesive film (III) Step of roughening the surface of the cured product (IV) Step of forming a conductor layer on the roughened surface of the cured product

  “Inner layer circuit board” used in step (I) is a glass epoxy board, metal board, polyester board, polyimide board, BT resin board, thermosetting polyphenylene ether board, pattern processing on one or both sides of the board. This means an intermediate product having a conductive layer (circuit) that is to be further formed with an insulating layer and a conductive layer when a multilayer printed wiring board is manufactured.

  The lamination of the adhesive film and the inner layer circuit board in the step (I) is preferably performed by roll pressing, press pressing, or the like so that the resin composition layer of the adhesive film is bonded to the inner layer circuit board. Among these, a vacuum laminating method of laminating under reduced pressure is more preferable. The laminating method may be a batch type or a continuous type.

Lamination generally crimping pressure in the range of ^{1kgf / cm 2 ~11kgf / cm 2} (0.098MPa~1.078MPa), the compression temperature in the range of 70 to 120 ° C., bonding time of 5 to 180 seconds It is preferable to carry out under a reduced pressure with a range of air pressure of 20 mmHg (26.7 hPa) or less.
Lamination treatment can be performed using a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nichigo Morton, and the like.

  In step (II), the resin composition layer of the adhesive film is thermally cured to form a cured product (insulating layer).

  The conditions of such a process (II) are as having demonstrated in the said [hardened | cured material] column. The support may be peeled off from the resin composition layer before the step (II) (that is, before thermosetting the resin composition layer), or after the step (II) (that is, the resin). After the composition layer is thermally cured to form a cured body, it may be peeled off from the cured body.

  In step (III), the surface of the cured product is roughened.

  The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming the insulating layer of the multilayer printed wiring board can be adopted. For example, the surface of the cured product can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. Although it does not specifically limit as a swelling liquid, An alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution, As this alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include Swelling Dip Securigans P and Swelling Dip Securigans SBU manufactured by Atotech Japan. Although the swelling process by a swelling liquid is not specifically limited, For example, it can carry out by immersing hardened | cured material in the swelling liquid of 30-90 degreeC for 1 minute-20 minutes. From the viewpoint of suppressing the swelling of the resin of the cured product to an appropriate level, it is preferable to immerse the cured product in a swelling solution at 40 to 80 ° C. for 5 seconds to 15 minutes. Although it does not specifically limit as an oxidizing agent, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the cured product in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as Concentrate Compact P and Dosing Solution Securigans P manufactured by Atotech Japan Co., Ltd. As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, for example, Reduction Sholysin Securigant P manufactured by Atotech Japan Co., Ltd. may be mentioned. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidant solution in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidant solution in a neutralizing solution at 40 to 70 ° C. for 5 to 20 minutes is preferable.

  In step (IV), a conductor layer is formed on the roughened surface of the cured product.

  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 the group consisting of gold, platinum, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Including. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy). Above all, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, silver or copper, or nickel-chromium alloy, copper-nickel alloy An alloy layer of copper / titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, silver or copper, or an alloy layer of nickel / chromium alloy is more preferable, and a single metal layer of copper is further preferable.

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

  The thickness of the conductor layer is generally 3 to 35 μm, preferably 5 to 30 μm, although it depends on the desired multilayer printed wiring board design.

  The conductor layer has a desired wiring pattern. For example, a conductor layer having a desired wiring pattern can be formed on the roughened surface of the cured product by a conventionally known technique such as a semi-additive method. Hereinafter, an example in which the conductor layer is formed by a semi-additive method will be described.

  First, a plating seed layer is formed on the roughened surface of the cured product by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. A metal layer is formed by electroplating on the exposed plating seed layer, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

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

[Semiconductor device]
A semiconductor device can be manufactured using the multilayer printed wiring board of the present invention.

  Examples of such semiconductor devices include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts). .

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, “parts” and “%” mean “parts by mass” and “% by mass”, respectively, unless otherwise specified. In the following, Examples 8 and 9 are reference examples.

<Measurement method / Evaluation method>
First, various measurement methods and evaluation methods will be described.

[Preparation of samples for measurement and evaluation]
(1) Base treatment of inner layer circuit board Glass cloth base epoxy resin double-sided copper-clad laminate with inner layer circuit (copper foil thickness 18 μm, substrate thickness 0.4 mm, “R1515A” manufactured by Panasonic Corporation) Both surfaces were immersed in “CZ8101” manufactured by Mec Co., Ltd. and etched by 1 μm to roughen the copper surface.

(2) Laminating treatment of adhesive film The adhesive film produced in the examples and comparative examples was obtained by using a batch type vacuum pressure laminator (“MVLP-500” manufactured by Meiki Co., Ltd.) and the resin composition layer was an inner layer circuit. Lamination was performed on both sides of the inner circuit board so as to be bonded to the board. The laminating process was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of resin composition layer The PET film as the support was peeled from the laminated adhesive film. Next, after preheating at 80 ° C. for 30 minutes, the resin composition layer was thermally cured at 180 ° C. for 30 minutes to form a cured product (insulating layer) on both surfaces of the inner circuit board.

(4) Roughening treatment of the cured product The inner layer circuit board on which the cured product was formed on both surfaces was swollen (Atotech Japan Co., Ltd. “Swelling Dip Securigant P”, aqueous solution of sodium hydroxide containing diethylene glycol monobutyl ether) And then immersed in a roughening solution (Atotech Japan Co., Ltd. “Concentrate Compact P”, an aqueous solution having a potassium permanganate concentration of about 6% by mass and a sodium hydroxide concentration of about 4% by mass). It was immersed at 20 ° C. for 20 minutes, and finally immersed in a neutralizing solution (Atotech Japan Co., Ltd. “Reduction Sholycine Securigant P”, hydroxylamine sulfate aqueous solution) at 40 ° C. for 5 minutes. Subsequently, it was dried at 80 ° C. for 30 minutes.

(5) Formation of conductor layer According to a semi-additive method, a conductor layer was formed on the roughened surface of the cured product.
That is, the roughened substrate was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes and then immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. Next, after annealing at 150 ° C. for 30 minutes, an etching resist was formed, and a pattern was formed by etching. Thereafter, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 30 μm. Annealing treatment was performed at 190 ° C. for 60 minutes to obtain an evaluation substrate.

[Measurement of peel strength between cured product surface and conductor layer]
When the conductor layer of the evaluation board is cut into a portion with a width of 10 mm and a length of 100 mm, this one end is peeled off and grasped with a gripping tool, and 35 mm is peeled off vertically at a speed of 50 mm / min at room temperature. The load (kgf / cm) was measured to determine the peel strength. For the measurement, a tensile testing machine (Autocom type testing machine “AC-50C-SL” manufactured by TSE Co., Ltd.) was used.

[Measurement of glass transition temperature (Tg) and linear thermal expansion coefficient of cured product]
The adhesive films prepared in Examples and Comparative Examples were heated at 200 ° C. for 90 minutes to thermally cure the resin composition layer. The obtained cured product was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Co., Ltd.), a thermal machine was formed by a tensile load method. Analysis was carried out. Specifically, after the test piece was mounted on the thermomechanical analyzer, the test piece was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. In the second measurement, the glass transition temperature (Tg) and the average linear thermal expansion coefficient (ppm) in the range from 25 ° C. to 150 ° C. were calculated.

(Measurement of melt viscosity of resin composition layer)
About the resin composition layer of the adhesive film produced in the Example and the comparative example, melt viscosity was measured using the dynamic viscoelasticity measuring apparatus ("Rhesol-G3000" by BM Corporation). About 1 g of the sample resin composition, using a parallel plate with a diameter of 18 mm, the temperature was raised from a starting temperature of 60 ° C. to 200 ° C. at a heating rate of 5 ° C./minute, a measurement interval temperature of 2.5 ° C., a frequency of 1 Hz, The dynamic viscoelastic modulus was measured under a measurement condition of 1 deg strain, and the minimum melt viscosity (poise) was calculated. For each resin composition layer, the initial minimum melt viscosity V ₁ (poise) immediately after production of the adhesive film and the minimum melt viscosity V ₂ (poise) after storage at 25 ° C. for 7 days were determined, and the viscosity increase ratio (V ₂ / V ₁ ) was calculated.

<Example 1>
10 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation "828US", epoxy equivalent of about 180), biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent of about 269), xylenol Type epoxy resin (Mitsubishi Chemical Corporation “YX4000HK”, epoxy equivalent of about 185), naphthol type epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd. “ESN475V”, epoxy equivalent of about 330), and phenoxy resin ( 10 parts of “YL7553BH30” manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass were dissolved in 25 parts of solvent naphtha with stirring. After cooling to room temperature, 10 parts of a triazine skeleton-containing phenol novolac curing agent (“LA3018-50P” manufactured by DIC Corporation, 2-methoxypropanol solution having a hydroxyl equivalent of about 151 and a solid content of 50%), active ester Curing agent (DIC Corporation "HPC8000-65T", active group equivalent of about 223, non-volatile component 65% by weight toluene solution) 40 parts, curing accelerator (4-benzoylpyridine having the following structure, solid content 10% by weight) 5 parts, spherical silica surface treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle size 0.5 μm, “SOC2” manufactured by Admatechs) 225 The parts were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish.

〔ピリジン４位に結合するベンゾイル基のσ_ｍ値は０．３４〕

[Σ _m value of benzoyl group bonded to 4-position of pyridine is 0.34]

  Next, the resin varnish is uniformly applied on the release layer of the PET film with a release layer (“AL5” manufactured by Lintec Corporation, thickness 38 μm) so that the thickness of the resin composition layer after drying is 30 μm. It apply | coated and dried at 80-120 degreeC (average 100 degreeC) for 4 minutes, and produced the adhesive film.

  Using the obtained adhesive film, an evaluation substrate was produced according to the procedure of [Preparation of measurement / evaluation sample]. Each evaluation result is shown in Table 1.

<Example 2>
10 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation "828US", epoxy equivalent of about 180) and glycidyl ester type epoxy resin (Nagase ChemteX Corporation "EX-721", epoxy equivalent of about 154) 10 Except having changed into the part, the adhesive film was produced like Example 1 and the evaluation board | substrate was manufactured. Each evaluation result is shown in Table 1.

<Example 3>
Biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269) was changed from 20 parts to 10 parts, and bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation). ”, 10 parts of an epoxy equivalent of about 185) and 5 parts of a naphthol type epoxy resin (“ ESN475V ”manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 330) are combined with a naphthylene ether type epoxy resin (“ HP6000 ”manufactured by DIC Corporation). , Epoxy equivalent of about 250) and dicyclopentadiene type epoxy resin (DIC Corporation "HP7200HH", epoxy equivalent of about 283). The evaluation board was manufactured. Each evaluation result is shown in Table 1.

<Example 4>
40 parts of an active ester curing agent (“HPC8000-65T” manufactured by DIC Corporation, a toluene solution having an active group equivalent of about 223 and 65% by mass of a non-volatile component) was added to an active ester curing agent (“EXB9416-70BK” manufactured by DIC Corporation). , Active group equivalent about 330, methyl isobutyl ketone solution with 70% by mass of non-volatile component) 40 parts, and 5 parts of curing accelerator (4-benzoylpyridine, MEK solution with a solid content of 10% by mass) An adhesive film was produced in the same manner as in Example 1 except that the part was changed from 8 parts to 8 parts, and an evaluation substrate was produced. Each evaluation result is shown in Table 1.

<Example 5>
Except for changing 5 parts of curing accelerator (4-benzoylpyridine, MEK solution having a solid content of 10% by mass) to 5 parts of curing accelerator (ethyl isonicotinate having the following structure, MEK solution having a solid content of 10% by mass). Produced an adhesive film in the same manner as in Example 1 to produce an evaluation substrate. Each evaluation result is shown in Table 1.

〔ピリジン４位に結合するエトキシカルボニル基のσ_ｍ値は０．３７〕

[Σ _m value of ethoxycarbonyl group bonded to 4-position of pyridine is 0.37]

<Example 6>
From 225 parts of the amount of spherical silica (average particle size 0.5 μm, “SOC2” manufactured by Admatechs Co., Ltd.) surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) An adhesive film was produced in the same manner as in Example 5 except that the amount was changed to 300 parts, and an evaluation substrate was produced. Each evaluation result is shown in Table 1.

<Example 7>
225 parts of spherical silica (average particle size 0.5 μm, “SOC2” manufactured by Admatechs Co., Ltd.) surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) Spherical silica surface treated with a ring agent (Shin-Etsu Chemical Co., Ltd., “KBM573”) (average particle size 0.3 μm, “SOC1” manufactured by Admatex Co., Ltd.) 225 parts, and curing acceleration An adhesive film was produced in the same manner as in Example 5 except that the compounding amount of the agent (ethyl isonicotinate, MEK solution having a solid content of 10% by mass) was changed from 5 parts to 8 parts, and an evaluation substrate was produced. . Each evaluation result is shown in Table 1.

<Example 8>
5 parts of a curing accelerator (4-benzoylpyridine, MEK solution having a solid content of 10% by mass) and 15 parts of a curing accelerator (1,1′-carbonyldiimidazole having the following structure, MEK solution having a solid content of 5% by mass) An adhesive film was prepared in the same manner as in Example 1 except that the evaluation substrate was manufactured. Each evaluation result is shown in Table 1.

〔イミダゾール１位に結合するイミダゾリルカルボニル基のσ_ｍ値は０．３４程度〕

[Σ _m value of imidazolylcarbonyl group bonded to imidazole 1-position is about 0.34]

<Example 9>
Except for changing 8 parts of the curing accelerator (ethyl isonicotinate, MEK solution having a solid content of 10% by mass) to 20 parts of the curing accelerator (1,1′-carbonyldiimidazole, MEK solution having a solid content of 5% by mass). Produced an adhesive film in the same manner as in Example 7 to produce an evaluation substrate. Each evaluation result is shown in Table 1.

<Example 10>
Except for changing 5 parts of the curing accelerator (4-benzoylpyridine, MEK solution having a solid content of 10% by mass) to 5 parts of the curing accelerator (4-cyanopyridine having the following structure, MEK solution having a solid content of 10% by mass). Produced an adhesive film in the same manner as in Example 1 to produce an evaluation substrate. Each evaluation result is shown in Table 1.

〔ピリジン４位に結合するシアノ基のσ_ｍ値は０．５６〕

[Σ _m value of cyano group bonded to 4-position of pyridine is 0.56]

<Example 11>
5 parts of a curing accelerator (4-benzoylpyridine, MEK solution having a solid content of 10% by mass) and 15 parts of a curing accelerator (1,1′-sulfonyldiimidazole having the following structure, DMAc solution having a solid content of 5% by mass) An adhesive film was prepared in the same manner as in Example 1 except that the evaluation substrate was manufactured. Each evaluation result is shown in Table 1.

〔イミダゾール１位に結合するイミダゾリルスルホニル基のσ_ｍ値は０．６２程度〕

[Σ _m value of imidazolylsulfonyl group bonded to 1-position of imidazole is about 0.62]

<Example 12>
5 parts of a curing accelerator (4-benzoylpyridine, MEK solution having a solid content of 10% by mass) is added to a curing accelerator (1- (4-cyanophenyl) imidazole having the following structure, MEK solution having a solid content of 5% by mass): 15 Except having changed into the part, the adhesive film was produced like Example 1 and the evaluation board | substrate was manufactured. Each evaluation result is shown in Table 1.

〔イミダゾール１位に結合する４−シアノフェニル基のσ_ｍ値は０．２０程度〕

[Σ _m value of 4-cyanophenyl group bonded to imidazole 1-position is about 0.20]

<Example 13>
5 parts of a curing accelerator (4-benzoylpyridine, MEK solution having a solid content of 10% by mass) is added to a curing accelerator (1- (4-nitrophenyl) -1H-imidazole having the following structure, MEK having a solid content of 5% by mass). Solution) An adhesive film was produced in the same manner as in Example 1 except that the amount was changed to 15 parts, and an evaluation substrate was produced. Each evaluation result is shown in Table 1.

〔イミダゾール１位に結合する４−ニトロフェニル基のσ_ｍ値は０．２５〕

[Σ _m value of 4-nitrophenyl group bonded to 1-position of imidazole is 0.25]

<Comparative Example 1>
5 parts of curing accelerator (4-benzoylpyridine, MEK solution having a solid content of 10% by mass) is added to a curing accelerator (N, N-dimethyl-4-aminopyridine having the following structure, MEK solution having a solid content of 10% by mass). Except for changing to 5 parts, an adhesive film was prepared in the same manner as in Example 1 to produce an evaluation substrate. Each evaluation result is shown in Table 1.

〔ピリジン４位に結合するジメチルアミノ基のσ_ｍ値は−０．１６〕

[Σ _m value of dimethylamino group bonded to 4-position of pyridine is −0.16]

<Comparative Example 2>
5 parts of a curing accelerator (4-benzoylpyridine, MEK solution having a solid content of 10% by mass) and 15 parts of a curing accelerator (1-benzyl-2-phenylimidazole having the following structure, MEK solution having a solid content of 5% by mass) An adhesive film was prepared in the same manner as in Example 1 except that the evaluation substrate was manufactured. Each evaluation result is shown in Table 1.

〔イミダゾール１位に結合するベンジル基のσ_ｍ値は−０．０８〕

[Σ _m value of benzyl group bonded to 1-position of imidazole is −0.08]

From Table 1, in Comparative Examples 1 and 2 in which a pyridine compound having an electron donating group at the 4-position or an imidazole compound having an electron donating group at the 1-position is used as a curing accelerator, the curing of the resin composition layer proceeds during storage. The viscosity of the resin composition layer was greatly increased.
In contrast, in Examples 1 to 13 in which a pyridine compound having an electron withdrawing group at the 4-position or an imidazole compound having an electron withdrawing group at the 1-position is used as a curing accelerator, the resin composition layer during storage It was confirmed that the increase in viscosity was suppressed. Furthermore, in Examples 1-13, the hardened | cured material (insulating layer) which has a high glass transition temperature (Tg) and a low linear thermal expansion coefficient compared with the comparative examples 1 and 2 is formed, and hardening at the time of thermosetting It was confirmed that the characteristics were extremely excellent.

Claims (21)

A resin composition comprising (A) an epoxy resin, (B) an active ester curing agent, and (C) a curing accelerator,
(C) component contains 1 or more types selected from the group which consists of a pyridine compound which has an electron withdrawing group in 4-position, and an imidazole compound which has an electron withdrawing group in 1-position,
The imidazole compound having an electron withdrawing group at the 1-position has a cyano group, an optionally substituted phenyl group, an optionally substituted vinyl group, and a substituted group at the 1-position. which may carboxymethylene group, or a resin composition is an imidazole compound having a sulfonyl group. 2. The resin composition according to claim 1, wherein the electron withdrawing group is a group having a Hammett's substituent constant [sigma] _m value larger than zero.   A pyridine compound having an electron withdrawing group at the 4-position is a halogen atom, a cyano group, a nitro group, or a phenyl group, a carbonyl group, a thiocarbonyl group, a sulfonyl group, or a phosphoryl group optionally having a substituent at the 4-position. The resin composition according to claim 1, wherein the resin composition is a pyridine compound.   The resin composition according to any one of claims 1 to 3, wherein the pyridine compound having an electron-attracting group at the 4-position is a pyridine compound having a cyano group or a carbonyl group at the 4-position.   The imidazole compound having an electron withdrawing group at the 1-position is an imidazole compound having a phenyl group, a carbonyl group, or a sulfonyl group which may have a substituent at the 1-position. The resin composition as described. Component (C) is 4-benzoylpyridine, 4-cyanopyridine, ethyl isonicotinate , 1,1′-sulfonyldiimidazole, 1- (4-cyanophenyl) imidazole, and 1- (4-nitrophenyl)- The resin composition according to any one of claims 1 to 5, comprising one or more selected from the group consisting of 1H-imidazole.   The resin according to any one of claims 1 to 6, wherein the ratio of the total number of epoxy groups in component (A) to the total number of reactive groups in component (B) is 1: 0.2 to 1: 2. Composition.   The resin composition according to any one of claims 1 to 7, further comprising (D) an inorganic filler.   The resin composition according to claim 8, wherein the content of the component (D) is 30 to 90 mass% when the nonvolatile component in the resin composition is 100 mass%.   The resin composition according to claim 8, wherein the content of the component (D) is 50 to 90 mass% when the nonvolatile component in the resin composition is 100 mass%.   (D) The resin composition of any one of Claims 8-10 whose average particle diameter of a component is 0.01-5 micrometers.   The component (A) is selected from the group consisting of bisphenol A type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin, and dicyclopentadiene type epoxy resin. The resin composition of any one of Claims 1-11 containing the above.   The resin composition according to any one of claims 1 to 12, further comprising (E) a thermoplastic resin.   It is a resin composition for insulating layers of a multilayer printed wiring board, The resin composition of any one of Claims 1-13.   The resin composition according to claim 1, which is a resin composition for a buildup insulating layer of a multilayer printed wiring board.   The sheet-like laminated material containing the layer of the resin composition of any one of Claims 1-15.   Hardened | cured material obtained by thermosetting the resin composition of any one of Claims 1-15.   The hardened | cured material of Claim 17 whose glass transition temperature (Tg) is 100-250 degreeC. When forming a conductive layer by plating the cured product surface after roughening treatment, the peel strength between the cured product surface and the conductor layer, Ri 0.25~0.8kgf / cm der,
In the roughening treatment, the cured product is immersed in a swelling liquid at 30 to 90 ° C. for 1 to 20 minutes, immersed in an oxidant solution at 60 to 80 ° C. for 10 to 30 minutes, and neutralized at 30 to 80 ° C. It is performed by immersing in the liquid for 5 to 30 minutes,
The cured product according to claim 17 or 18 , wherein the peel strength is a peel strength between the surface of the cured product and the conductor layer when the conductor layer is peeled in a direction perpendicular to the surface of the cured product.   The multilayer printed wiring board containing the insulating layer formed with the hardened | cured material of any one of Claims 17-19.   A semiconductor device comprising the multilayer printed wiring board according to claim 20.