JP2013087165A - Insulating adhesive film, laminate, cured material, and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insulating adhesive film which is reduced in deformation by thermal history, has low surface roughness, and provides high peel strength when a conductor layer is formed on a surface thereof after being cured, and a laminate, a cured material and a printed wiring board obtained using the same.SOLUTION: The insulating adhesive film includes a thermosetting resin composition layer (A) and a photo-curable resin composition layer (B) which are laminated on a support in this order. The laminate, cured material and printed wiring board are obtained using the same.

Description

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

  With the pursuit of miniaturization, multi-functionality, and high-speed communication of electronic devices, there is a demand for further increases in the density of circuit boards used in electronic devices. To meet these demands for higher density, Thinning and multilayering of circuit boards have been attempted. Such a multilayer circuit board is obtained by, for example, laminating an electric insulating layer made of a resin on an inner layer substrate made of an electric insulating layer and a conductor layer formed on the surface thereof, and a conductor layer on the electric insulating layer. In addition, these electrical insulation layers and conductor layers are formed repeatedly. The electrical insulating layer and the conductor layer can be laminated in several stages as required.

As a material for constituting such an electrical insulating layer of the multilayer circuit board, a ceramic or a thermosetting resin is generally used. Among these, epoxy resins as thermosetting resins are widely used because they are excellent in terms of balance between economy and performance.

  Further, various display elements such as organic EL elements and liquid crystal display elements, semiconductor elements such as integrated circuit elements and solid-state imaging elements have a protective film for preventing deterioration and damage, and for planarizing the element surface and wiring. Functional resin layers such as a planarizing film and an interlayer insulating film for maintaining electrical insulation between the wirings arranged in layers are provided, and there is a demand for higher density and thinner thickness.

  However, the resin films forming these electrical insulating layers are liable to undergo dimensional changes due to the expansion and contraction of the resin due to thermal history, and there is a problem that the substrate, the element, etc. obtained by lamination are deformed such as warpage. When such a deformation occurs, there is a possibility that the mounting becomes difficult or the reliability is poor.

As a measure to suppress the expansion and contraction of the resin due to the thermal history, a method of adding a large amount of inorganic filler to the resin is generally effective, but it is sufficient to suppress the deformation of the obtained substrate although the thermal expansion is suppressed. In addition, when the conductor layer is formed on the resin surface by electroless plating, there is a problem that the interface roughness increases.
On the other hand, for example, in Patent Document 1, a prepreg having a glass cloth as a support for a resin insulating layer is used as a material for providing a build-up type multilayer printed wiring board having excellent warpage and dimensional accuracy during reflow. It is disclosed.

JP 11-233941 A

  However, when the inventor examined, when using the prepreg of the above-mentioned Patent Document 1, although some improvement was observed for the expansion and contraction of the resin due to the thermal history, the interface roughness between the resin surface and the conductor is large, Moreover, it became clear that there exists a problem that sufficient contact | adherence with the base-material surface etc. which are laminated | stacked cannot be obtained.

  An object of the present invention is an insulating adhesive film that is small in deformation due to heat history, has a low surface roughness, and has a high peel strength when a conductor layer is formed on the surface after curing. It is providing the laminated body, hardened | cured material, and printed wiring board which are manufactured.

  As a result of intensive studies to achieve the above object, the present inventor is laminated on a support in the order of a thermosetting resin composition layer (A) and a photocurable resin composition layer (B). The inventors have found that an insulating adhesive film can satisfy desired characteristics, and have completed the present invention.

That is, according to the present invention,
[1] An insulating adhesive film obtained by laminating a thermosetting resin composition layer (A) and a photocurable resin composition layer (B) in this order on a support,
[2] The insulating adhesive film according to [1], wherein the thermosetting resin composition contains a thermosetting resin having a weight average molecular weight of 1,000 or more,
[3] The insulating adhesive film according to [2], wherein the thermosetting resin is an alicyclic olefin polymer,
[4] The insulating property according to any one of [1] to [3], wherein the total thickness of the two layers of the thermosetting resin composition layer (A) and the photocurable resin composition layer (B) is 50 μm or less. Adhesive film,
[5] A laminate formed by laminating the surface of the photocurable resin composition layer (B) of the insulating adhesive film according to any one of [1] to [4] so as to match the substrate,
[6] A cured product obtained by curing the thermosetting resin composition layer (A) and / or the photocurable resin composition layer (B) of the laminate according to [5],
[7] In the laminate according to [5] or the cured product according to [6], after forming a via hole from the surface opposite to the substrate to the substrate surface by a laser, or further, uncured Alternatively, after curing the semi-cured thermosetting resin composition layer (A) and / or the photocurable resin composition layer (B), the surface of the cured thermosetting resin composition layer (A) and / or Or a composite formed by forming a conductor layer on the surface of the via hole,
[8] A multilayer composite comprising two or more layers comprising the composite according to [7], and
[9] A printed wiring board comprising the composite according to [7] or the multilayer composite according to [8] is provided.

  According to the present invention, an insulating adhesive film having a small deformation due to a heat history, a low surface roughness, a high peel strength when a conductor layer is formed on the surface after curing, and a film obtained using the insulating adhesive film. The laminated body, hardened | cured material, and printed wiring board which can be provided can be provided.

  The insulating adhesive film of the present invention is formed by laminating a thermosetting resin composition layer (A) and a photocurable resin composition layer (B) in this order on a support.

(Support)
Examples of the support used in the present invention include resin films and metal foils. 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 because of excellent 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 thickness of the support is not particularly limited, but is usually 1 μm to 200 μm, preferably 2 μm to 150 μm, more preferably 3 to 100 μm from the viewpoint of workability and the like. 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.

(Thermosetting resin composition)
The thermosetting resin contained in the thermosetting resin composition used in the present invention is not limited as long as the resin alone or in combination with a curing agent exhibits thermosetting and has electrical insulation. For example, epoxy resin, bismaleimide triazine resin, (meth) acrylic resin, diallyl phthalate resin, alicyclic olefin polymer, aromatic polyether polymer, benzocyclobutene polymer, cyanate ester polymer, polyimide, etc. Can be mentioned. These resins are used alone or in combination of two or more. Among these, when an electroless plating process is performed when a conductive layer is formed on the surface of a cured product obtained by curing an insulating adhesive film as an electrical insulating layer, roughening due to the pretreatment is suppressed, From the viewpoint of easily obtaining an electrical insulating layer having a low surface roughness, an alicyclic olefin polymer, an aromatic polyether polymer, a benzocyclobutene polymer, a cyanate ester polymer, and a polyimide are preferable. Polymers and aromatic polyether polymers are more preferred, and alicyclic olefin polymers are particularly preferred. In the present specification, “(meth) acryl” means methacryl or acryl.

  The thermosetting resin composition has a weight average molecular weight (Mw) of usually 1,000 or more, preferably 1,000 to 1,000,000 from the viewpoint that the insulating adhesive film is excellent in flexibility and handleability. , More preferably 3,000 to 500,000, still more preferably 5,000 to 300,000, preferably 20% by weight or more of the whole thermosetting resin contained in the composition, More preferably, it is contained in a proportion of 40% by weight or more. The upper limit of the ratio is preferably 95% by weight, more preferably 80% by weight. If the weight average molecular weight is too small, the mechanical strength of a cured product obtained by curing the insulating adhesive film is lowered, and if it is too large, the workability of forming the insulating adhesive film tends to deteriorate. The thermosetting resin may include those having a weight average molecular weight (Mw) of less than 1,000 or more than 1,000,000. In the present specification, the weight average molecular weight (Mw) is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent.

Examples of the alicyclic structure constituting the alicyclic olefin polymer suitably used as the thermosetting resin in the present invention include a cycloalkane structure and a cycloalkene structure, but from the viewpoint of mechanical strength and heat resistance. Therefore, a cycloalkane structure is preferable. 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 structure of the alicyclic olefin polymer used in the present invention is an olefin monomer unit having an alicyclic structure formed of carbon atoms, or a monomer unit that can be regarded as the monomer unit ( Hereinafter, it is collectively referred to as an alicyclic olefin monomer unit. The alicyclic olefin polymer may contain other monomer units in addition to the alicyclic olefin monomer units. The ratio of the alicyclic olefin monomer unit in the alicyclic olefin polymer is not particularly limited, but is usually 30 to 100% by weight, preferably 50 to 100% by weight, more preferably 70 to 100% by weight. . When the ratio of the alicyclic olefin monomer unit is too small, the heat resistance is inferior. The monomer unit other than the alicyclic olefin monomer unit is not particularly limited and is appropriately selected depending on the purpose.

  The alicyclic olefin polymer used in the present invention preferably has a reactive group, particularly a reactive group having reactivity with a curing agent described later, and particularly preferably has a polar group. The polar group 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 group, carboxylic acid anhydride group, sulfone An acid group, a phosphoric acid group, etc. are mentioned, Among these, a carboxyl group, a carboxylic acid anhydride group, and a phenolic hydroxyl group are preferable, and a carboxylic acid anhydride group is more preferable. The alicyclic olefin polymer may have two or more types of reactive groups. In addition, even if the reactive group is directly bonded to the atoms constituting the main chain of the polymer, it is bonded via another divalent group such as a methylene group, an oxy group, an oxycarbonyloxyalkylene group, or a phenylene group. You may do it. The content of the monomer unit having a reactive group in the alicyclic olefin polymer is not particularly limited, but is usually 4 to 60 in 100 mol% of all monomer units constituting the alicyclic olefin polymer. It is mol%, preferably 8 to 50 mol%.

When the alicyclic olefin polymer used in the present invention has a polar group as a reactive group, it 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 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 [6.2.1.13, 6.02,7] dodeca- 4-ene, 9-methyl-9-hydroxycarbonyltetracyclo [6.2.13, 6.02,7] dodec-4-ene, 9-carboxymethyl-9-hydroxycarbonyltetracyclo [6.2. 1.13, 6.02, 7] dodec-4-ene, 5-exo-6-endo-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 9-ex Alicyclic olefins having a carboxyl group such as -10-endo-dihydroxycarbonyltetracyclo [6.2.13, 6.02,7] dodec-4-ene; bicyclo [2.2.1] hept 2-ene-5,6-dicarboxylic anhydride, tetracyclo [6.2.13,6.02,7] dodec-4-ene-9,10-dicarboxylic anhydride, hexacyclo [10.2 1.13, 10.15, 8.02, 11.04,9] cycloaliphatic olefins having carboxylic anhydride groups such as heptadec-6-ene-13,14-dicarboxylic anhydride; 9-methyl -9-methoxycarbonyltetracyclo [6.2.13,6.02,7] dodec-4-ene, 5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl -5-me Cycloaliphatic olefins having a carboxylic ester group such as xyloxycarbonyl-bicyclo [2.2.1] hept-2-ene; (5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2- Ene, 9- (4-hydroxyphenyl) tetracyclo [6.2.13,6.02,7] dodec-4-ene, N- (4-hydroxyphenyl) bicyclo [2.2.1] hept- Examples include alicyclic olefins having a phenolic hydroxyl group such as 5-ene-2,3-dicarboximide, 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 [5.2.1.02,6] deca-3,8-diene (common name: dicyclo Pentadiene), tetracyclo [6.2.13,6.02,7] dodec-4-ene (common name: tetracyclododecene), 9-methyl-tetracyclo [6.2.1.13, 6. 02,7] dodec-4-ene, 9-ethyl-tetracyclo 6.2.13, 6.02, 7] dodec-4-ene, 9-methylidene-tetracyclo [6.2.13,6.02,7] dodec-4-ene, 9-ethylidene- Tetracyclo [6.2.13,6.02,7] dodec-4-ene, 9-methoxycarbonyl-tetracyclo [6.2.13,6.02,7] dodec-4-ene, 9 -Vinyl-tetracyclo [6.2.13,6.02,7] dodec-4-ene, 9-propenyl-tetracyclo [6.2.13,6.02,7] dodec-4-ene 9-phenyl-tetracyclo [6.2.13, 6.02,7] dodec-4-ene, tetracyclo [9.2.1.02,10.03,8] tetradec-3,5,7 , 12-tetraene, cyclopentene, cyclopentadiene, etc. It is. 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.

  A conventionally known metathesis polymerization catalyst can be used as a polymerization catalyst when the alicyclic olefin polymer used in the present invention is obtained by a ring-opening polymerization method. 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 to 10 mole parts with respect to 100 mole parts of the monomer used for polymerization, according to the target molecular weight.

  As a polymerization catalyst for obtaining the alicyclic olefin polymer used in the present invention 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.

  In the case of using a hydrogenated ring-opening polymer as the alicyclic olefin polymer used in the present invention, hydrogenation 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, and the production efficiency tends to be inferior.

  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 is usually 50 mol% or more, preferably 70 mol% or more, out of 100 mol% of the carbon-carbon double bond of the main chain in the polymer. Preferably 80 mol% or more, particularly preferably 90 mol% 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 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, but the thermosetting resin composition may be used. 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.

  In the thermosetting resin composition used in the present invention, the content of the alicyclic olefin polymer is the content of the alicyclic olefin polymer when the thermosetting resin composition layer (A) is used. The range is preferably 30 to 90% by weight, more preferably 40 to 80% by weight, and still more preferably 50 to 70% by weight. When the content of the alicyclic olefin polymer in the thermosetting resin composition layer (A) is in the above range, the surface of the resulting cured product is roughened as a pretreatment for electroless plating. It is preferable that the surface roughness can be kept small and a high peel strength is obtained when a conductor layer is formed on the surface.

(Curing agent)
The hardening | curing agent used by this invention is not specifically limited, The hardening | curing agent mix | blended with the resin composition for general electrical insulation film formation can be used. In a preferred embodiment of the present invention, it is preferable to use a compound having two or more functional groups capable of reacting with the reactive group of the alicyclic olefin polymer to form a bond.

  For example, as an alicyclic olefin polymer, a curing agent suitably used when using an alicyclic olefin polymer having a polar group, in particular, a carboxyl group, a carboxylic acid anhydride group, or a phenolic hydroxyl group, may be a polyvalent olefin polymer. Examples thereof include an epoxy compound, a polyvalent isocyanate compound, a polyvalent amine compound, a polyvalent hydrazide compound, an aziridine compound, a basic metal oxide, and an organic metal halide. These may be used alone or in combination of two or more. Among these, a polyvalent epoxy compound is preferable from the viewpoint that the reactivity with the reactive group of the alicyclic olefin polymer is moderate and the handling of the thermosetting resin composition becomes easy. In the present specification, “multivalent” and “polyfunctional” are synonymous.

  Examples of the polyvalent epoxy compound include a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, a polyphenol type epoxy compound such as a cresol type epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, and a hydrogenated bisphenol A type epoxy. Bisphenol glycidyl ether type epoxy compounds such as compounds; alicyclic epoxy compounds such as epoxy compounds having an alicyclic olefin structure, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, epoxy compounds having a fluorene structure, isocyanurate type epoxies Compounds having two or more epoxy groups in the molecule, such as compounds, polyvalent epoxy compounds such as phosphorus-containing epoxy compounds; It may be used one kind alone or in a combination of two or more kinds. Among these, the insulating adhesive film of the present invention and the bisphenol A type epoxy from the point that the mechanical properties of the laminates, cured products and composites obtained using the same can be improved. A compound, a polyphenol type epoxy compound, and an epoxy compound having an alicyclic olefin structure or a fluorene structure are preferred. Furthermore, an epoxy compound having an alicyclic olefin structure is particularly preferable from the viewpoint of improving the resin fluidity of the thermosetting resin composition during heating. 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 DIC,“ Epicron ”is a registered trademark), and the like. As a polyphenol type epoxy compound, a brand name "1032H60, XY-4000" (above, Mitsubishi Chemical Corporation make) etc. are mentioned, for example. As an epoxy compound having an alicyclic olefin 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 HP7200HHH” (above, manufactured by DIC Corporation) ); Trade name “Tactix 558” (manufactured by Huntsman Advanced Material); trade names “XD-1000-1L, XD-1000-2L” (manufactured by Nippon Kayaku Co., Ltd.)] and epoxy resins having a fluorene skeleton [For example, the product names “ONCOAT EX-1010, ONCOAT EX-1011, ONCOAT EX-1012, ONCOAT EX-1020, ONCOAT EX-1030, ONCOAT EX-1040, ONCOAT E -1050, ONCOAT EX-1051 "(Nagase Sangyo Co., Ltd.," ONCOAT "is a registered trademark); trade name" Ogsol PG-100, Ogsol EG-200, Ogsol EG-250) "(Osaka Gas) Chemical Company, “Ogsol” is a registered trademark)] and the like.

  As the polyvalent isocyanate compound, diisocyanates and triisocyanates having 6 to 24 carbon atoms are preferable. Examples of diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, etc. Is mentioned. Examples of triisocyanates include 1,3,6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate, bicycloheptane triisocyanate, etc., and these are used alone. You may use 2 or more types together.

  Examples of the polyvalent amine compound include aliphatic polyamine compounds having 4 to 30 carbon atoms having two or more amino groups, aromatic polyamine compounds, and the like, and non-conjugated nitrogen-carbon such as guanidine compounds. Those having a double bond are not included. Examples of the aliphatic polyvalent amine compound include hexamethylene diamine, N, N′-dicinnamylidene-1,6-hexane diamine, and the like. Examples of aromatic polyvalent amine compounds include 4,4′-methylenedianiline, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4 ′-(m-phenylenediisopropylidene) dianiline, 4,4 ′-( p-phenylenediisopropylidene) dianiline, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 1,3,5-benzenetriamine and the like. These may be used alone or in combination of two or more.

  Examples of polyhydric hydrazide compounds include isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthalenedicarboxylic acid dihydrazide, maleic acid dihydrazide, itaconic acid dihydrazide, trimellitic acid dihydrazide, 1,3,5-benzenetricarboxylic acid dihydrazide, Examples include pyromellitic acid dihydrazide. These may be used alone or in combination of two or more.

  Examples of the aziridine compounds include tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, tris [1- (2-methyl) aziridinyl] phosphinoxide, hexa [1- (2-methyl) aziridinyl. ] Triphosphatriazine and the like. These may be used alone or in combination of two or more.

  Among the curing agents described above, a polyvalent epoxy compound is preferred from the viewpoint that the reactivity with the reactive group of the alicyclic olefin polymer is moderate and the handling of the thermosetting resin composition is easy, glycidyl ether Type epoxy compounds and alicyclic polyvalent epoxy compounds are particularly preferably used.

  The blending amount of the curing agent in the thermosetting resin composition used in the present invention is such that the content of the curing agent in the thermosetting resin composition layer (A) is preferably 5 to 50% by weight, The range is more preferably 10 to 40% by weight, and still more preferably 15 to 30% by weight. By making the content rate of the hardening | curing agent in a thermosetting resin composition layer (A) into the said range, since the mechanical strength and electrical property of the obtained hardened | cured material can be made favorable, it is preferable.

In addition to the thermosetting resin (preferably alicyclic olefin polymer) and the curing agent, the thermosetting resin composition may contain a curing accelerator, a curing aid, and the like. As a hardening accelerator, the well-known hardening accelerator used for insulating layer formation can be used. When a polyvalent epoxy compound is used as the curing agent, a tertiary amine compound (excluding a compound having a 2,2,6,6-tetramethylpiperidyl group having a tertiary amine at the 4-position) or trifluoride is used. Boron complex compounds and the like are suitably used as the curing accelerator.
A hardening accelerator can be used individually by 1 type or in combination of 2 or more types. The blending amount of the curing accelerator may be appropriately selected according to the purpose of use. For example, it is usually 0.001 to 30 parts by weight, preferably 100 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer having a polar group. Is 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight.

As the curing aid, a known curing aid used for forming the insulating layer can be used. Curing aids include oxime and nitroso curing aids such as quinonedioxime, benzoquinonedioxime, and p-nitrosophenol; maleimide curing aids such as N, N-m-phenylenebismaleimide; diallyl phthalate, triary Allyl curing aids such as lucyanurate and triallyl isocyanurate; Methacrylate curing aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; Vinyl curing aids such as vinyltoluene, ethylvinylbenzene and divinylbenzene; Etc. These curing aids can be used singly or in combination of two or more.
The amount of the curing aid is usually in the range of 1 to 100 parts by weight, preferably 10 to 50 parts by weight with respect to 100 parts by weight of the curing agent.

  If necessary, the thermosetting resin composition can be blended with a rubbery polymer or an arbitrary thermoplastic resin. By blending them in the thermosetting resin composition, the flexibility of the resulting cured product is improved, which is preferable.

The rubbery polymer is a polymer having a glass transition temperature of room temperature (25 ° C.) or less, and includes general rubbery polymers and thermoplastic elastomers.
A rubber polymer and a thermoplastic resin can be used individually by 1 type or in combination of 2 or more types, respectively.
Although these compounding quantities are suitably selected in the range which does not impair the objective of this invention, it is preferable to set it as 30 weight part or less with respect to 100 weight part of alicyclic olefin polymers, for example.

A hindered phenol compound and a hindered amine compound can be mix | blended with a thermosetting resin composition. By blending these, the mechanical strength of the resulting cured product is improved, which is preferable.
Although the compounding quantity of a hindered phenol compound is not specifically limited, For example, it is 0.04-20 weight part normally with respect to 100 weight part of alicyclic olefin polymers, Preferably it is 0.4-10 weight part. Preferably it is the range of 0.5-5 weight part.
Although the compounding quantity of a hindered amine compound is not specifically limited, For example, it is 0.002-30 weight part normally with respect to 100 weight part of alicyclic olefin polymers, Preferably it is 0.02-10 weight part, More preferably It is the range of 0.025-5 weight part.
Moreover, it is preferable to use a hindered phenol compound and a hindered amine compound in combination. By using these together, for example, when electroless plating is performed on the resulting cured product, the surface of the cured product is efficiently brought into contact with an oxidizing agent aqueous solution and roughened with a low surface roughness. It can be kept and is preferred.
Since such an effect is easily obtained, the blending ratio of the hindered phenol compound and the hindered amine compound is a weight ratio of “hindered phenol compound / hindered amine compound”, preferably 1 / 0.05 to 1/25. Yes, more preferably 1 / 0.1 to 1/10, still more preferably 1 / 0.25 to 1/5.

A flame retardant can be mix | blended with a thermosetting resin composition. By mix | blending a flame retardant, the flame retardance of the hardened | cured material obtained improves.
Examples of the flame retardant include a halogen flame retardant and a phosphate ester flame retardant. The blending amount of the flame retardant is, for example, preferably 100 parts by weight or less, more preferably 60 parts by weight or less with respect to 100 parts by weight of the alicyclic olefin polymer.

  The thermosetting resin composition can be blended with a polymer or an inorganic filler that is soluble in the oxidizing agent aqueous solution. By blending such a polymer or inorganic filler, for example, when electroless plating is performed on the resulting cured product, when the surface of the cured product is brought into contact with an oxidizing agent aqueous solution and roughened, Since the coalescence and inorganic filler are selectively dissolved and dropped, the surface roughness of the surface can be controlled.

Polymers soluble in the oxidizer aqueous solution include liquid epoxy resins, polyester resins, bismaleimide-triazine resins, silicone resins, polymethylmethacrylate resins, natural rubber, styrene rubber, isoprene rubber, butadiene rubber, and nitrile rubber. Examples thereof include rubber, ethylene-propylene rubber, urethane rubber, butyl rubber, silicone rubber, fluorine rubber, norbornene rubber, and ether rubber.
The blending amount of these polymers is usually 1 to 60 parts by weight, preferably 3 to 50 parts by weight, and more preferably 4 to 40 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer. .

  Inorganic fillers include calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, hydrated alumina, magnesium hydroxide, aluminum hydroxide, barium sulfate. , Silica, talc, clay and the like. Among these, calcium carbonate and silica are preferable, and silica is particularly preferable because fine particles can be easily obtained and dropout with an oxidizing agent aqueous solution can be easily controlled. These inorganic fillers may be treated with a silane coupling agent or an organic acid such as stearic acid.

  The inorganic filler is preferably non-conductive which does not deteriorate the dielectric properties of the resulting cured product. The shape of the inorganic filler is not particularly limited, and may be spherical, fibrous, plate-like, or the like, but in order to obtain a fine rough surface shape, a fine spherical shape is preferable. The average particle size of the inorganic filler is usually 0.008 μm or more and less than 2 μm, preferably 0.01 μm or more and less than 1.5 μm, particularly preferably 0.02 μm or more and less than 1 μm. The blending amount of the inorganic filler is appropriately selected according to the required degree of adhesion, but is preferably 1 to 40% by weight, more preferably 2 to 2% in the thermosetting resin composition layer (A). It is preferable that the range be 30% by weight, more preferably 3 to 25% by weight.

  In addition, the thermosetting resin composition further includes a heat stabilizer, a weather stabilizer, an anti-aging agent, an ultraviolet absorber (laser processability improver), a leveling agent, an antistatic agent, a slip agent, if necessary. You may mix | blend arbitrary components, such as an antiblocking agent, an antifogging agent, a lubricant, a dye, a natural oil, a synthetic oil, a wax, an emulsion, a magnetic body, a dielectric property modifier, 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.

(Photocurable resin composition)
The photocurable resin composition used in the present invention is not limited as long as it exhibits a curing reaction upon irradiation with light, but usually contains a photocurable compound and a photopolymerization initiator.

(Photocurable compound)
As the photocurable compound, a photocationic curable compound, a photoradical curable compound, or a combination of these compounds can be used. Among these, a photocation curable compound is preferable because it is not inhibited by oxygen.

Examples of the photocationic curable compound include epoxy compounds, vinyl ether compounds, oxetane compounds, carbonate compounds, dithiocarbonate compounds, and the like. Many functional groups exhibiting photocationic curable properties are known, but epoxy groups, vinyl ether groups, oxetanyl groups, and the like are widely used as particularly practical products.

The epoxy compound is preferably a polyvalent epoxy compound having two or more epoxy groups in one molecule, and examples thereof include an aliphatic polyvalent epoxy compound, an aromatic polyvalent epoxy compound, and an alicyclic polyvalent epoxy compound. .

The aliphatic polyvalent epoxy compound is a polyvalent epoxy compound that does not contain an aromatic ring and / or an alicyclic epoxy structure, and specifically includes neopentyl glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diester. Glycidyl ether, cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hepta Examples thereof include glycidyl ether and sorbitol hexaglycidyl ether.

The aromatic polyvalent epoxy compound is a polyvalent epoxy compound that does not contain an alicyclic epoxy structure but contains an aromatic ring, and specifically includes a biphenyl type epoxy compound, a bisphenol A type epoxy compound, and a bisphenol F type epoxy. Compound, bisphenol AD type epoxy compound, stilbene type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, triphenolmethane type epoxy compound, alkyl-modified triphenolmethane type epoxy compound, phenol aralkyl type epoxy compound having phenylene skeleton , Phenol aralkyl type epoxy compounds having a biphenylene skeleton, naphthalene skeleton glycidyl ether type epoxy compounds, naphthol aralkyl type epoxy compounds having a phenylene skeleton Naphthol aralkyl type epoxy compound having biphenylene skeleton, dicyclopentadiene modified phenol type epoxy compound, epoxy compound having skeleton of anthracene or hydrogenated product thereof, hydroquinone type epoxy compound, phenolic hydroxyl group-containing aromatics, aldehydes and alkoxy groups Or the epoxy compound etc. which glycidyl-etherified the phenol resin obtained by co-condensing with aromatics containing a thioalkyl group by epichlorohydrin etc. are mentioned.

In the alicyclic epoxy compound, one oxygen atom is bonded to two carbon atoms (usually carbon atoms adjacent to each other) of the cyclically bonded carbon atoms forming the aliphatic ring of the alicyclic compound. A compound containing an epoxy ring structure in a state, specifically, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (for example, Celoxide (registered trademark) 2021P: manufactured by Daicel Chemical Industries), Ε-caprolactone adduct of epoxidized 3-cyclohexene-1,2-dicarboxylic acid bis-3-cyclohexenyl methyl ester (for example, Epolide (registered trademark) GT301, manufactured by Daicel Chemical Industries), epoxidized butanetetracarboxylic acid tetrakis- Ε-caprolactone adduct of 3-cyclohexenyl methyl ester (for example, epoxide Lead GT401: manufactured by Daicel Chemical Industries, Ltd.), 1,2-epoxy-4- (2-oxiranyl) cyclohexene adduct of 2,2-bis (hydroxymethyl) -1-butanol (for example, EHPE3150: manufactured by Daicel Chemical Industries, Ltd.) And the like, and monofunctional alicyclic epoxy compounds such as 4-vinylepoxycyclohexane (for example, Celoxide 2000: manufactured by Daicel Chemical Industries, Ltd.).
Moreover, the hybrid compound which has an epoxy group and a (meth) acryl group can be used. Examples thereof include 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl methacrylate, vinyl glycidyl ether and the like. These can be used alone or in combination of two or more.

The vinyl ether compound is not particularly limited as long as it is a compound having a vinyl ether structure. Commercially available products include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 2-hydroxybutyl vinyl ether, triethylene glycol divinyl ether, and the like. Moreover, the vinyl ether compound containing cyclic ether groups, such as an epoxy group and / or an oxetane group, can be used. Examples thereof include oxynorbornene divinyl ether and 3,3-dimethanol oxetane divinyl ether. These can be used alone or in combination of two or more.

The oxetane compound is not particularly limited as long as it is a compound having an oxetanyl group. Commercially available products include polyfunctional oxetane compounds such as di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl). And monofunctional oxetane compounds such as oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, oxetanylsilsesquioxane, and phenol novolac oxetane. Alternatively, a hybrid compound (1-ethyl-3-oxetanylmethyl (meth) acrylate) having an oxetanyl group and a (meth) acryl group can be used. These can be used alone or in combination of two or more.

Each of the carbonate compound and the dithiocarbonate compound is not particularly limited as long as it is a compound having a carbonate group or a dithiocarbonate group in the molecule.

In addition, the photocurable resin composition in the present invention can control the curing shrinkage by using a curing expandable compound as one component as a photocationic curable compound, and for example, can produce an excellent pattern shape. Become. Examples of the curable expandable compound include epoxy compounds and carbonate compounds.

  As the photocationic curable compound, a polyvalent epoxy compound or a polyvalent oxetane compound is preferable, and an alicyclic polyvalent epoxy compound is more preferable because of excellent reactivity with light and small deformation after curing. In addition, a photocationic curable compound may be used individually by 1 type, respectively, and may use 2 or more types together.

  The compounding amount of the photocurable compound in the photocurable resin composition used in the present invention is usually 10 to 90% by weight, preferably 20 to 80% by weight, more preferably in the photocurable resin composition layer (B). Is in the range of 30 to 70% by weight. When there are too few compounding quantities of a photocurable compound, hardening will become inadequate and there exists a possibility that the mechanical strength of the hardened | cured material obtained may deteriorate. On the other hand, when there is too much compounding quantity of a photocurable compound, there exists a possibility that it may become weak.

(Photopolymerization initiator)
The photopolymerization initiator used in the photocurable resin composition used in the present invention is a photoacid generator that generates Bronsted acid or Lewis acid in response to light, or generates radicals in response to light. Photo radical generators such as benzoin / benzoin alkyl ethers, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, etc. are preferable, and photo acid generators are preferred.

  Examples of the photoacid generator used in the present invention include onium salts, halogenated organic compounds, α, α-bis (sulfonyl) diazomethane compounds, α-carbonyl-α-sulfonyl-diazomethane compounds, sulfone compounds, and organic acid esters. It is selected from compounds, organic acid amide compounds, organic acid imide compounds and the like.

  Specific examples of onium salts include sulfonium salts, diazonium salts, ammonium salts, iodonium salts, phosphonium salts, arsonium salts, oxonium salts, etc. having alkyl groups, alkenyl groups, aralkyl groups, aryl groups, and heterocyclic groups. In particular, sulfonium salts are preferred. The counter anion of these onium salts is not particularly limited, and examples thereof include antimonic acid, boric acid, arsenic acid, phosphoric acid, sulfonic acid, carboxylic acid, and halides thereof, and antimonic acid is particularly preferable. Specific examples include triarylsulfonium hexafluoroantimonate.

Examples of the photoacid generator used in the present invention include arylsulfonium salt derivatives [e.g., Syracure UVI-6990, Syracure UVI-6990, Syracure UVI-6974 ("Syracure" is a registered trademark) manufactured by Dow Chemical Co., Ltd .; Adeka optomer SP-150, Adeka optomer SP-152, Adeka optomer SP-170, Adeka optomer SP-172 ("Adeka optomer" is a registered trademark); CPI-100P, CPI- 101A, CPI-200K, CPI-210S], allyl iodonium salt derivatives (for example, PI-2074 manufactured by Rhodia), allene-ion complex derivatives (for example, Irgacure (registered trademark) 261 manufactured by BASF), diazonium salt derivatives Triazine series started , And acid generator such as other halides.

  The compounding amount of the photoacid generator in the photocurable resin composition used in the present invention is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the photocurable compound. More preferably, it is 1 to 4 parts by weight. If the amount of the photoacid generator is too small, curing may be insufficient. On the other hand, if the amount is too large, the reliability of the resulting composite or the like may be reduced.

  Moreover, it is preferable to mix | blend an inorganic filler with the photocurable resin composition used for this invention in addition to the photocurable compound and photoacid generator which were mentioned above. The inorganic filler is not particularly limited as long as it is generally used industrially. For example, calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, Examples thereof include zirconium silicate, hydrated alumina, magnesium hydroxide, aluminum hydroxide, barium sulfate, silica, talc, and clay. By blending the inorganic filler, the linear expansion of the obtained cured product can be lowered.

  Among the inorganic fillers described above, silica is preferable from the viewpoint of excellent heat resistance, low water absorption, dielectric properties, low impurity properties, heat dissipation, and the like. In particular, silica obtained by treating the surface with a silane coupling agent. Is more preferable. In addition, it does not specifically limit as a silane coupling agent, A well-known thing can be used.

  The average particle diameter of the inorganic filler used in the photocurable resin composition is preferably 0.05 to 1.5 μm, more preferably 0.1 to 1 μm. If the average particle size of the inorganic filler is too small, when laminating the insulating adhesive film of the present invention on the substrate, the melt viscosity may be high and the embedding flatness may not be ensured. When the wiring pattern is embedded, a short circuit between the wirings may be caused. In the present specification, the average particle size can be measured by a particle size distribution measuring device.

  The blending amount of the inorganic filler in the photocurable resin composition of the present invention is usually 30 to 90% by weight, preferably 40 to 80% by weight, more preferably in the photocurable resin composition layer (B). Is in the range of 50 to 70% by weight. When the blending amount of the inorganic filler is too small, it is difficult to obtain the effect of blending the inorganic filler. On the other hand, when the blending amount is too large, the insulating adhesive film and the cured product may be brittle.

Moreover, you may mix | blend a photosensitizer with the photocurable resin composition used for this invention as needed. Examples of the photosensitizer include thioxanthone, thioxanthone derivatives, anthraquinone, anthraquinone derivatives, anthracene, anthracene derivatives, perylene, perylene derivatives, benzophenone, and benzoin isopropyl ether. When the photosensitizer is contained in an amount of 0.1 to 20 parts by weight when the photocurable compound is taken as 100 parts by weight, the effect increases and is effective. By using a photosensitizer, photocurability and photoreactivity can be improved, and adhesive strength can be improved.
Moreover, you may mix | blend a solvent with the photocurable resin composition used for this invention as needed. By mix | blending a solvent, the moldability at the time of shape | molding to a film form can be improved. Note that the solvent is volatilized and removed by heating or the like when the photocurable resin composition is formed into a film and formed into an insulating adhesive film.

  The solvent preferably has a boiling point of 30 to 250 ° C, more preferably 50 to 200 ° C, from the viewpoint of volatilization and removal by heating or the like when forming into a film. Specific examples of such solvents include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, trimethylbenzene, and anisole; aliphatics such as n-pentane, n-hexane, n-heptane, methyl ethyl ketone, and methyl isobutyl ketone. Hydrocarbons; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclopentanone, and cyclohexanone; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene.

  The mixing ratio of the solvent in the photocurable resin composition used in the present invention is preferably 90% by weight or less, more preferably 70% by weight or less, and further preferably 50% by weight or less.

  Furthermore, the photocurable resin composition used in the present invention can be blended with a rubbery polymer or an arbitrary thermoplastic resin as necessary. The rubbery polymer is a polymer having a glass transition temperature of room temperature (25 ° C.) or lower, and includes general rubbery polymers and thermoplastic elastomers. The rubbery polymer and the thermoplastic resin can be blended as long as the effects of the present invention are not inhibited.

  The photocurable resin composition used in the present invention is for the purpose of improving the flame retardancy when used as a cured product, for example, for forming a general electric insulation film such as a halogen flame retardant or a phosphate ester flame retardant. You may mix | blend the flame retardant mix | blended with this curable resin composition. When the flame retardant is blended in the photocurable resin composition, the 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 photocurable compound.

  In addition, the photo-curable resin composition used in the present invention may further include a flame retardant aid, a heat stabilizer, a weather stabilizer, an anti-aging agent, a leveling agent, an antistatic agent, a slip agent, and an anti-blocking as necessary. Optional components such as an agent, an antifogging agent, a lubricant, a dye, a natural oil, a synthetic oil, a wax, an emulsion, a magnetic substance, a dielectric property adjusting agent, and a toughening agent may be blended. 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.

(Insulating adhesive film)
The insulating adhesive film of the present invention comprises a layer (A) composed of the above-mentioned thermosetting resin composition and a layer (B) composed of the above-mentioned photocurable resin composition in this order on the above-mentioned support. And are formed into a sheet shape or a film shape.

  The thermosetting resin composition and the photocurable resin composition used in the present invention can be produced by appropriately mixing the above components by a known method. In the case of using a solvent, for example, a composition in which a part of each of the above components is dissolved or dispersed in a solvent is prepared, and the remaining components can be mixed with the composition to produce.

  The insulating adhesive film of the present invention is prepared by, for example, the following two methods: (1) Applying, spreading or casting the above-described thermosetting resin composition on a support, drying as required, On top of that, a method for producing the above-mentioned photo-curable resin composition by further applying, dispersing or casting, and drying as necessary; (2) the above-mentioned thermosetting resin composition on the support The molded body formed by coating, spreading or casting and drying as necessary is formed into a sheet or film, and the above-mentioned photocurable resin composition is coated, spread or flowed on the support. It can be produced by a method of producing by laminating, drying as necessary, forming a sheet or film, and laminating and integrating these formed bodies. 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 thermosetting resin composition is applied, spread or cast on a support, and the applied, spread or cast thermosetting resin composition is a photocurable resin composition. When a product is applied, spread or cast, or in the above-described production method (2), the thermosetting resin composition and the photocurable resin composition are formed into a sheet or film to form a thermosetting resin layer. When forming a molded article for a product and a molded article for a photocurable resin layer, an organic solvent is added to the thermosetting resin composition or the photocurable resin composition as necessary, and then applied to the support and spread. Or it is preferable to cast.

For the thermosetting resin composition and the photocurable resin composition in the production method (1) described above, or for the thermosetting resin layer molded body and the photocurable resin in the production method (2) above. Although the thickness of a molded object is not specifically limited, When it is set as an insulating adhesive film, the thickness of the thermosetting resin composition layer (A) becomes like this. Preferably it is 1-10 micrometers, More preferably, it is 1-8 micrometers, More preferably The thickness of the photo-curable resin composition layer (B) is preferably 3 to 45 μm, more preferably 5 to 35 μm, and still more preferably 10 to 25 μm. If the thickness of the thermosetting resin composition layer (A) is too thin, the formability of the conductor layer is 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 thermosetting resin composition layer (A) is too thick, the linear expansion of a cured product obtained by curing the insulating adhesive film may be increased. On the other hand, if the thickness of the photocurable resin composition layer (B) is too thin, the wiring embedding property of the insulating adhesive film may be lowered, whereas the thickness of the photocurable resin composition layer (B). If the thickness is too thick, the resulting cured product may be greatly deformed.
In addition, with respect to the insulating adhesive film laminated | stacked on the base material, a thermosetting resin composition layer (A) and light are used from a viewpoint of hardening the whole photocurable resin composition layer (B) with active radiation uniformly. The total thickness of the two layers of the curable resin composition layer (B) is preferably 50 μm or less.

  Examples of the method for applying the thermosetting resin composition and the photocurable resin composition include dip coating, roll coating, curtain coating, die coating, slit coating, and gravure coating.

  Further, in the production method of (1) described above, after the thermosetting resin composition is applied, spread or cast on the support, or the photocurable resin composition is applied on the thermosetting resin composition, After spraying or casting, or after applying the thermosetting resin composition and the photocurable resin composition on the support in the production method (2) described above, drying may be performed as necessary. Good. The drying temperature is preferably a temperature at which the thermosetting resin composition and the photocurable resin composition 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 photocurable resin composition layer (B) which comprises an insulating adhesive film is an uncured or semi-hardened state. By making this layer into an uncured or semi-cured state, the photocurable resin composition layer (B) constituting the insulating adhesive film of the present invention can be made highly adhesive.

  And the insulating adhesive film of this invention obtained in this way is used in the state made to adhere on a support body, or peeling from a support body.

(Laminate)
The laminate of the present invention is formed by laminating so that the surface of the above-mentioned photocurable resin composition layer (B) of the insulating adhesive film of the present invention is matched with the substrate. The laminate of the present invention may be at least formed by laminating the above-described insulating adhesive film of the present invention, but the above-described insulating property of the present invention using a substrate having a conductor layer on the surface as a base material. What laminated | stacked an adhesive film is preferable. In this case, the insulating adhesive film of the present invention is configured to be laminated with the substrate via the photocurable resin composition layer (B). That is, in the laminated body of the present invention, the surface is a thermosetting resin among the thermosetting resin composition layer (A) and the photocurable resin composition layer (B) of the insulating adhesive film of the present invention. It will be formed by the composition layer (A).

  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 is a resin composition containing a known electrically insulating material (for example, alicyclic olefin polymer, epoxy resin, bismaleimide triazine resin, (meth) acrylic resin, diallyl phthalate resin, polyphenylene ether, glass, etc.). It is formed by curing a product. 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 may be pretreated on the surface of the conductor layer in order to improve adhesion to the electrical insulating layer formed by the insulating adhesive film of the present invention. preferable. 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, reduction with sodium borohydride or formalin, etc., method of depositing and roughening the plating on the conductor layer, and elution of copper grain boundaries by contacting the conductor layer with organic acid and roughening 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 be produced, for example, by heat-pressing the above-described 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 and applied so that the photocurable resin composition layer (B) constituting the insulating adhesive film is in contact with the conductor layer of the substrate described above. Examples thereof include a method of thermocompression bonding (lamination) using a pressurizer such as a pressure laminator, a press, a vacuum laminator, a vacuum press, and a roll laminator. 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. According to the above thermocompression bonding operation, the insulating adhesive film of the present invention can be laminated on the substrate in an uncured state, a semi-cured state, or a cured state by appropriately adjusting temperature conditions and the like. In addition, when a support body transmits light like a resin film, the laminated body is used in a state where the support body is attached or peeled off from the support body. On the other hand, when the support does not transmit light like a metal foil, it is peeled off from the support and used.

(Cured product)

The cured product of the present invention is obtained by curing the thermosetting resin composition layer (A) and / or the photocurable resin composition layer (B) of the laminate of the present invention.
The thermosetting resin composition layer (A) can be cured, for example, by appropriately heating the layer within the temperature and time range of the thermocompression bonding operation mentioned in the production of the laminate of the present invention. .
On the other hand, the photocurable resin composition layer (B) can be cured by, for example, irradiating the layer with actinic radiation, thereby activating the photoacid generator and causing a curing reaction. .

  The actinic radiation is not particularly limited as long as it can activate the photoacid generator and cause a curing reaction. Specifically, ultraviolet rays, ultraviolet rays having a single wavelength such as g-line or i-line, light rays such as KrF excimer laser light and ArF excimer laser light; particle beams such as electron beams; When light is used as the active radiation, it may be single wavelength light or mixed wavelength light.

The irradiation condition of the active radiation is appropriately selected according to the active radiation to be used. For example, when using a light beam having a wavelength of 200 to 450 nm, the irradiation amount is usually 10 to 10,000 mJ / cm ² , preferably 50. It is in the range of ˜5,000 mJ / cm ² and is determined according to the irradiation time and illuminance. In addition, the obtained hardened | cured material is used in the state which peeled the support body, when the support body has adhered to the surface.
After irradiation with actinic radiation, the obtained cured product may be further heated as desired. Examples of the heating method include a method of heating the obtained cured product in a hot plate or an oven. The temperature is usually in the range of 100 to 300 ° C, preferably 120 to 200 ° C.

  In the production of the cured product of the present invention, from the viewpoint of suppressing the deformation of the cured product due to thermal history, when a laminate is produced by laminating an insulating adhesive film on a substrate by thermocompression bonding, the thermosetting resin composition is used at that stage After the physical layer (A) is in a semi-cured state and then irradiated with actinic radiation to complete the curing of the photocurable resin composition layer (B), it is further heated to be a semi-cured thermosetting resin composition It is preferable to harden the physical layer (A).

(Complex)
In the laminate or cured product of the present invention, the composite of the present invention is a thermoset of uncured or semi-cured after forming a via hole from the surface opposite to the substrate to the substrate surface by a laser, or then further. After the curable resin composition layer (A) and / or the photocurable resin composition layer (B) is cured, a conductor layer is formed on the surface of the cured photocurable resin composition layer (B) and / or the surface of the via hole. Is formed. Since the insulating adhesive film of this invention used for manufacture of the said laminated body or hardened | cured material is a resin film which does not contain a fiber material, it can make thin the composite obtained. In addition, the via hole formability is also excellent, and the electrical properties of the resulting composite (for example, the insulating property of the conductor wiring between the insulating layers and the insulating property between the via hole and the via hole) are well maintained.
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. In the multilayer circuit board, the cured insulating adhesive film of the present invention forms an electrical insulating layer.

  First, as described above, the insulating adhesive film of the present invention is laminated using a substrate (inner layer substrate) having a conductor layer on the surface as a base material, and the thermosetting resin composition layer (A) and / or photocurable resin is laminated. In the cured product obtained by curing the composition layer (B), a via hole penetrating from the surface opposite to the substrate to the substrate surface is formed. The via hole is formed in the multilayer circuit board to electrically connect the conductor layers constituting the board. The via hole can be formed by physical treatment such as drilling, laser, plasma etching, etc., but in the present invention, a finer via hole can be formed without degrading the characteristics of the electrical insulating layer. A via hole is formed using a carbon dioxide laser, excimer laser, UV-YAG laser, or the like. Here, when the thermosetting resin composition layer (A) and / or the photocurable resin composition layer (B) is still uncured or semi-cured, the cured product is further heated, Harden. In addition, in this specification, semi-curing means the state hardened to the middle to such an extent that it can harden further, if it heats or actinic radiation irradiation.

Next, the surface of the cured electrically insulating layer, specifically, the surface of the cured thermosetting resin composition layer (A) is roughened. The roughening treatment is performed in order to improve the adhesion with the conductor 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 roughening processing method, The method etc. which contact an electrically insulating layer surface (namely, the surface of the thermosetting resin composition layer (A) after hardening) 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 roughening treatment is washed with water in order to remove the oxidizing compound after the 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.

After roughening the surface of the electrically insulating layer of the cured product as described above, the surface of the electrically insulating layer (that is, the surface of the cured thermosetting resin composition layer (A)) and / or the via hole A conductor layer is formed on the surface (inner wall surface).
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 (that is, the cured thermosetting resin composition layer (A It is common to deposit catalyst nuclei such as silver, palladium, zinc, cobalt on)). 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.

(Multilayer composite)
The multilayer composite of the present invention comprises two or more layers comprising the composite of the present invention. In such a multilayer composite, the composite obtained as described above is used as a base material for producing the above-mentioned cured product. For example, the insulating adhesive film of the present invention is heat-pressed and cured on this base material. By forming an electrically insulating layer and further forming a conductor layer on the electrically insulating layer according to the above-described method, and repeating these, it is possible to manufacture by further multilayering.

  The composite of the present invention (including a multilayer composite; hereinafter the same) has an electrical insulating layer made of the insulating adhesive film of the present invention, and the electrical insulating layer has little deformation due to thermal history, Since the surface roughness is low and the peel strength is high, the conductor layer is formed on the electrical insulating layer, the formed conductor layer is patterned, and when the fine wiring is formed, the conductor layer is patterned. In addition to being able to be performed satisfactorily, there are few defects in the mounting process and excellent reliability.

(Printed wiring board)
The printed wiring board of the present invention includes the above-described composite of the present invention as a constituent material. Such a printed wiring board of the present invention includes a mobile phone, a PHS, a notebook personal computer, a PDA (personal digital assistant), a mobile video phone, a personal computer, a supercomputer, a server, a router, a liquid crystal projector, an engineering workstation (EWS), It can be suitably used for various electronic devices such as pagers, word processors, televisions, viewfinder type or monitor direct view type video tape recorders, electronic notebooks, electronic desk calculators, car navigation devices, POS terminals, and devices equipped with touch panels.

  Further, as an embodiment of the printed wiring board of the present invention, a semiconductor device having a wafer level package structure may be mentioned. The semiconductor device includes a semiconductor element, an external connection terminal connected to an electrode on the surface of the semiconductor element, and an electrically insulating layer made of a cured insulating adhesive film covering the surface of the semiconductor element excluding the external connection terminal. Have. As a manufacturing method of the semiconductor device, a step of adhering the insulating adhesive film of the present invention so as to cover the surface of a semiconductor wafer, the insulating adhesive film is cured, and then the cured insulating adhesive film is coated with a semiconductor. A step of forming an opening at a portion to be an electrode position of the element, a step of forming a conductor layer on the surface of the insulating adhesive film cured through the opening, and the above three steps are repeated as appropriate, thereby It consists of the process of connecting an electrode and the terminal for external connection. By cutting the wafer thus obtained into individual elements, a semiconductor device having a wafer level package structure can be obtained.

  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), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of alicyclic olefin polymer
It was measured by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent, and was determined as a polystyrene equivalent value.

(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 alicyclic olefin polymer before hydrogenation was determined as ¹ H of 400 MHz. -It calculated | required by NMR spectrum measurement and made this hydrogenation rate.

(3) Content of repeating unit having carboxylic acid anhydride group of alicyclic olefin polymer Number of moles of repeating unit having carboxylic acid anhydride group with respect to the total number of moles of monomer units in alicyclic olefin polymer Was determined by 400 MHz ¹ H-NMR spectrum measurement.

(4) Adhesion between the insulating layer and the metal layer (peel strength)
The peel strength between the insulating layer and the copper plating layer where there is no via hole in the composite was measured according to JIS C6481-1996.
○: Peel strength is 5 N / cm or more ×: Peel strength is less than 5 N / cm

(5) Surface roughness of the insulating layer (arithmetic mean roughness Ra)
The surface roughness (arithmetic mean roughness Ra) of the surface of the electrical insulating layer of the composite was measured in a measurement range of 91 μm × 120 μm using a surface shape measuring device (manufactured by Beeco Instruments, WYKO NT1100).
○: Surface roughness Ra is less than 300 μm ×: Surface roughness Ra is 300 μm or more

(6) Deformation (warpage) of the cured product of the laminate
The cured product of the laminate was placed on a flat surface with its convex surface down, and the distance from the flat surface to the end of the cured product that floated highest was measured as the amount of warpage of the cured product.
○: Warpage amount is less than 2 mm ×: Warpage amount is 2 mm or more

Production Example 1
Tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene 70 mol parts, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride 30 mol parts, 1-hexene 0 .9 mol part, 590 mol part of anisole and 4-acetoxybenzylidene (dichloro) (4,5-dibromo-1,3-dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium (ruthenium) 0.015 mol part (manufactured by Wako Pure Chemical Industries, Ltd.) was put into a pressure-resistant glass reactor substituted with nitrogen, and a polymerization reaction was carried out at 80 ° C. for 1 hour with stirring to obtain a ring-opening polymer solution. Next, the obtained ring-opened polymer solution was placed in an autoclave equipped with a stirrer purged with nitrogen, and stirred for 5 hours at 150 ° C. under a hydrogen pressure of 7 MPa to conduct a hydrogenation reaction, whereby an alicyclic olefin polymer (P A solution of -1) was obtained. The obtained alicyclic olefin polymer (P-1) had a weight average molecular weight of 50,000, a number average molecular weight of 26,000, and a molecular weight distribution of 1.9. The hydrogenation rate was 97%, and the content of repeating units having a carboxylic anhydride group was 30 mol%. The solid content concentration of the solution of the alicyclic olefin polymer (P-1) was 25%.

Production Example 2
Tetracyclo [9.2.1.02,10.03,8] tetradeca-3,5,7,12-tetraene (MTF) 70 mol parts, bicyclo [2.2.1] hept-2-ene-5 30 mol parts of 6-dicarboxylic anhydride (NDCA), 0.9 mol parts of 1-hexene, 590 mol parts of anisole and 0.015 mol parts of C1063 were charged into a pressure-resistant glass reactor purged with nitrogen, and stirred at 80 ° C. A norbornene-based ring-opening polymer solution was obtained by performing a polymerization reaction for 1 hour. 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 and stirred for 5 hours at 150 ° C. and a hydrogen pressure of 7 MPa to carry out a hydrogenation reaction, whereby hydrogen of the norbornene-based ring-opening polymer was obtained. A solution of an alicyclic olefin polymer (P-2) as an additive was obtained. The weight average molecular weight of the obtained polymer (P-2) was 50,000, the number average molecular weight was 26,000, and the molecular weight distribution was 1.9. The hydrogenation rate was 97%, and the content of monomer units having a carboxylic anhydride group was 30 mol%. The solid content concentration of the polymer (P-2) solution was 22%.

Example 1
(Thermosetting resin composition)
45 parts of the solution of the alicyclic olefin polymer (P-1) obtained in Production Example 1 and untreated spherical silica as an inorganic filler (Admafine (registered trademark) SO-C1, manufactured by Admatechs, volume) Anisole was added to 98% of the average particle size of 0.25 μm) and 2% of the alicyclic olefin polymer (P-2) obtained in Production Example 2 so as to have a solid content of 75%, and dispersed with a high-pressure homogenizer. 3.3 parts of silica slurry was mixed and stirred with a planetary stirrer for 3 minutes.
To this, 3.5 parts of dicyclopentadiene type polyfunctional epoxy resin (EPICLON HP-7200L, manufactured by DIC, epoxy equivalents 242-252) as a curing agent, 2- [2-hydroxy-3, 5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate as a hindered phenol compound ( IRGANOX (registered trademark) 3114 (manufactured by BASF) 0.1 part, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate (as hindered amine compound) ADK STAB (registered trademark) LA52, manufactured by ADEKA) 0.05 part, and anisole 63. Part were mixed and stirred for 3 minutes with a planetary stirrer.
Further, 0.1 part of a solution in which 50% 1-benzyl-2-phenylimidazole was dissolved in anisole as a curing accelerator was mixed and stirred for 5 minutes with a planetary stirrer to make a varnish of a thermosetting resin composition. Got.

(Photocurable resin composition)
70% cyclohexane solution 10 of ε-caprolactone adduct (Epolide GT 401, manufactured by Daicel Chemical Industries) of epoxidized butanetetracarboxylic acid tetrakis-3-cyclohexenylmethyl ester as an alicyclic epoxy compound, which is a photocurable compound Part, 1,1-bis (2,7-diglycidyloxy-1-naphthyl) methane (Epicron HP-4700, manufactured by DIC) as a naphthalene skeleton glycidyl ether type epoxy compound, 28 parts, photopolymerization initiator (B2) As a photoacid generator, arylsulfonium salt ([(phenylthio) phenyl] diphenylsulfonium hexafluoroantimonate, CPI-101A, manufactured by San Apro Co.) 0.7 parts, silica as an inorganic filler (Admafine SO-C2 , Volume average particle size 0.5 μm, 88 parts of silica slurry in which cyclohexane is added so that the solid content is 70% and dispersed with a high-pressure homogenizer, and tris (3,5-di-t-butyl-4-hydroxybenzyl) as an anti-aging agent ) -Isocyanate 0.1 part and 9,10-diethoxyanthracene 0.07 part as a photosensitizer are mixed and mixed so that the compounding agent concentration becomes 75%. I got a thing.

(Preparation of insulating adhesive film)
The thermosetting resin composition obtained as described above was applied on a poly (ethylene terephthalate) film (Lumirror (registered trademark) T60, manufactured by Toray Industries, Inc.) having a thickness of 38 μm as a support using a bar coater, and then nitrogen. It dried at 80 degreeC for 5 minute (s) in atmosphere, and obtained the film molding of the thermosetting resin composition of thickness 3 micrometers on a support body.

  Next, the photocurable resin composition obtained above was applied to the molding surface of the layer comprising the thermosetting resin composition with a support using a bar coater, and then dried at 80 ° C. for 10 minutes in a nitrogen atmosphere. Thus, a film in which a thermosetting resin composition layer (A) and a photocurable resin composition layer (B) having a total thickness of 20 μm were formed on a support was obtained.

(Production of laminate)
Next, the film with a support obtained above is photocured in a state where the support is attached to one surface of a circular glass substrate having a diameter of 4 inches (D263, manufactured by Schott Corp., thickness 150 μm) as a base material. Using a vacuum laminator equipped with heat-resistant rubber press plates at the top and bottom so that the resin composition layer (B) fits on the glass surface, the pressure was reduced to 200 Pa and pressure-bonded at a temperature of 90 ° C. and a pressure of 0.1 MPa for 60 seconds. . Furthermore, it pressure-bonded for 90 second at the temperature of 90 degreeC and 1 Mpa using the hydraulic press apparatus provided with the metal press board up and down. Next, the laminate was obtained by peeling off the support.

(Curing the laminate)
The surface of the thermosetting resin composition of the obtained laminate was irradiated with ultraviolet rays having a light intensity at 365 nm of 25 mW / cm ² in air for 80 seconds. Thereafter, heating is performed from 30 ° C. to 180 ° C. over 30 minutes, further heating at 180 ° C. for 30 minutes, and then cooling from 180 ° C. to 30 ° C. over 1 hour to laminate a film having a thickness of 20 μm on the glass. A cured product of the body was obtained and the warpage was evaluated. The results are shown in Table 1.

(Composite formation)
Next, separately from the above, a copper foil having a thickness of 35 μm was pasted on the surface of the core material obtained by impregnating glass fiber with a varnish containing a glass filler and a halogen-free epoxy resin. A double-sided copper-clad laminate (inner layer substrate) was obtained by microetching the copper surface of an 8 mm double-sided copper-clad plate by contact with an organic acid.

After laminating the insulating adhesive film with a support obtained above on both sides of the inner layer substrate so that the surface on the photocurable resin composition layer (B) side is inside, the primary press is applied. went. The primary press is thermocompression bonding at a temperature of 90 ° C. and a pressure of 0.1 MPa for 60 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 apparatus provided with metal press plates at the top and bottom, thermocompression bonding was performed at a bonding temperature of 90 ° C. and 1 MPa for 90 seconds. Subsequently, the support body was peeled off to obtain a laminate of a resin layer and an inner layer substrate made of a thermosetting resin composition and a photocurable resin composition. Further, the laminate was heated at 30 ° C. to 180 ° C. over 30 minutes in an air atmosphere, further heated at 180 ° C. for 30 minutes, and then cooled from 180 ° C. to 30 ° C. over 1 hour, An electrical insulating layer was formed on the inner layer substrate by curing.
Using the carbon dioxide laser processing machine (manufactured by Hitachi Via Mechanics Co., Ltd .: LC-2K212 / 2C), the laminated body obtained above is punched with a pulse width of 17 μs, a frequency of 1000 Hz, and two shots. A via hole having an opening diameter of 60 μm up to the copper foil surface was obtained.

(Swelling process)
The obtained cured product was prepared by adding a swelling liquid (“Swelling Dip Securigant P”, manufactured by Atotech, “Securigant” is a registered trademark) to 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 dipping for 10 minutes in an aqueous solution of permanganate (“Concentrate Compact CP”, manufactured by Atotech Co., Ltd.) at 500 mL / L and an aqueous solution of 80 ° C. prepared to have a sodium hydroxide concentration of 40 g / L. , Washed with water.

(Neutralization reduction process)
Subsequently, an aqueous solution of hydroxyamine sulfate (“Reduction Securigant P500”, manufactured by Atotech Co., Ltd., “Securigant” is a registered trademark) is 100 mL / L, and an aqueous solution at 40 ° C. prepared to be 35 mL / L of sulfuric acid is cured with a cured product. Was immersed for 5 minutes, neutralized and reduced, and then washed with water.

(Cleaner / conditioner process)
Next, the cured product is 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 cured product was immersed in 40 ° C. washing water for 1 minute and then washed with water.

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

(Pickling process)
Next, the cured product was immersed in an aqueous solution prepared 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., “ The Alcup “registered trademark” was immersed in an aqueous solution adjusted to 200 mL / L at 35 ° C. for 3 minutes to reduce the plating catalyst, and then washed with water.

(Accelerator process)
Next, the cured product was immersed in an aqueous solution prepared so that Alcup 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 cured product that has undergone the above-described steps is 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 Kogyo Co., Ltd.). 50 mL / L, Sulcup PEA-6-C (trade name, manufactured by Uemura Kogyo) 14 mL / L, Sulcup PEA-6-D (trade name, manufactured by Uemura Kogyo) 15 mL / L, Sulcup PEA-6-E (Trade name, manufactured by Uemura Kogyo Co., Ltd.) Electroless copper is immersed for 20 minutes at a temperature of 36 ° C. while blowing air into an electroless copper plating solution prepared to be 50 mL / L, 37% formalin aqueous solution 5 mL / L An electroless plating film was formed on the surface of the cured product (the surface of the insulating layer made of the cured thermosetting resin composition) by plating. Next, annealing was performed at 150 ° C. for 30 minutes in an air atmosphere.

  The cured product subjected to the annealing treatment was subjected to electrolytic copper plating to form an electrolytic copper plating film having a thickness of 30 μm. Next, the cured product was heat-treated at 180 ° C. for 60 minutes to obtain a printed wiring board (composite) in which a circuit was formed on the cured product 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 1.

  The surface average roughness Ra of the electrical insulating layer obtained by removing the conductor layer by etching the metal thin film layer and the electrolytic copper plating film on the cured product was measured according to the above method. The results are shown in Table 1.

Comparative Example 1
As an aromatic sulfonate ([(phenylthio) phenyl] diphenylsulfonium hexafluoroantimonate, CPI-101A, manufactured by San Apro Co.) as a photoacid generator of a photocurable resin composition and a photosensitizer Example 1 except that 0.7 part of a thermal acid generator SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) was used instead of 0.07 part of 9,10-diethoxyanthracene in Example 1, and ultraviolet rays were not irradiated. In the same manner as above, a film, a laminate, and a cured product were obtained and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 2
A film, a laminate, and a cured product are obtained in the same manner as in Example 1 except that the thermosetting resin composition layer (A) is not formed and the thickness of the photocurable resin composition layer (B) is 20 μm. Were similarly evaluated. These evaluation results are shown in Table 1.

Comparative Example 3
Aromatic sulfonate ([(phenylthio) phenyl] diphenylsulfonium hexafluoroantimonate, CPI-101A as a photoacid generator of the photocurable resin composition without forming the thermosetting resin composition layer (A) In addition to 0.7 part of Sun Apro) and 0.07 part of 9,10-diethoxyanthracene as a photosensitizer, 0.7 part of thermal acid generator SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) A laminate and a cured product were obtained in the same manner as in Example 1 except that the film was used and the film thickness was 20 μm and no ultraviolet ray was irradiated. The results are shown in Table 1.

As shown in Table 1, the insulating adhesive film formed by laminating the thermosetting resin composition layer (A) and the photocurable resin composition layer (B) has a low roughness of the insulating layer surface and warpage. It can be seen that a cured product having a small peel strength is obtained. Example 1
On the other hand, when a photoacid generator was not blended in the photocurable resin composition layer (B), and a thermal acid generator was blended and cured by heat, a large warp was obtained. (Comparative Example 1)
When only the photocurable resin composition layer (B) was formed without forming the thermosetting resin composition layer (A), the surface roughness was high and the peel strength was small. (Comparative Example 2)
Also, when the thermosetting resin composition layer (A) is not formed, the photoacid generator is not blended with the photocurable resin composition layer (B), and the thermoacid generator is blended and cured by heat. As a result, surface roughness, warpage, and peel strength deteriorated. (Comparative Example 3)

Claims (9)

  An insulating adhesive film obtained by laminating a thermosetting resin composition layer (A) and a photocurable resin composition layer (B) in this order on a support.   The insulating adhesive film according to claim 1, wherein the thermosetting resin composition contains a thermosetting resin having a weight average molecular weight of 1,000 or more.   The insulating adhesive film according to claim 2, wherein the thermosetting resin is an alicyclic olefin polymer.   Insulative adhesion according to any one of claims 1 to 3, wherein the total thickness of the two layers of the thermosetting resin composition layer (A) and the photocurable resin composition layer (B) is 50 µm or less. the film.   The laminated body formed by laminating | stacking the surface of the photocurable resin composition layer (B) of the insulating adhesive film in any one of Claims 1-4 according to a base material.   Hardened | cured material formed by hardening | curing the thermosetting resin composition layer (A) and / or photocurable resin composition layer (B) of the laminated body of Claim 5.   In the laminate according to claim 5 or the cured product according to claim 6, after forming a via hole from the surface opposite to the substrate to the substrate surface by a laser, or further further, uncured or semi-cured, After the thermosetting resin composition layer (A) and / or the photocurable resin composition layer (B) is cured, the surface of the cured thermosetting resin composition layer (A) and / or the surface of the via hole is used. A composite comprising a conductor layer.   A multilayer composite comprising two or more layers comprising the composite according to claim 7.   A printed wiring board comprising the composite according to claim 7 or the multilayer composite according to claim 8.