JP2013010895A - Insulating adhesive film, laminate, cured product and composite body - Google Patents

Abstract

Disclosed is an insulating adhesive film having low linear expansion, excellent wiring embedding properties, and high peel strength.
A plating layer comprising a resin composition for a plating layer containing an alicyclic olefin polymer (A1) having a polar group and an inorganic filler (A2), an organic solvent-soluble polyimide (B1), And an adhesive layer made of a resin composition for an adhesive layer containing an inorganic filler (B2).
[Selection figure] None

Description

  The present invention relates to an insulating adhesive film, a laminate, a cured product, and a composite.

  With the pursuit of downsizing, multi-functionalization, high-speed communication, etc. of electronic devices, there is a need for higher density circuit boards used in electronic devices. To meet such demands for higher density, Circuit boards are being made multilayered. In such a multilayer circuit board, for example, an electrical insulation layer is laminated on an inner layer substrate composed of an electrical insulation layer and a conductor layer formed on the surface thereof, and a conductor layer is formed on the electrical insulation layer. Further, it is formed by repeatedly stacking these electrical insulating layers and forming the conductor layer. The electrical insulating layer and the conductor layer can be laminated in several stages as required.

  In such a multilayer circuit board, a circuit breakage may occur due to a difference in linear expansion between the conductor layer and the electrical insulating layer, particularly when the conductor layer has a high-density pattern. The problem of disconnection was significant. Therefore, in the multilayer circuit board, it is required to reduce the linear expansion of the electrical insulating layer. In general, it is effective to add an inorganic filler to reduce the linear expansion of the electrical insulating layer. However, the addition of the inorganic filler increases the surface roughness of the electrical insulating layer, and thus the electrical insulation. When a conductor layer is formed on the surface of the layer and fine wiring is formed by etching the conductor layer, there is a problem that the conductor remains between patterns due to defective etching or the conductor is lifted or peeled off. Will occur.

  On the other hand, in order to achieve low linear expansion while reducing the surface roughness of the electrical insulating layer, for example, in Patent Document 1, a first layer containing a polyimide resin and an inorganic filler, a polyimide resin, and There has been proposed an adhesive sheet for an electrical insulating layer comprising an inorganic filler and a second layer containing a smaller amount of the inorganic filler than the first layer.

JP 2006-45388 A

  However, as a result of investigations by the present inventors, the technique described in Patent Document 1 described above can reduce the surface roughness of the obtained electrical insulating layer, but low linear expansion is not always sufficient. In addition, there is a problem that the peel strength is low and the reliability is poor.

  An object of the present invention is to provide an insulating adhesive film capable of forming an electrically insulating layer having low linear expansion, excellent wiring embedding property, and high peel strength, and a laminate, a cured product, and a composite obtained by using the insulating adhesive film Is to provide a body.

As a result of diligent research to achieve the above object, the inventors of the present invention obtained an insulating adhesive film, a plated layer containing an alicyclic olefin polymer having a polar group and an inorganic filler, and an organic solvent-soluble polyimide. And an insulating layer containing an inorganic filler, the insulating adhesive film forms an electrically insulating layer with low linear expansion, excellent wiring embedding, and high peel strength. The inventors have found that this is possible and have completed the present invention.
In particular, according to the present invention, the insulative adhesive film is composed of a different resin for the plated layer and the adhesive layer and has a two-layer structure of these different resins, specifically, adhesion between the two layers. It is possible to realize the formation of an electrical insulating layer having low linear expansion and excellent wiring embedding while effectively preventing the occurrence of a problem that the property is poor and the peel strength is lowered.

That is, according to the present invention,
[1] A plated layer comprising a resin composition for a plated layer containing an alicyclic olefin polymer (A1) having a polar group and an inorganic filler (A2), an organic solvent-soluble polyimide (B1), and An insulating adhesive film having an adhesive layer made of a resin composition for an adhesive layer containing an inorganic filler (B2),
[2] The resin composition for a plated layer further contains a curable compound (A3) having two or more functional groups capable of reacting with the polar group in the molecule, and the resin composition for an adhesive layer is The insulating adhesive film according to [1], further including an epoxy resin (B3), a phenol compound (B4), and a curing accelerator (B5),
[3] The insulating adhesive film according to [1] or [2], wherein the plated layer has a thickness of 1 to 10 μm, and the adhesive layer has a thickness of 10 to 100 μm.
[4] A laminate formed by laminating the insulating adhesive film according to any one of [1] to [3] on a base material,
[5] A cured product obtained by curing the insulating adhesive film according to any one of [1] to [3] or the laminate according to [4],
[6] A composite formed by forming a conductor layer by electroless plating on the surface of the cured product according to [5], and
[7] The cured material according to [5], or the electronic material substrate including the composite according to [6] as a constituent material,
Is provided.

  According to the present invention, an insulating adhesive film having a low linear expansion, excellent wiring embedding property, and capable of forming an electrical insulating layer having high peel strength, and a laminate, a cured product, and a composite obtained using the same The body is provided.

The insulating adhesive film of the present invention comprises a plated layer comprising a resin composition for a plated layer containing an alicyclic olefin polymer (A1) having a polar group and an inorganic filler (A2), and is soluble in an organic solvent. It has an adhesive layer which consists of a resin composition for adhesive layers containing a polyimide (B1) and an inorganic filler (B2).
In the present specification, the alicyclic olefin polymer means a repeating unit derived from an olefin (alicyclic olefin) monomer having an alicyclic structure, or a repeating unit that can be regarded as the repeating unit (hereinafter referred to as convenience). In other words, both are collectively referred to as a repeating unit derived from an alicyclic olefin monomer).

(Resin composition for plated layer)
First, the resin composition for to-be-plated layers for forming a to-be-plated layer is demonstrated. The resin composition for to-be-plated layer used by this invention contains the alicyclic olefin polymer (A1) which has a polar group, and an inorganic filler (A2).

(Aliphatic olefin polymer having a polar group (A1))
The resin composition for to-be-plated layer used by this invention contains the alicyclic olefin polymer (A1) which has a polar group as a resin component.
As the alicyclic structure constituting the alicyclic olefin polymer (A1) having a polar group used in the present invention (hereinafter abbreviated as “alicyclic olefin polymer (A1)” as appropriate), a cycloalkane structure is used. And a cycloalkene structure are preferable, but a cycloalkane structure is preferable from the viewpoint of mechanical strength and heat resistance. Examples of the alicyclic structure include monocycles, polycycles, condensed polycycles, bridged rings, and polycycles formed by combining these. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually in the range of 4 to 30, preferably 5 to 20, more preferably 5 to 15, and the carbon constituting the alicyclic structure. When the number of atoms is in this range, the mechanical strength, heat resistance, and moldability are highly balanced and suitable. The alicyclic olefin polymer (A1) is usually thermoplastic.

  In the present invention, an alicyclic olefin polymer (A1) is used as a resin component constituting the layer to be plated, so that the insulating adhesive film of the present invention is an organic solvent-soluble polyimide (B1) described later as a resin component. As a result, the surface roughness on the surface of the layer to be plated can be kept low while the adhesion between the adhesive layer and the adhesive layer is good. Thus, when the conductive layer is formed on the layer to be plated by electroless plating or the like, the adhesion between the layer to be plated and the adhesive layer, and the adhesion between the layer to be plated and the conductive layer Either of these can be made excellent. That is, the peel strength when the conductive layer is formed on the layer to be plated by electroless plating or the like can be made excellent.

  The ratio of the repeating unit derived from the alicyclic olefin monomer in the alicyclic olefin polymer (A1) is not particularly limited, but is usually 30 to 100% by weight, preferably 50 to 100% by weight, more preferably 70. ~ 100% by weight. When the ratio of the repeating unit derived from the alicyclic olefin monomer is too small, the heat resistance is inferior, which is not preferable. The repeating unit other than the repeating unit derived from the alicyclic olefin monomer is not particularly limited and is appropriately selected depending on the purpose.

  The polar group possessed by the alicyclic olefin polymer (A1) is not particularly limited, but alcoholic hydroxyl group, phenolic hydroxyl group, carboxyl group, alkoxyl group, epoxy group, glycidyl group, oxycarbonyl group, carbonyl group, amino group. , Ester groups, carboxylic acid anhydride groups, sulfonic acid groups, phosphoric acid groups, etc., among these, carboxyl groups, carboxylic acid anhydride groups, and phenolic hydroxyl groups are preferred, and carboxylic acid anhydride groups are preferred. More preferred. The alicyclic olefin polymer (A1) may have two or more polar groups. In addition, the polar group of the alicyclic olefin polymer (A1) may be directly bonded to an atom constituting the main chain of the polymer, but may be a methylene group, an oxy group, an oxycarbonyloxyalkylene group, a phenylene group, or the like. And may be bonded via a divalent group. The content of the polar group in the alicyclic olefin polymer (A1) is not particularly limited, but is usually 5 to 60 mol% in 100 mol% of all repeating units constituting the alicyclic olefin polymer (A1). Preferably it is 10-50 mol%.

The alicyclic olefin polymer (A1) used in the present invention can be obtained, for example, by the following method. That is, (1) a method of polymerizing an alicyclic olefin having a polar group by adding another monomer as necessary, (2) an alicyclic olefin having no polar group having a polar group (3) Aromatic olefin having a polar group is polymerized by adding another monomer if necessary, and the aromatic ring portion of the polymer obtained by this is hydrogenated. (4) A method of copolymerizing an aromatic olefin having no polar group with a monomer having a polar group and hydrogenating the aromatic ring portion of the polymer obtained thereby, or (5) Polarity A method in which a compound having a polar group is introduced into a cycloaliphatic olefin polymer having no group by a modification reaction, or (6) a polar group (for example, a carboxylic acid ester) obtained as described in (1) to (5) above Group of alicyclic olefin polymer having Sex group can be obtained by a method of converting into other polar groups (e.g., carboxyl group) by, for example, hydrolysis. Among these, a polymer obtained by the method (1) described above is preferable.
As the polymerization method for obtaining the alicyclic olefin polymer (A1) used in the present invention, ring-opening polymerization or addition polymerization is used. In the case of ring-opening polymerization, it is preferable to hydrogenate the obtained ring-opened polymer. .

Specific examples of the alicyclic olefin having a polar group include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo [2.2.1] hept- 2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-carboxymethyl-9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 5-exo-6-endo-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 9-exo-10-endo-dihydroxycarbonyltetracyclo [6. 2.1.1 ^3,6 . Alicyclic olefin having a carboxyl group such as 0 ^2,7 ] dodec-4-ene; bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, tetracyclo [6.2 1.1 ^{3, 6} . 0 ^2,7] dodeca-4-ene-9,10-dicarboxylic anhydride, hexacyclo [10.2.1.1 ^{3, 10.} 1 ^5,8 . 0 ^2,11 . Alicyclic olefins having a carboxylic anhydride group such as 0 ^4,9 ] heptadeca-6-ene-13,14-dicarboxylic anhydride; 9-methyl-9-methoxycarbonyltetracyclo [6.2.1. 1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2 Cycloaliphatic olefins having a carboxylic acid ester group such as -ene; (5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 9- (4-hydroxyphenyl) tetracyclo [6. 2.1.13, 6.02,7] Phenols such as dodec-4-ene, N- (4-hydroxyphenyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide And alicyclic olefins having a functional hydroxyl group, etc. These may be used alone or in combination of two or more.

Specific examples of the alicyclic olefin having no polar group include bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethyl-bicyclo [2.2.1] hept-2. -Ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] ] Hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene (common name: di) Cyclopentadiene), tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (common name: tetracyclododecene), 9-methyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methoxycarbonyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-vinyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-propenyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-phenyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7] dodeca-4-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene, cyclopentene, cyclopentadiene and the like. These may be used alone or in combination of two or more.

  Examples of the aromatic olefin having no polar group include styrene, α-methylstyrene, divinylbenzene and the like. When these specific examples have the said polar group, it is mentioned as an example of the aromatic olefin which has a polar group. These may be used alone or in combination of two or more.

  Examples of the monomer having a polar group other than the alicyclic olefin having a polar group that can be copolymerized with an alicyclic olefin or an aromatic olefin include ethylenically unsaturated compounds having a polar group, Specific examples thereof include unsaturated carboxylic acid compounds such as acrylic acid, methacrylic acid, α-ethylacrylic acid, 2-hydroxyethyl (meth) acrylic acid, maleic acid, fumaric acid and itaconic acid; maleic anhydride, butenyl anhydride And unsaturated carboxylic acid anhydrides such as succinic acid, tetrahydrophthalic anhydride and citraconic anhydride. These may be used alone or in combination of two or more.

  Examples of the monomer having no polar group other than the alicyclic olefin that can be copolymerized with the alicyclic olefin or the aromatic olefin include ethylenically unsaturated compounds having no polar group. Examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1- Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, Ethylene or α-olefin having 2 to 20 carbon atoms such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; 1,4-hexadi And the like; emission, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene nonconjugated dienes such. These may be used alone or in combination of two or more.

  The molecular weight of the alicyclic olefin polymer (A1) used in the present invention is not particularly limited, but is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrohydrofuran as a solvent, and is 500 to 1, The range is preferably in the range of 1,000,000, more preferably in the range of 1,000 to 500,000, and particularly preferably in the range of 5,000 to 300,000. If the weight average molecular weight is too small, the mechanical strength of the cured product obtained by curing the resin composition is lowered, and if it is too large, workability tends to deteriorate when forming into a sheet or film to form a molded body. There is.

  As a polymerization catalyst when the alicyclic olefin polymer (A1) used in the present invention is obtained by a ring-opening polymerization method, a conventionally known metathesis polymerization catalyst can be used. Examples of the metathesis polymerization catalyst include transition metal compounds containing atoms such as Mo, W, Nb, Ta, and Ru. Among them, compounds containing Mo, W, or Ru are preferable because of high polymerization activity. Specific examples of particularly preferred metathesis polymerization catalysts include: (1) Molybdenum or tungsten compounds having a halogen group, an imide group, an alkoxy group, an allyloxy group or a carbonyl group as a ligand as a main catalyst, and an organometallic compound. Examples thereof include a catalyst as a second component and (2) a metal carbene complex catalyst having Ru as a central metal.

Examples of compounds used as the main catalyst in the catalyst of (1) above are halogenated molybdenum compounds such as MoCl ₅ and MoBr _5, and halogenated compounds such as WCl ₆ , WOCl ₄ , tungsten (phenylimide) tetrachloride / diethyl ether, etc. A tungsten compound is mentioned. Examples of the organometallic compound used as the second component in the catalyst of (1) above include organometallic compounds of Group 1, Group 2, Group 12, Group 13 or Group 14 of the periodic table. Of these, organolithium compounds, organomagnesium compounds, organozinc compounds, organoaluminum compounds, and organotin compounds are preferred, and organolithium compounds, organoaluminum compounds, and organotin compounds are particularly preferred. Examples of the organic lithium compound include n-butyllithium, methyllithium, phenyllithium, neopentyllithium, neophyllithium, and the like. Examples of the organic magnesium include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, allylmagnesium bromide, neopentylmagnesium chloride, neophyllmagnesium chloride and the like. Examples of the organic zinc compound include dimethyl zinc, diethyl zinc, and diphenyl zinc. Examples of organoaluminum compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum ethoxide, ethylaluminum diethoxide, and the like. An aluminoxane compound obtained by a reaction between an organoaluminum compound and water can also be used. Examples of the organic tin compound include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin. The amount of these organometallic compounds varies depending on the organometallic compound used, but is preferably 0.1 to 10,000 times, preferably 0.2 to 5,000 times in terms of molar ratio to the central metal of the main catalyst. More preferably, 0.5 to 2,000 times is particularly preferable.

  The metal carbene complex catalyst (2) having Ru as a central metal includes (1,3-dimesityl-imidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, bis (tricyclohexylphosphine) benzylidene. Ruthenium dichloride, tricyclohexylphosphine- [1,3-bis (2,4,6-trimethylphenyl) -4,5-dibromoimidazol-2-ylidene]-[benzylidene] ruthenium dichloride, 4-acetoxybenzylidene (dichloro) ( 4,5-dibromo-1,3-dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium and the like.

  The use ratio of the metathesis polymerization catalyst is usually in the range of 1: 100 to 1: 2,000,000 in terms of the molar ratio of (transition metal in the metathesis polymerization catalyst: monomer) to the monomer used for the polymerization. Preferably, it is the range of 1: 200-1: 1,000,000. If the amount of catalyst is too large, it is difficult to remove the catalyst. If the amount is too small, sufficient polymerization activity may not be obtained.

  The polymerization reaction is usually performed in an organic solvent. The organic solvent to be used is not particularly limited as long as the polymer is dissolved or dispersed under predetermined conditions and does not affect the polymerization, but industrially used solvents are preferable. Specific examples of the organic solvent include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, and tricyclodecane. , Hexahydroindenecyclohexane, cyclooctane and other alicyclic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; dichloromethane, chloroform, 1,2-dichloroethane and other halogenated aliphatic hydrocarbons; chlorobenzene, dichlorobenzene Halogenated aromatic hydrocarbons such as: Nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene, and acetonitrile; Diethyl ether, tetrahydrofuran, etc. Et - ether solvents; and the like; anisole, aromatic ether solvents such as phenetole. Among these, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, an ether solvent, and an aromatic ether solvent that are widely used industrially are preferable.

  The amount of the organic solvent used is preferably such that the monomer concentration in the polymerization solution is 1 to 50% by weight, more preferably 2 to 45% by weight, and 3 to 40%. It is particularly preferable that the amount be% by weight. When the concentration of the monomer is less than 1% by weight, the productivity is deteriorated, and when it exceeds 50% by weight, the solution viscosity after polymerization is too high, and the subsequent hydrogenation reaction may be difficult.

  The polymerization reaction is started by mixing a monomer used for polymerization and a metathesis polymerization catalyst. As a method of mixing these, the metathesis polymerization catalyst solution may be added to the monomer solution, or vice versa. When the metathesis polymerization catalyst to be used is a mixed catalyst composed of a transition metal compound as a main catalyst and an organometallic compound as a second component, the reaction solution of the mixed catalyst may be added to the monomer solution, The reverse is also possible. Further, the transition metal compound solution may be added to the mixed solution of the monomer and the organometallic compound, or vice versa. Furthermore, the organometallic compound may be added to the mixed solution of the monomer and the transition metal compound, or vice versa.

  Although there is no restriction | limiting in particular in superposition | polymerization temperature, Usually, -30 degreeC-200 degreeC, Preferably it is 0 degreeC-180 degreeC. The polymerization time is not particularly limited, but is usually 1 minute to 100 hours.

  Examples of a method for adjusting the molecular weight of the obtained alicyclic olefin polymer include a method of adding an appropriate amount of a vinyl compound or a diene compound. The vinyl compound used for molecular weight adjustment is not particularly limited as long as it is an organic compound having a vinyl group, but α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrene, vinyltoluene and the like Styrenes; Ethers such as ethyl vinyl ether, i-butyl vinyl ether, and allyl glycidyl ether; Halogen-containing vinyl compounds such as allyl chloride; Oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol, and glycidyl methacrylate; Nitrogen-containing vinyl compounds such as acrylamide Can be mentioned. Diene compounds used for molecular weight adjustment include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl-1 Non-conjugated dienes such as 1,5-hexadiene, or 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3- Mention may be made of conjugated dienes such as hexadiene. The addition amount of a vinyl compound or a diene compound can be arbitrarily selected between 0.1 and 10 mol% with respect to the monomer used for polymerization according to the target molecular weight.

  As the polymerization catalyst when the alicyclic olefin polymer (A1) used in the present invention is obtained by an addition polymerization method, for example, a catalyst comprising a titanium, zirconium or vanadium compound and an organoaluminum compound is preferably used. These polymerization catalysts can be used alone or in combination of two or more. The amount of the polymerization catalyst is a molar ratio of the metal compound in the polymerization catalyst to the monomer used for the polymerization, and is usually in the range of 1: 100 to 1: 2,000,000.

  As the alicyclic olefin polymer (A1) used in the present invention, hydrogenation of the ring-opening polymer when using a hydrogenated product of the ring-opening polymer is usually performed using a hydrogenation catalyst. The hydrogenation catalyst is not particularly limited, and a catalyst generally used for hydrogenation of an olefin compound may be appropriately employed. Specific examples of the hydrogenation catalyst include cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, titanocene dichloride and n-butyllithium, zirconocene dichloride and sec-butyllithium, tetrabutoxytitanate and dimethylmagnesium. Ziegler catalyst comprising a combination of a transition metal compound and an alkali metal compound; dichlorotris (triphenylphosphine) rhodium, JP-A-7-2929, JP-A-7-149823, JP-A-11-209460, For example, bis (tricyclohexylphosphine) benzylidine described in JP-A-11-158256, JP-A-11-193323, JP-A-11-209460, etc. Noble metal complex catalyst comprising a ruthenium compound such as ruthenium (IV) dichloride; include homogeneous catalysts such as. Also, heterogeneous catalysts in which metals such as nickel, palladium, platinum, rhodium, ruthenium are supported on a carrier such as carbon, silica, diatomaceous earth, alumina, titanium oxide, such as nickel / silica, nickel / diatomaceous earth, nickel / Alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina, and the like can also be used. Further, the above-described metathesis polymerization catalyst can be used as it is as a hydrogenation catalyst.

  The hydrogenation reaction is usually performed in an organic solvent. The organic solvent can be appropriately selected depending on the solubility of the generated hydrogenated product, and the same organic solvent as the organic solvent used in the polymerization reaction described above can be used. Therefore, after the polymerization reaction, the hydrogenation catalyst can be added and reacted as it is without replacing the organic solvent. Furthermore, among the organic solvents used in the polymerization reaction described above, from the viewpoint of not reacting during the hydrogenation reaction, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, an ether solvent, an aromatic solvent Aromatic ether solvents are preferred, and aromatic ether solvents are more preferred.

  The hydrogenation reaction conditions may be appropriately selected according to the type of hydrogenation catalyst used. The reaction temperature is usually -20 to 250 ° C, preferably -10 to 220 ° C, more preferably 0 to 200 ° C. If it is less than −20 ° C., the reaction rate is slow, and if it exceeds 250 ° C., side reactions tend to occur. The pressure of hydrogen is usually 0.01 to 10.0 MPa, preferably 0.05 to 8.0 MPa. When the hydrogen pressure is less than 0.01 MPa, the hydrogen addition rate is slow, and when it exceeds 10.0 MPa, a high pressure reactor is required.

  The time for the hydrogenation reaction is appropriately selected in order to control the hydrogenation rate. The reaction time is usually in the range of 0.1 to 50 hours, and 50% or more, preferably 70% or more, more preferably 80% or more, in particular, of the carbon-carbon double bonds of the main chain in the polymer. Preferably 90% or more can be hydrogenated.

After the hydrogenation reaction, a treatment for removing the catalyst used in the hydrogenation reaction may be performed. The method for removing the catalyst is not particularly limited, and examples thereof include centrifugation and filtration. Furthermore, the catalyst removal can be promoted by adding a catalyst deactivator such as water or alcohol, or by adding an adsorbent such as activated clay, alumina, or silicon earth.
The alicyclic olefin polymer (A1) used in the present invention may be used as a polymer solution after polymerization or hydrogenation reaction, or may be used after removing the solvent. It is preferable to use it as a polymer solution since the dissolution and dispersion of the additive are improved during preparation and the process can be simplified.

(Inorganic filler (A2))
Although it does not specifically limit as an inorganic filler (A2), For example, calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, hydrated alumina, water Examples thereof include magnesium oxide, aluminum hydroxide, barium sulfate, silica, talc, and clay. Among these, silica is preferable because fine particles can be easily obtained. These inorganic fillers (A2) may be those treated with a silane coupling agent or an organic acid such as stearic acid.

  In addition, the inorganic filler (A2) is preferably non-conductive so as not to deteriorate the dielectric properties of the obtained electrical insulating layer. The shape of the inorganic filler (A2) is not particularly limited, and may be spherical, fibrous, plate-like, etc., but in order to obtain a fine rough surface shape, it is preferably a fine spherical shape. .

  The average particle diameter of the inorganic filler (A2) is preferably 0.1 to 10 μm, more preferably 0.2 to 2 μm. By making the average particle diameter of an inorganic filler into the said range, the surface roughness of an insulating adhesive film can be made into an appropriate range. The average particle diameter can be measured with a particle size distribution measuring device.

  The blending ratio of the inorganic filler (A2) is preferably 0.1 to 40% by weight, preferably 5 to 30% by weight, more preferably 10 to 20% by weight, in the resin composition for a plated layer. . By setting the blending ratio of the inorganic filler (A2) in the above range, the linear expansion coefficient and peel strength of a cured product obtained by curing the resin composition for a layer to be plated can be improved.

(Curable compound (A3))
Moreover, the resin composition for to-be-plated layers used by this invention accelerates | stimulates hardening of the resin composition for to-be-plated layers in addition to the alicyclic olefin polymer (A1) and inorganic filler (A2) which were mentioned above. As a component, a curable compound (A3) having two or more functional groups capable of reacting with the polar group of the alicyclic olefin polymer (A1) in the molecule (hereinafter referred to as “curable compound (A3)” as appropriate) ". ) May be further contained.

  The curable compound (A3) is not particularly limited as long as it is a compound having a functional group capable of reacting with the polar group of the alicyclic olefin polymer (A1). For example, the alicyclic olefin polymer (A1) When an alicyclic olefin polymer having a carboxyl group or a carboxylic acid anhydride group is used as a preferable curable compound (A3), epoxy resin, polyvalent isocyanate compound, polyvalent amine compound, polyhydric hydrazine Compounds, aziridine compounds and the like. Among these, an epoxy resin is more preferable because it is excellent in terms of balance between economy and performance.

  Specific examples of epoxy resins include phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, cresol type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, polyphenol type epoxy compounds, brominated bisphenol A type epoxy compounds, Glycidyl ether type epoxy compounds such as brominated bisphenol F type epoxy compounds and hydrogenated bisphenol A type epoxy compounds, alicyclic epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, isocyanurate type epoxy compounds, and alicyclic rings Examples thereof include an epoxy resin having a formula olefin structure or a fluorene structure. Among these, bisphenol A type epoxy compounds, alicyclic olefin structures, naphthalene structures or fluorenes can be obtained from the point that the mechanical properties of the obtained insulating adhesive film, laminate and cured product can be improved. An epoxy resin having a structure is preferable, and an epoxy resin having an alicyclic olefin structure is more preferable. In addition, these may be used individually by 1 type and may use 2 or more types together.

  As the bisphenol A type epoxy compound, for example, trade names “jER827, jER828, jER828EL, jER828XA, jER834” (manufactured by Mitsubishi Chemical Corporation), trade names “Epicron 840, Epicron 840-S, Epicron 850, Epicron 850-S”. , Epicron 850-LC "(manufactured by Dainippon Ink and Chemicals," Epicron "is a registered trademark). As an epoxy resin having an alicyclic olefin structure, a naphthalene structure or a fluorene structure, an epoxy resin having a dicyclopentadiene skeleton [for example, trade names "Epicron HP7200L, Epicron HP7200, Epicron HP7200H, Epicron HP7200HH" “Epicron” is a registered trademark); trade name “Tactix558” (manufactured by Huntsman Advanced Materials); trade names “XD-1000-1L, XD-1000-2L” (Nippon Kayaku Co., Ltd.) )] Or epoxy resin having a naphthalene skeleton [for example, trade names “Epicron HP4032, HP4032D, HP4700, HP4710, HP4770, HP5000” (above, Dainippon Ink & Chemicals, “Epicron”) Registered trademark), epoxy resin having a fluorene skeleton [e.g., trade names "ONCOAT EX-1010, ONCOAT EX-1011, ONCOAT EX-1012, ONCOAT EX-1020, ONCOAT EX-1030, ONCOAT EX- 1040, ONCOAT EX-1050, ONCOAT EX-1051 ”(above, manufactured by Nagase Sangyo Co., Ltd., ONCOAT is a registered trademark); trade name“ Ogsol PG-100, Ogsol EG-200, Ogsol EG-250 ”” , Manufactured by Osaka Gas Chemical Company, Ogsol is a registered trademark)].

  The compounding amount of the curable compound (A3) in the resin composition for a layer to be plated of the present invention is preferably 1 to 100 parts by weight, more preferably 100 parts by weight of the alicyclic olefin polymer (A1). Is in the range of 5 to 60 parts by weight, more preferably 10 to 50 parts by weight. Even if there are too few compounding quantities of a sclerosing | hardenable compound (A3), the effect | action which hardens the resin composition for to-be-plated layers will become inadequate, and hardening obtained by hardening the resin composition for to-be-plated layers There is a possibility that the peel strength of the object may be lowered.

(Other ingredients)
Moreover, the resin composition for to-be-plated layer used by this invention may contain the hardening accelerator as needed. The curing accelerator is not particularly limited, and examples thereof include aliphatic polyamines, aromatic polyamines, secondary amines, tertiary amines, imidazole derivatives, organic acid hydrazides, dicyandiamide and derivatives thereof, and urea derivatives. Among these, imidazole derivatives are particularly preferable.

  The imidazole derivative is not particularly limited as long as it is a compound having an imidazole skeleton, and examples thereof include 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, and 1-methyl. Alkyl-substituted imidazole compounds such as 2-ethylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-heptadecylimidazole; 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2- Aryl groups and aralkyl groups such as methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, benzimidazole, 2-ethyl-4-methyl-1- (2′-cyanoethyl) imidazole, etc. ring Imidazole compounds substituted with a hydrocarbon group containing a granulation; and the like. These can be used individually by 1 type or in combination of 2 or more types.

  The blending amount in the case of blending the curing accelerator may be appropriately selected according to the purpose of use, but is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer (A1). More preferably, it is 0.1-10 weight part, More preferably, it is 0.1-5 weight part.

  Furthermore, the resin composition for a layer to be plated used in the present invention has a general electrical insulating film such as a halogen-based flame retardant or a phosphate ester-based flame retardant for the purpose of improving the flame retardancy of the insulating adhesive film. You may mix | blend the flame retardant mix | blended with the resin composition for formation. The amount of the flame retardant blended is preferably 100 parts by weight or less, more preferably 60 parts by weight or less, based on 100 parts by weight of the alicyclic olefin polymer (A1).

  In addition, the resin composition for the layer to be plated used in the present invention may further include a flame retardant aid, a heat resistance stabilizer, a weather resistance stabilizer, an anti-aging agent, an ultraviolet absorber (laser processability improver), if necessary. Contains optional ingredients such as leveling agents, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, natural oils, synthetic oils, waxes, emulsions, magnetic materials, dielectric property modifiers, toughening agents, etc. Also good. What is necessary is just to select suitably the mixture ratio of these arbitrary components in the range which does not impair the objective of this invention.

  The method for producing the resin composition for a layer to be plated used in the present invention is not particularly limited, and the above components may be mixed as they are, or mixed in a state dissolved or dispersed in an organic solvent. Alternatively, a composition in which a part of each of the above components is dissolved or dispersed in an organic solvent may be prepared, and the remaining components may be mixed with the composition.

(Adhesive layer resin composition)
Next, the adhesive layer resin composition for forming the adhesive layer will be described. The resin composition for an adhesive layer used in the present invention contains an organic solvent-soluble polyimide (B1) and an inorganic filler (B2).

(Organic solvent soluble polyimide (B1))
The resin composition for adhesive layers used in the present invention contains an organic solvent-soluble polyimide (B1) as a resin component.
The organic solvent-soluble polyimide (B1) is not particularly limited as long as it is a polyimide that can be dissolved in an organic solvent at 23 ° C. by 20% by weight or more. Examples of such an organic solvent include N, N-dimethylacetamide, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, toluene, xylene and the like.

  In the present invention, the organic solvent-soluble polyimide (B1) is used as the resin component constituting the adhesive layer, so that the insulating adhesive film of the present invention is the above-described alicyclic olefin polymer (A1) as the resin component. It is possible to form an electrically insulating layer having a low linear expansion and excellent wiring embedding property while maintaining good adhesion with the layer to be plated.

  In the present invention, the organic solvent-soluble polyimide (B1) is obtained by reacting an acid dianhydride component and a diamine component, or obtained by reacting an acid dianhydride component and a polyvalent isocyanate compound. Those are preferably used.

  Examples of the acid dianhydride component include 4,4′-oxydiphthalic anhydride, 3,4′-oxydiphthalic anhydride, 3,3′-oxydiphthalic anhydride, 4,4 ′-(4,4 ′. -Isopropylidenediphenoxy) bis (phthalic anhydride), 4,4'-hydroquinonebis (phthalic anhydride), 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4' -Tetracarboxylic dianhydride, 1,2-ethylenebis (trimellitic acid monoester anhydride), p-phenylenebis (trimellitic acid monoester anhydride), pyromellitic dianhydride, 3,3 ', 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic Dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropanoic dianhydride, 3,3 ′, 4,4′-biphenyltetra Carboxylic dianhydrides, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides such as p-phenylenediphthalic anhydride, 4,4′-hexafluoro Examples thereof include isopropylidene diphthalic anhydride. These may be used individually by 1 type and can also be used in combination of 2 or more type.

  Examples of the diamine component include 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl thioether, and 3,4′-diaminodiphenyl thioether. 3,3′-diaminodiphenylthioether, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenyl Sulfone, 3,3′-diaminodiphenylsulfone, 4,4′-diaminobenzanilide, 3,4′-diaminobenzanilide, 3,3′-diaminobenzanilide, 4,4′-diaminobenzophenone, 3,4 ′ -Diaminobenzo Enone, 3,3′-diaminobenzophenone, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (3- Aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4 -(4-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2 -Bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropyl Pan, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene, 1,4′-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl ] Ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- ( 3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] Ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] Benzene, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- ( 4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4- {4- (4 -Aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] ben 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [ 4- (3-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2, 2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis ( 3-aminophenoxy) benzene, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phene Ru] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) Benzoyl] benzene, 4,4′-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, and the like. These may be used individually by 1 type and can also be used in combination of 2 or more type.

  Examples of the polyvalent isocyanate compound include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4. '-Diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4'-diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, 1,3-bis Aromatic polyisocyanates such as (α, α-dimethylisocyanatomethyl) benzene, tetramethylxylylene diisocyanate, diphenylene ether-4,4′-diisocyanate and naphthalene diisocyanate And aliphatic polyisocyanates such as 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate and norbornylene diisocyanate, and the like. . These may be used individually by 1 type and can also be used in combination of 2 or more type.

  The acid value of the organic solvent-soluble polyimide (B1) is preferably 2 to 100 mg (KOH) / g, more preferably 3 to 80 mg (KOH) / g, and particularly preferably in the range of 5 to 60 mg (KOH) / g. preferable.

(Inorganic filler (B2))
Although it does not specifically limit as an inorganic filler (B2), For example, the thing similar to the inorganic filler (A2) used for the resin composition for to-be-plated layers mentioned above can be used. However, in this invention, as an inorganic filler (B2) used for the resin composition for contact bonding layers, the inorganic used for the resin composition for to-be-plated layers mentioned above from a viewpoint of the fluidity | liquidity improvement of the resin composition for contact bonding layers. It is preferable to use one having an average particle size larger than that of the filler (A2).

  The blending ratio of the inorganic filler (B2) in the adhesive layer resin composition is preferably larger than the blending ratio of the inorganic filler (A2) in the above-described resin composition for a plating layer. That is, in the insulating adhesive film of the present invention, the composition ratio of the inorganic filler (B2) in the adhesive layer is larger than the composition ratio of the inorganic filler (A2) in the plated layer. It is preferable to do.

  The specific blending ratio of the inorganic filler (B2) in the adhesive layer resin composition is preferably 30 to 80% by weight, more preferably 40 to 75% by weight in the adhesive layer resin composition. Preferably it is 50 to 70% by weight. If the blending ratio of the inorganic filler (B2) is too small, the linear expansion coefficient of the cured product obtained by curing the resin composition for the adhesive layer may be increased. On the other hand, if the blending ratio is too large, the adhesive layer. The fluidity of the resin composition for use may deteriorate.

(Epoxy resin (B3))
In addition to the organic solvent-soluble polyimide (B1) and the inorganic filler (B2) described above, the adhesive layer resin composition used in the present invention is a component for accelerating the curing of the adhesive layer resin composition. Further, an epoxy resin (B3) may be further contained.

  The epoxy resin (B3) may be one having two or more epoxy groups, but in the present invention, it is the same as the epoxy resin exemplified as the curable compound (A3) of the above-described resin composition for a layer to be plated. Can be used. Moreover, as an epoxy resin (B3) mix | blended with the resin composition for contact bonding layers, among what was illustrated as a sclerosing | hardenable compound (A3) of the resin composition for to-be-plated layers mentioned above, a bisphenol A type epoxy compound and fat Epoxy resins having a cyclic olefin structure, a naphthalene structure or a fluorene structure are preferred, and an epoxy resin having a naphthalene structure is particularly preferred.

  The compounding amount of the epoxy resin (B3) in the adhesive layer resin composition of the present invention is preferably 10 to 1,000 parts by weight, more preferably 50 parts per 100 parts by weight of the organic solvent-soluble polyimide (B1). It is -700 weight part, More preferably, it is the range of 100-500 weight part. If the blending amount of the organic solvent-soluble polyimide (B1) is too small or too large, the curability of the adhesive layer resin composition may be insufficient.

(Phenol compound (B4))
The adhesive layer resin composition used in the present invention may further contain a phenol compound (B4) in addition to the epoxy resin (B3) as a component for curing the adhesive layer resin composition. .

  The phenol compound (B4) is not particularly limited as long as it has a phenolic hydroxyl group in the molecule. Examples of such a phenol compound (B4) include bisphenol A, phenol novolac resin, xylylene-modified phenol resin, dicyclopentadiene-modified phenol resin, fluorene-modified phenol resin, triphenol methane resin, or modified resins thereof. Of these, fluorene-modified phenolic resins are preferred. Moreover, as a phenol compound (B4), it is preferable to use that whose hydroxyl equivalent of a phenol compound is 50-300 from a sclerosing | hardenable viewpoint of the resin composition for contact bonding layers.

  The compounding amount of the phenol compound (B4) in the adhesive layer resin composition of the present invention is preferably 50 to 2000 parts by weight, more preferably 65 to 100 parts by weight with respect to 100 parts by weight of the organic solvent-soluble polyimide (B1). The amount is 900 parts by weight, more preferably 100 to 550 parts by weight. If the blending amount of the phenol compound (B4) is too small, the fluidity of the adhesive layer resin composition may be deteriorated. On the other hand, if the amount is too large, the cured product obtained by curing the adhesive layer resin composition may be deteriorated. There is a possibility that the linear expansion property deteriorates.

(Curing accelerator (B5))
Moreover, in addition to an epoxy resin (B3) and a phenolic compound (B4), the resin composition for adhesive layers used by this invention adds a hardening accelerator (B5) as a component for hardening the resin composition for adhesive layers. Furthermore, you may contain.

  Although it does not specifically limit as a hardening accelerator (B5), The thing similar to what was illustrated as a hardening accelerator which can be used for the resin composition for to-be-plated layers mentioned above can be used.

  The blending amount of the curing accelerator (B5) in the adhesive layer resin composition of the present invention may be appropriately selected depending on the purpose of use, but is preferably based on 100 parts by weight of the organic solvent-soluble polyimide (B1). Is 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, still more preferably 5 to 30 parts by weight. If the blending amount of the curing accelerator (B5) is too small, curing of the adhesive layer resin composition may be insufficient, while if too large, the storage stability of the adhesive layer resin composition may be inferior. There is a risk that the flow will be insufficient.

  The resin composition for an adhesive layer used in the present invention further includes an epoxy resin (B3), a phenol compound (B4), and a curing accelerator (B5) in addition to the organic solvent-soluble polyimide (B1) and the inorganic filler (B2). You may contain.

(Other ingredients)
In addition, the adhesive layer resin composition used in the present invention is, for example, for forming a general electric insulating film such as a halogen-based flame retardant or a phosphate ester-based flame retardant, as with the above-described resin composition for a plated layer. You may mix | blend the flame retardant mix | blended with this resin composition. When the flame retardant is blended, the blending amount is preferably 100 parts by weight or less, more preferably 60 parts by weight or less with respect to 100 parts by weight of the organic solvent-soluble polyimide (B1).

  Further, the adhesive layer resin composition used in the present invention may further include a flame retardant aid, a heat resistance stabilizer, a weather resistance stabilizer, and an anti-aging agent, as necessary, in the same manner as the above-described resin composition for a layer to be plated. , UV absorber (laser processability improver), leveling agent, antistatic agent, slip agent, anti-blocking agent, anti-fogging agent, lubricant, dye, natural oil, synthetic oil, wax, emulsion, magnetic substance, dielectric property adjustment You may mix | blend arbitrary components, such as an agent and a toughening agent. What is necessary is just to select suitably the mixture ratio of these arbitrary components in the range which does not impair the objective of this invention.

  The method for producing the resin composition for the adhesive layer used in the present invention is not particularly limited, and the above components may be mixed as they are, or mixed in a state dissolved or dispersed in an organic solvent. Alternatively, a composition in which a part of each of the above components is dissolved or dispersed in an organic solvent may be prepared, and the remaining components may be mixed with the composition.

(Insulating adhesive film)
The insulating adhesive film of this invention has a to-be-plated layer which consists of the resin composition for to-be-plated layers mentioned above, and an adhesive layer which consists of the resin composition for above-mentioned adhesive layers.

  The insulating adhesive film of the present invention can be obtained, for example, by the following two methods: (1) Applying, spreading or casting the above-described resin composition for a layer to be plated on a support, drying as necessary, and then And a method for producing the adhesive layer resin composition by further applying or casting the above-described resin composition for an adhesive layer and drying as necessary; (2) the above-described resin composition for a layer to be plated on a support; Coating, spreading or casting, and applying the above-mentioned resin composition for a bonding layer and the above-mentioned resin composition for an adhesive layer formed into a sheet or film obtained by drying as necessary. , By spraying or casting, drying as necessary, forming a sheet or film and then laminating the molded product for the adhesive layer, and by integrating these molded products, Can be manufactured. Among these production methods, the production method (1) is preferred because it is an easier process and is excellent in productivity.

  In the production method of (1) described above, when the resin composition for a plating layer is applied, dispersed or cast onto a support, and applied to the resin composition for a plated layer applied, dispersed or cast, for the adhesive layer When the resin composition is applied, dispersed or cast, or in the production method (2) described above, the resin composition for the plating layer and the resin composition for the adhesive layer are formed into a sheet or film to be plated. When the layered molded body and the adhesive layer molded body are used, the resin composition for the layer to be plated or the resin composition for the adhesive layer is added to an organic solvent as necessary, applied to the support, spread, or It is preferable to cast.

  Examples of the support used in this case include a resin film and a metal foil. Examples of the resin film include polyethylene terephthalate film, polypropylene film, polyethylene film, polycarbonate film, polyethylene naphthalate film, polyarylate film, and nylon film. Among these films, a polyethylene terephthalate film or a polyethylene naphthalate film is preferable from the viewpoint of heat resistance, chemical resistance, peelability, and the like. Examples of the metal foil include copper foil, aluminum foil, nickel foil, chrome foil, gold foil, and silver foil. The average surface roughness Ra of the support is usually 300 nm or less, preferably 150 nm or less, more preferably 100 nm or less.

  The thickness of the plated layer resin composition and the adhesive layer resin composition in the manufacturing method (1) described above, or the thickness of the plated layer molded body and the adhesive layer molded body in the manufacturing method (2) described above. The thickness is not particularly limited, but when the insulating adhesive film is formed, the thickness of the layer to be plated is preferably 1 to 10 μm, more preferably 1 to 8 μm, still more preferably 1 to 5 μm, and the thickness of the adhesive layer. However, the thickness is preferably 10 to 100 μm, more preferably 10 to 80 μm, and still more preferably 15 to 60 μm. If the thickness of the layer to be plated is too thin, the formability of the conductor layer may be reduced when the conductor layer is formed by electroless plating on the cured product obtained by curing the insulating adhesive film. On the other hand, if the thickness of the layer to be plated is too thick, the linear expansion of the cured product obtained by curing the insulating adhesive film may increase. Moreover, when the thickness of the adhesive layer is too thin, the wiring embedding property of the insulating adhesive film may be lowered.

  Examples of the method for applying the resin composition for the plating layer and the resin composition for the adhesive layer include dip coating, roll coating, curtain coating, die coating, slit coating, and gravure coating.

  In addition, after the resin composition for a plating layer in the production method of (1) described above is applied, dispersed or cast on a support, or the resin composition for an adhesive layer is applied on the resin composition for a plating layer. After coating, spreading, or casting, or after coating the plated layer resin composition and the adhesive layer resin composition on the support in the production method of (2) above, drying is performed as necessary. You may go. The drying temperature is preferably set to a temperature at which the resin composition for the plating layer and the resin composition for the adhesive layer are not cured, and is usually 20 to 300 ° C, preferably 30 to 200 ° C. The drying time is usually 30 seconds to 1 hour, preferably 1 minute to 30 minutes.

  In addition, in the insulating adhesive film of this invention, it is preferable that the to-be-plated layer and adhesive layer which comprise an insulating adhesive film are an uncured or semi-hardened state. By making these into an uncured or semi-cured state, the adhesive layer constituting the insulating adhesive film of the present invention can be made highly adhesive. Here, uncured means that the insulating adhesive film of the present invention is immersed in a solvent capable of dissolving the alicyclic olefin polymer (A1) and a solvent capable of dissolving the organic solvent-soluble polyimide (B1), respectively. In addition, substantially all of the alicyclic olefin polymer (A1) and the organic solvent-soluble polyimide (B1) are dissolved. Semi-cured is a state in which the resin is cured halfway to the extent that it can be further cured by heating. Preferably, a solvent capable of dissolving the alicyclic olefin polymer (A1) and an organic solvent-soluble polyimide ( A part of the alicyclic olefin polymer (A1) and the organic solvent-soluble polyimide (B1) (specifically 7% by weight or more) is dissolved in a solvent capable of dissolving B1), or a solvent The volume after the molded body is immersed for 24 hours inside is 200% or more of the volume before the immersion (swelling rate).

(Laminate)
The laminate of the present invention is formed by laminating the above-described insulating adhesive film of the present invention on a substrate. As the laminate of the present invention, at least the insulating adhesive film of the present invention described above may be laminated. From the substrate having a conductor layer on the surface and the above described insulating adhesive film of the present invention. What laminates | stacks the electrical insulating layer which becomes is preferable. In this case, the insulating adhesive film of the present invention is configured to be laminated with the substrate via an adhesive layer. That is, in the laminated body of the present invention, the surface of the electrical insulating layer is formed by the layer to be plated among the layer to be plated and the adhesive layer of the insulating adhesive film of the present invention.

  A substrate having a conductor layer on the surface has a conductor layer on the surface of the electrically insulating substrate. The electrically insulating substrate contains a known electrically insulating material (for example, alicyclic olefin polymer, epoxy resin, maleimide resin, (meth) acrylic resin, diallyl phthalate resin, triazine resin, polyphenyl ether, glass, etc.). The resin composition is formed by curing. Although a conductor layer is not specifically limited, Usually, it is a layer containing the wiring formed with conductors, such as an electroconductive metal, Comprising: Various circuits may be included further. The configuration and thickness of the wiring and circuit are not particularly limited. Specific examples of the substrate having a conductor layer on the surface include a printed wiring board and a silicon wafer substrate. The thickness of the substrate having a conductor layer on the surface is usually 10 μm to 10 mm, preferably 20 μm to 5 mm, more preferably 30 μm to 2 mm.

  The substrate having a conductor layer on the surface used in the present invention is preferably pretreated on the surface of the conductor layer in order to improve adhesion to the electrical insulating layer. As a pretreatment method, a known technique can be used without any particular limitation. For example, if the conductor layer is made of copper, an oxidation treatment method in which a strong alkali oxidizing solution is brought into contact with the surface of the conductor layer to form a copper oxide layer on the conductor surface and roughened, After oxidation with this method, reduce with sodium borohydride, formalin, etc., deposit and roughen the plating on the conductor layer, contact the organic acid with the conductor layer to elute the copper grain boundaries and roughen And a method of forming a primer layer with a thiol compound or a silane compound on the conductor layer. Among these, from the viewpoint of easy maintenance of the shape of a fine wiring pattern, a method in which an organic acid is brought into contact with a conductor layer to elute and roughen the grain boundaries of copper, and a primer using a thiol compound or a silane compound A method of forming a layer is preferred.

  The laminate of the present invention can usually be produced by heat-pressing the above-mentioned insulating adhesive film of the present invention on a substrate having a conductor layer on the surface.

  As a method of thermocompression bonding, an insulating adhesive film with a support is superposed so that the adhesive layer constituting the insulating adhesive film is in contact with the conductor layer of the substrate described above, a pressure laminator, a press, a vacuum laminator, The method of carrying out thermocompression bonding (lamination) using pressurizers, such as a vacuum press and a roll laminator, is mentioned. By heating and pressurizing, bonding can be performed so that there is substantially no void at the interface between the conductor layer on the substrate surface and the insulating adhesive film.

  The temperature of the thermocompression bonding operation is usually 30 to 250 ° C., preferably 70 to 200 ° C., the pressure applied is usually 10 kPa to 20 MPa, preferably 100 kPa to 10 MPa, and the time is usually 30 seconds to 5 seconds. Time, preferably 1 minute to 3 hours. The thermocompression bonding is preferably performed under reduced pressure in order to improve the embedding property of the wiring pattern and suppress the generation of bubbles. The pressure under reduced pressure at which thermocompression bonding is performed is usually 100 kPa to 1 Pa, preferably 40 kPa to 10 Pa.

(Cured product)
The hardened | cured material of this invention can be made into hardened | cured material by performing the process which hardens the insulating adhesive film of this invention about the laminated body of this invention obtained by the method mentioned above. Curing is usually performed by heating the entire substrate on which the insulating adhesive film of the present invention is formed on the conductor layer. Curing can be performed simultaneously with the above-described thermocompression bonding operation. Alternatively, the thermocompression may be performed after the thermocompression operation is performed under conditions that do not cause curing, that is, at a relatively low temperature for a short time.

(Complex)
In the composite of the present invention, another conductor layer is formed on the electrical insulating layer of the laminate of the present invention described above, that is, on the plated layer of the cured product of the insulating adhesive film by electroless plating. It will be. Hereinafter, the method for producing a composite according to the present invention will be described using a multilayer circuit board as an example of the composite according to the present invention.

  First, a via hole or a through hole that penetrates the electrical insulating layer is formed in the laminate. The via hole is formed to connect the respective conductor layers constituting the multilayer circuit board when the multilayer circuit board is used. The via hole or the through hole can be formed by chemical processing such as photolithography or physical processing such as drilling, laser, or plasma etching. Among these methods, a laser method (carbon dioxide laser, excimer laser, UV-YAG laser, or the like) is preferable because a finer via hole can be formed without degrading the characteristics of the electrical insulating layer.

Next, surface roughening treatment is performed to roughen the surface of the electrically insulating layer of the laminate, specifically, the surface of the layer to be plated of the insulating adhesive film constituting the laminate. The surface roughening treatment is performed in order to improve the adhesiveness with the conductive layer formed on the electrical insulating layer.
The surface average roughness Ra of the electrical insulating layer is preferably 0.05 μm or more and less than 0.5 μm, more preferably 0.06 μm or more and 0.3 μm or less, and the surface 10-point average roughness Rzjis is preferably 0.00. They are 3 micrometers or more and less than 4 micrometers, More preferably, they are 0.5 micrometers or more and 2 micrometers or less. In this specification, Ra is the arithmetic average roughness shown in JIS B0601-2001, and the surface ten-point average roughness Rzjis is the ten-point average roughness shown in JIS B0601-2001 appendix 1.

  Although it does not specifically limit as a surface roughening processing method, The method etc. which contact an electrically insulating layer surface (namely, surface of the to-be-plated layer of the hardened | cured material of an insulating adhesive film) and an oxidizing compound are mentioned. Examples of the oxidizing compound include known compounds having oxidizing ability, such as inorganic oxidizing compounds and organic oxidizing compounds. In view of easy control of the average surface roughness of the electrical insulating layer, it is particularly preferable to use an inorganic oxidizing compound or an organic oxidizing compound. Examples of inorganic oxidizing compounds include permanganate, chromic anhydride, dichromate, chromate, persulfate, activated manganese dioxide, osmium tetroxide, hydrogen peroxide, periodate, and the like. . Examples of the organic oxidizing compound include dicumyl peroxide, octanoyl peroxide, m-chloroperbenzoic acid, peracetic acid, and ozone.

There is no particular limitation on the method of roughening the surface of the electrical insulating layer using an inorganic oxidizing compound or an organic oxidizing compound. For example, there is a method in which an oxidizing compound solution prepared by dissolving the oxidizing compound in a soluble solvent is brought into contact with the surface of the electrical insulating layer.
The method for bringing the oxidizing compound solution into contact with the surface of the electrical insulating layer is not particularly limited. For example, the dipping method in which the electrical insulating layer is immersed in the oxidizing compound solution, the surface tension of the oxidizing compound solution is used. Any method may be used, such as a liquid filling method in which the oxidizing compound solution is placed on the electric insulating layer, or a spray method in which the oxidizing compound solution is sprayed on the electric insulating layer. By performing the surface roughening treatment, it is possible to improve the adhesion between the electrical insulating layer and another layer such as a conductor layer.

  The temperature and time for bringing these oxidizing compound solutions into contact with the surface of the electrical insulating layer may be set arbitrarily in consideration of the concentration and type of the oxidizing compound, the contact method, etc. It is 150 degreeC, Preferably it is 20-100 degreeC, and time is 0.5 to 60 minutes normally, Preferably it is 1 to 40 minutes.

  Note that the surface of the electrical insulating layer after the surface roughening treatment is washed with water in order to remove the oxidizing compound after the surface roughening treatment. In addition, if a substance that cannot be washed with water is attached, the substance can be further washed with a dissolvable cleaning solution or brought into contact with other compounds to make it soluble in water. Wash with water. For example, when an alkaline aqueous solution such as an aqueous potassium permanganate solution or an aqueous sodium permanganate solution is brought into contact with the electrical insulating layer, a mixed solution of hydroxyamine sulfate and sulfuric acid is used to remove the generated manganese dioxide film. It can wash | clean with water, after neutralizing-reducing process with the acidic aqueous solution of this.

Next, after performing a surface roughening treatment on the electrical insulating layer of the laminate, on the surface of the electrical insulating layer (that is, the surface of the layer to be plated of the cured adhesive adhesive film) and the inner wall surface of the via hole or the through hole, A conductor layer is formed.
The conductive layer is formed by electroless plating from the viewpoint that a conductive layer having excellent adhesion can be formed.

  For example, when forming a conductor layer by an electroless plating method, first, before forming the metal thin film on the surface of the electrical insulation layer, the electrical insulation layer (ie, the plated layer of the cured product of the insulating adhesive film) It is common to deposit catalyst nuclei such as silver, palladium, zinc, cobalt on the top. The method for attaching the catalyst nucleus to the electrical insulating layer is not particularly limited. For example, a metal compound such as silver, palladium, zinc, or cobalt, or a salt or complex thereof is added to water or an organic solvent such as alcohol or chloroform to 0.001. Examples include a method of reducing a metal after dipping in a solution (which may contain an acid, an alkali, a complexing agent, a reducing agent, etc., if necessary) dissolved at a concentration of 10 to 10% by weight.

  As the electroless plating solution used in the electroless plating method, a known autocatalytic electroless plating solution may be used, and the metal species, reducing agent species, complexing agent species, hydrogen ion concentration, The dissolved oxygen concentration is not particularly limited. For example, electroless copper plating solution using ammonium hypophosphite, hypophosphorous acid, ammonium borohydride, hydrazine, formalin, etc. as a reducing agent; electroless nickel-phosphorous plating solution using sodium hypophosphite as a reducing agent Electroless nickel-boron plating solution using dimethylamine borane as a reducing agent; electroless palladium plating solution; electroless palladium-phosphorous plating solution using sodium hypophosphite as a reducing agent; electroless gold plating solution; electroless silver Plating solution: An electroless plating solution such as an electroless nickel-cobalt-phosphorous plating solution using sodium hypophosphite as a reducing agent can be used.

  After forming the metal thin film, the substrate surface can be brought into contact with a rust preventive agent to carry out a rust prevention treatment. Moreover, after forming a metal thin film, a metal thin film can also be heated in order to improve adhesiveness. The heating temperature is usually 50 to 350 ° C, preferably 80 to 250 ° C. In this case, heating may be performed under a pressurized condition. As a pressurizing method at this time, for example, a method using a physical pressurizing means such as a hot press machine or a pressurizing and heating roll machine can be cited. The applied pressure is usually 0.1 to 20 MPa, preferably 0.5 to 10 MPa. If it is this range, the high adhesiveness of a metal thin film and an electrically insulating layer is securable.

  A resist pattern for plating is formed on the metal thin film thus formed, and further, plating is grown thereon by wet plating such as electrolytic plating (thick plating), then the resist is removed, and further etched. The metal thin film is etched into a pattern to form a conductor layer. Therefore, the conductor layer formed by this method usually consists of a patterned metal thin film and plating grown thereon.

  The multilayer circuit board obtained as described above is used as a substrate for manufacturing the above-described laminate, and this is thermocompression-bonded with the above-described molded body or composite molded body and cured to form an electrical insulating layer. Further, by further forming a conductive layer in accordance with the above-described method and repeating these, further multilayering can be performed, and thereby a desired multilayer circuit board can be obtained.

  The composite of the present invention thus obtained (and the multilayer circuit board as an example of the composite of the present invention) has an electrical insulation layer comprising the insulating adhesive film of the present invention, and the electrical insulation layer Is a low linear expansion, excellent wiring embedding, and excellent peel strength, so when a conductor layer is formed on the electrical insulating layer, the formed conductor layer is patterned, and fine wiring is formed. Thus, the conductor layer can be satisfactorily patterned. In particular, according to the present invention, in the insulating adhesive film of the present invention, the layer to be plated is formed by containing the alicyclic olefin polymer (A1) as a resin component, and the adhesive layer is made of an organic solvent-soluble polyimide. By including (B1) as a resin component, the problem caused by the two-layer structure of these different resins, specifically, the adhesion between the two layers is poor and the peel strength is reduced. It is intended to realize low linear expansion and excellent wiring embedding while effectively preventing the occurrence of defects. Therefore, the composite of the present invention (and the multilayer circuit board as an example of the composite of the present invention) can be suitably used for various applications.

(Electronic material substrate)
The board | substrate for electronic materials of this invention consists of the hardened | cured material or composite_body | complex of this invention mentioned above. The substrate for electronic material of the present invention comprising such a cured product or composite of the present invention is a mobile phone, PHS, notebook computer, PDA (personal digital assistant), mobile video phone, personal computer, supercomputer, server, Router, liquid crystal projector, engineering workstation (EWS), pager, word processor, TV, viewfinder type or monitor direct view type video tape recorder, electronic notebook, electronic desk calculator, car navigation device, POS terminal, device with touch panel It can use suitably for various electronic devices.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, the part and% in each example are a basis of weight unless there is particular notice. Various physical properties were evaluated according to the following methods.

(1) Number average molecular weight (Mn) and weight average molecular weight (Mw) of alicyclic olefin polymer
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the alicyclic olefin polymer were measured by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent, and were determined as polystyrene equivalent values.

(2) Hydrogenation rate of alicyclic olefin polymer The ratio of the number of moles of unsaturated bonds hydrogenated to the number of moles of unsaturated bonds in the polymer before hydrogenation was measured by ¹ H-NMR spectrum at 400 MHz. This was taken as the hydrogenation rate.

(3) The content of the repeating unit having a carboxylic anhydride group of the alicyclic olefin polymer The ratio of the number of moles of the repeating unit having a carboxylic acid anhydride group to the total number of monomer units in the polymer, determined by ^{1 H-NMR} spectrum measurement of 400MHz, which was used as a content of the repeating unit having a carboxylic acid anhydride groups of the polymer.

(4) Tensile strength, elastic modulus, and elongation The tensile strength, elastic modulus, and elongation of the film composite were measured using an autograph (AGS-5kNH, manufactured by Shimadzu Corporation) with a sample shape of 70 mm × 5 mm, a tensile speed of 2 mm / min, Measurement was performed under the condition of a distance between chucks of 50 mm.

(5) Linear expansion coefficient A small piece having a width of 5.95 mm and a length of 15.4 mm was cut out from the film composite, and a thermomechanical analyzer (TMA / SDTA840 was used under the conditions of a distance between supporting points of 10 mm and a heating rate of 10 ° C / min. : Mettler Toledo Co., Ltd.), the linear expansion coefficient was measured at 30 ° C. to 150 ° C.

(6) Wiring embedding
The inner layer circuit board (IPC MULTI-PURPOSE TESTBOARD No. IPC-B-25, conductor thickness 25 μm, 0.8 mm thickness) was laminated so that the adhesive layer side surface of the film composite was in contact with both surfaces. Specifically, the primary press is performed by thermocompression bonding at a temperature of 110 ° C. and a pressure of 0.1 MPa for 90 seconds under a reduced pressure of 200 Pa in a vacuum laminator equipped with heat-resistant rubber press plates at the top and bottom, A laminate was obtained by thermocompression bonding at a pressure bonding temperature of 110 ° C. and a pressure of 1 MPa for 90 seconds using a hydraulic press device having upper and lower press plates. And the support film was peeled off from this laminated body, and it hardened | cured for 60 minutes at 180 degreeC. After curing, the step between the portion with and without the conductor of the comb pattern portion having a conductor width of 165 μm and a conductor interval of 165 μm was measured with a stylus type step thickness meter (P-10, manufactured by Tencor Instruments). Then, the wiring embedding property was evaluated.
○: Step is less than 2 μm ×: Step is 2 μm or more

(7) Peel strength The peel strength between the insulating layer and the copper plating layer in the multilayer printed wiring board was measured according to JIS C6481-1996.

Synthesis example 1
As the first stage of polymerization, 35 mol part of 5-ethylidene-bicyclo [2.2.1] hept-2-ene (hereinafter abbreviated as “EdNB”), 0.9 mol part of 1-hexene, 340 mol part of anisole and 4-acetoxybenzylidene (dichloro) (4,5-dibromo-1,3-dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium (C1063, manufactured by Wako Pure Chemical Industries) as a ruthenium-based polymerization catalyst 005 mol part was charged into a pressure-resistant glass reactor substituted with nitrogen, and a polymerization reaction was carried out at 80 ° C. for 30 minutes with stirring to obtain a solution of a norbornene-based ring-opening polymer.
Then, tetracyclo ^{[9.2.1.0 2,10} in the solution obtained in the polymerization the first stage as the polymerization second stage. 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (methanotetrahydrofluorene) 45 mol part, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride 20 mol part In addition, 250 mol parts of anisole and 0.01 mol parts of C1063 were added, and a polymerization reaction was performed at 80 ° C. for 1.5 hours with stirring to obtain a solution of a norbornene ring-opening polymer. When this solution was measured by gas chromatography, it was confirmed that substantially no monomer remained, and the polymerization conversion rate was 99% or more.
Next, the solution of the obtained ring-opening polymer was charged into an autoclave equipped with a stirrer substituted with nitrogen, 0.03 mol part of C1063 was added, and the mixture was stirred at 150 ° C. and a hydrogen pressure of 7 MPa for 5 hours to conduct a hydrogenation reaction. Thus, a solution of an alicyclic olefin polymer (A1-1), which is a hydrogenated product of a norbornene-based ring-opening polymer, was obtained. The weight average molecular weight of the obtained polymer (A1-1) was 60,000, the number average molecular weight was 30,000, and the molecular weight distribution was 2. The hydrogenation rate was 95%, and the content of repeating units having a carboxylic anhydride group was 20 mol%. The solid content concentration of the polymer (A1-1) solution was 22%.

Example 1
(Alicyclic olefin polymer-containing resin composition (A-1))
454 parts of the solution of the alicyclic olefin polymer (A1-1) obtained in Synthesis Example 1 (100 parts in terms of the alicyclic olefin polymer (A1-1)), di as the curable compound (A3) 36 parts of an epoxy resin having a cyclopentadiene skeleton (“Epiclon HP7200L”, manufactured by Dainippon Ink and Chemicals, “Epicron” is a registered trademark), silica as an inorganic filler (A2) (“Admafine SO-C1”, Made by Mattex, average particle size 0.25 μm, “Admafine” is a registered trademark 24.5 parts, tris (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate (anti-aging agent) "Irganox 3114", manufactured by Ciba Specialty Chemicals) 1 part, 2- [2-hydroxy-3,5-bis (α, α-dimethyl) as an ultraviolet absorber [Tilbenzyl) phenyl] -2H-benzotriazole 0.5 part and 0.5 part of 1-benzyl-2-phenylimidazole as a curing accelerator are mixed with anisole so that the concentration of the compounding agent is 16%. By mixing, the varnish of the alicyclic olefin polymer containing resin composition (A-1) was obtained. Table 1 shows the composition of the alicyclic olefin polymer-containing resin composition (A-1).

(Polyimide-containing resin composition (B-1))
Polyimide resin as organic solvent-soluble polyimide (B1) ("ELG-485", manufactured by Dainippon Ink & Chemicals, Inc., acid value 28 mg (KOH) / g) 100 parts, epoxy having naphthalene skeleton as epoxy resin (B3) 290 parts of resin ("Epiclon HP4710", manufactured by Dainippon Ink and Chemicals, "Epicron" is a registered trademark), a mixture of fluorene-modified phenolic resin as a phenolic compound (B4) and bisphenol A ("CP002", Osaka Gas Chemical) 233 parts, inorganic filler (B2) silica ("HPS-0500", Toagosei Co., Ltd., average particle size 0.5 μm) 960 parts, and curing accelerator (B5) imidazole compound (" Cureazole 2PZCNS-PW ”, manufactured by Shikoku Kasei Co., Ltd.,“ Cureazole ”is a registered trademark) 16 7 parts, N, mixed into N- dimethylacetamide, formulation concentration by mixing to be 65% to obtain a varnish of polyimide-containing resin composition (B-1). Table 1 shows the composition of the polyimide-containing resin composition (B-1).

(Production of film composite)
The varnish of the curable resin composition (A-1) was applied onto a polyethylene terephthalate film (support) having a thickness of 100 μm using a wire bar, and then dried at 80 ° C. for 5 minutes in a nitrogen atmosphere. A film with a support on which a resin layer having an uncured curable resin composition (A-1) thickness of 3 μm was formed was obtained.

  Next, on the surface of the curable resin composition (A-1) of the film with the support, a varnish of the curable resin composition (B-1), a doctor blade (manufactured by Tester Sangyo Co., Ltd.) and an auto film applicator ( A film composite with a support on which a resin layer having a total thickness of 40 μm is formed by drying at 80 ° C. for 10 minutes in a nitrogen atmosphere. Obtained. The film composite with a support was formed in the order of the support, the resin layer of the curable resin composition (A-1), and the resin layer of the curable resin composition (B-1).

  And about the obtained film composite with a support body, the wiring embedding property was measured according to the said method. In addition, a 10 μm thick copper foil is placed on the copper-clad laminate, and the obtained film composite with a support is placed on the inner side of the curable resin composition with the support attached. In this way, using a vacuum laminator equipped with heat-resistant rubber press plates at the top and bottom, the pressure was reduced to 200 Pa, thermocompression bonded at a temperature of 110 ° C. and a pressure of 0.1 MPa for 60 seconds, and then at 180 ° C. for 120 minutes in air. And cured by heating. After curing, a cured resin with a copper foil was cut out and the copper foil was dissolved in a 1 mol / L ammonium persulfate aqueous solution to obtain a film-like cured product. With respect to this cured film, the tensile strength, elastic modulus, elongation, and linear expansion coefficient were measured according to the above-described method. In Example 1, a layer made of the alicyclic olefin polymer-containing resin composition (A-1) is a layer to be plated, and a layer made of the polyimide-containing resin composition (B-1) is an adhesive layer. Each measurement was performed. The results are shown in Table 2.

(Production of laminate)
Next, separately from the above, the surface of the core material obtained by impregnating glass fiber with a varnish containing a glass filler and a halogen-free epoxy resin, copper having a thickness of 18 μm was stuck, thickness 0.8 mm, On a 150 mm square (150 mm long, 150 mm wide) double-sided copper-clad substrate surface, a conductor layer having a wiring width and distance between wirings of 50 μm, a thickness of 18 μm, and a microetched surface by contact with an organic acid is formed. An inner layer substrate was obtained.

  A laminate of the film composite with a support obtained above was cut into 150 mm square on both surfaces of the inner layer substrate so that the surfaces on the polyimide-containing resin composition (B-1) side were inside. After that, a primary press was performed. The primary press is thermocompression bonding at a temperature of 110 ° C. and a pressure of 0.1 MPa for 90 seconds under a reduced pressure of 200 Pa using a vacuum laminator provided with heat-resistant rubber press plates at the top and bottom. Furthermore, using a hydraulic press device provided with metal press plates at the top and bottom, thermocompression bonding was performed at a pressure bonding temperature of 110 ° C. and 1 MPa for 90 seconds. Subsequently, the laminated body of the resin layer which consists of an alicyclic olefin polymer containing resin composition (A-1) and a polyimide containing resin composition (B-1), and the inner layer board | substrate was obtained by peeling a support body. Further, the laminate was left in an air atmosphere at 180 ° C. for 60 minutes to cure the resin layer and form an electrical insulating layer on the inner layer substrate.

(Swelling process)
The obtained laminate was prepared to have a swelling liquid (“Swelling Dip Securigant P”, manufactured by Atotech, “Securigant” is a registered trademark) of 500 mL / L, sodium hydroxide 3 g / L. After dipping in the aqueous solution for 15 minutes, it was washed with water.

(Oxidation process)
Next, after 15 minutes of rocking immersion in an aqueous solution of permanganate (“Concentrate Compact CP”, manufactured by Atotech) at 500 mL / L and a 70 ° C. aqueous solution prepared to a sodium hydroxide concentration of 40 g / L , Washed with water.

(Neutralization reduction process)
Subsequently, an aqueous solution of hydroxyamine sulfate (“Reduction Securigant P 500”, manufactured by Atotech Co., Ltd., “Securigant” is a registered trademark) is 100 mL / L, and an aqueous solution at 40 ° C. prepared to have 35 mL / L of sulfuric acid is added to the laminate. Was immersed for 5 minutes, neutralized and reduced, and then washed with water.

(Cleaner / conditioner process)
Next, the laminate was immersed in an aqueous solution at 50 ° C. adjusted to a concentration of 50 ml / L of an aqueous cleaner / conditioner aqueous solution (“Alcup MCC-6-A”, manufactured by Uemura Kogyo Co., Ltd., “Alcup” is a registered trademark) for 5 minutes. Cleaner and conditioner treatment was performed. Next, the laminate was immersed in 40 ° C. washing water for 1 minute and then washed with water.

(Soft etching process)
Next, the laminate was immersed in an aqueous solution prepared to have a sulfuric acid concentration of 100 g / L and sodium persulfate of 100 g / L for 2 minutes to perform soft etching treatment, and then washed with water.

(Pickling process)
Next, the laminate was dipped in an aqueous solution prepared so as to have a sulfuric acid concentration of 100 g / L for 1 minute to perform pickling treatment, and then washed with water.

(Catalyst application process)
Next, Alcup Activator MAT-1-A (trade name, manufactured by Uemura Kogyo Co., Ltd., “Alcup” is a registered trademark) is 200 mL / L, Alcup Activator MAT-1-B (upper product name, manufactured by Mura Kogyo Co., Ltd., “Alcup”) Was immersed in a 60 ° C. Pd salt-containing plating catalyst aqueous solution prepared so that the registered trademark was 30 mL / L and sodium hydroxide was 0.35 g / L, and then washed with water.

(Activation process)
Subsequently, Alcup Redeusa MAB-4-A (trade name, manufactured by Uemura Kogyo Co., Ltd., “Alcup” is a registered trademark) is 20 mL / L, Alcup Redeusa MAB-4-B (trade name, manufactured by Uemura Kogyo Co., Ltd., “ Alcup "is a registered trademark) in an aqueous solution adjusted to 200 mL / L. The laminate was immersed at 35 ° C. for 3 minutes to reduce the plating catalyst, and then washed with water.

(Accelerator process)
Next, the laminate was immersed in an aqueous solution prepared so that Alcap Accelerator MEL-3-A (trade name, manufactured by Uemura Kogyo Co., Ltd., “Alcup” is a registered trademark) at 50 mL / L at 25 ° C. for 1 minute. .

(Electroless plating process)
The laminated body thus obtained was obtained by using Sulcup PEA-6-A (trade name, manufactured by Uemura Kogyo Co., Ltd., “Sulcup” is a registered trademark), 100 mL / L, Sulcup PEA-6-B-2X (trade name, Uemura). Industrial product) 50 mL / L, Sulcup PEA-6-C (trade name, manufactured by Uemura Industrial Co., Ltd.) 14 mL / L, Sulcup PEA-6-D (trade name, manufactured by Uemura Industrial Co., Ltd.) 15 mL / L, Sulcup PEA-6 -E (trade name, manufactured by Uemura Kogyo Co., Ltd.) 50 mL / L, 37% by weight immersion in formalin aqueous solution 5 mL / L Electroless copper plating treatment was performed to form an electroless plating film on the surface of the laminate (the surface of the layer made of the alicyclic olefin polymer-containing resin composition (A-1)). And about the laminated body which formed the electroless-plated film on the surface of the layer which consists of an alicyclic olefin polymer containing resin composition (A-1), the electroless-plated film deposition property was evaluated according to the said method. The results are shown in Table 2.

  Next, the laminate on which the electroless plating film was formed was immersed in an antirust solution prepared so that AT-21 (trade name, manufactured by Uemura Kogyo Co., Ltd.) was 10 mL / L at room temperature for 1 minute, and then washed with water. Furthermore, the antirust treatment laminated body was produced by drying. The laminate subjected to the rust prevention treatment was annealed at 150 ° C. for 30 minutes in an air atmosphere.

  The laminated body subjected to the annealing treatment was subjected to electrolytic copper plating to form an electrolytic copper plating film having a thickness of 18 μm. Next, the laminate was heat-treated at 180 ° C. for 60 minutes to obtain a double-sided, two-layer multilayer printed wiring board in which a circuit was formed on the laminate with a conductor layer composed of the metal thin film layer and the electrolytic copper plating film. And the peel strength of the obtained circuit board was measured according to the said method. The results are shown in Table 2.

Comparative Example 1
(Polyimide-containing resin composition (B-2))
Except for changing the compounding amount of silica (“HPS-0500”, manufactured by Toagosei Co., Ltd.) as the inorganic filler (B2) to 113 parts and changing the compounding agent concentration to 16%, the same as in Example 1, A varnish of the polyimide-containing resin composition (B-2) was obtained. Table 1 shows the composition of the polyimide-containing resin composition (B-2).

  And, instead of the varnish of the alicyclic olefin polymer-containing resin composition (A-1), the polyimide of the polyimide-containing resin composition (B-2) obtained above was used, and a polyimide having a thickness of 3 μm. Except having obtained the film of the containing resin composition (B-2), it carried out similarly to Example 1, and obtained the film of the obtained polyimide containing resin composition (B-2), and the polyimide containing resin composition (B- A film composite with a support composed of the film of 1) was obtained and evaluated in the same manner as in Example 1.

  Next, using the obtained film composite with a support, a multilayer printed wiring board was obtained in the same manner as in Example 1, and evaluation was performed in the same manner as in Example 1. In Comparative Example 1, when the film composite with a support was bonded to both surfaces of the inner layer substrate, the bonding was performed so that the polyimide-containing resin composition (B-1) side surface was inside, Moreover, when performing electroless plating, electroless plating was performed on the surface of the polyimide-containing resin composition (B-2). That is, in the comparative example 1, the layer which consists of a polyimide containing resin composition (B-2) was used as the to-be-plated layer, and the layer which consists of a polyimide containing resin composition (B-1) was used as the contact bonding layer.

Comparative Example 2
(Alicyclic olefin polymer-containing resin composition (A-2))
Except for changing the compounding amount of silica (“Admafine SO-C1”, manufactured by Admatechs) as inorganic filler (A2) to 207 parts and changing the compounding agent concentration to 65%, the same as Example 1 And the varnish of the alicyclic olefin polymer containing resin composition (A-2) was obtained. Table 1 shows the composition of the alicyclic olefin polymer-containing resin composition (A-2).

  And instead of the varnish of the polyimide-containing resin composition (B-1), using the varnish of the alicyclic olefin polymer-containing resin composition (A-2) obtained above, a fat having a thickness of 37 μm The film of the obtained alicyclic olefin polymer containing resin composition (A-1) is carried out similarly to Example 1 except having obtained the film of the cyclic olefin polymer containing resin composition (A-2). And the film composite with a support which consists of a film of an alicyclic olefin polymer containing resin composition (A-2) was obtained, and it evaluated similarly to Example 1. FIG.

  Next, using the obtained film composite with a support, a multilayer printed wiring board was obtained in the same manner as in Example 1, and evaluation was performed in the same manner as in Example 1. In Comparative Example 2, when the film composite with a support is bonded to both surfaces of the inner layer substrate, the surface on the alicyclic olefin polymer-containing resin composition (A-2) side is on the inside. When bonding was performed and electroless plating was performed, electroless plating was performed on the surface of the alicyclic olefin polymer-containing resin composition (A-1). That is, in Comparative Example 2, a layer made of the alicyclic olefin polymer-containing resin composition (A-1) is used as a layer to be plated, and a layer made of the alicyclic olefin polymer-containing resin composition (A-2). Was used as an adhesive layer.

  As shown in Table 1 and Table 2, it has the layer which consists of an alicyclic olefin polymer containing resin composition (A-1) as a to-be-plated layer, and consists of a polyimide containing resin composition (B-1). By using an insulating adhesive film having a layer as an adhesive layer, the film had a low coefficient of linear expansion, and the resulting electrical insulating layer was able to have excellent wiring embedding properties and peel strength (Example 1). ).

On the other hand, a layer made of a polyimide-containing resin composition (B-1) having a relatively high silica content ratio, with a layer made of a polyimide-containing resin composition (B-2) having a relatively low silica content ratio as a layer to be plated. When used as an adhesive layer, the resulting film was not sufficiently low in linear expansion, and the peel strength of the electrical insulating layer was inferior (Comparative Example 1).
Moreover, the layer which consists of an alicyclic olefin polymer containing resin composition (A-1) with a comparatively little silica content rate is used as a to-be-plated layer, and an alicyclic olefin polymer containing resin with a comparatively much silica content rate is used. When the layer made of the composition (A-2) was used as an adhesive layer, the resulting film was inferior in low linear expansion (Comparative Example 2).
In addition, by comparing Example 1 and Comparative Examples 1 and 2, Example 1 has a lower linear expansion coefficient than that of either Comparative Example 1 or Comparative Example 2 while making the peel strength comparable to that of Comparative Example 2. It can be confirmed that it can be achieved.

Claims (7)

A plated layer comprising a resin composition for a plated layer containing an alicyclic olefin polymer having a polar group (A1) and an inorganic filler (A2);
An insulating adhesive film comprising: an organic solvent-soluble polyimide (B1); and an adhesive layer made of a resin composition for an adhesive layer containing an inorganic filler (B2). The resin composition for a layer to be plated further contains a curable compound (A3) having two or more functional groups capable of reacting with the polar group in the molecule;
The insulating adhesive film according to claim 1, wherein the resin composition for an adhesive layer further contains an epoxy resin (B3), a phenol compound (B4), and a curing accelerator (B5).   The insulating adhesive film according to claim 1 or 2, wherein the plated layer has a thickness of 1 to 10 µm, and the adhesive layer has a thickness of 10 to 100 µm.   The laminated body formed by laminating | stacking the insulating adhesive film in any one of Claims 1-3 on a base material.   Hardened | cured material formed by hardening | curing the insulating adhesive film in any one of Claims 1-3, or the laminated body of Claim 4.   A composite comprising a conductive layer formed on the surface of the cured product according to claim 5 by electroless plating.   An electronic material substrate comprising the cured product according to claim 5 or the composite according to claim 6 as a constituent material.