JP6528226B2 - Curable resin composition, film, laminated film, prepreg, laminate, cured product, and composite - Google Patents

Description

  The present invention relates to a curable resin composition, a film, a laminated film, a prepreg, a laminate, a cured product, and a composite.

  With the pursuit of miniaturization, multi-functionalization, high-speed communication, etc. of electronic devices, further densification of circuit boards used for electronic devices is required, and in order to meet such demands for high density, Multilayering of circuit boards has been achieved. In such a multilayer circuit board, for example, an electric insulating layer is laminated on an inner layer substrate consisting of an electric insulating layer and a conductor layer formed on the surface, and a conductor layer is formed on the electric insulating layer. Furthermore, it is formed by repeating the lamination | stacking of these electric-insulation layers, and formation of a conductor layer.

  In such a multilayer circuit board, disconnection of the circuit may occur due to a difference in linear expansion between the conductor layer and the electrical insulating layer, particularly when the conductor layer has a high density pattern. The problem of disconnection was remarkable. Therefore, in the multilayer circuit board, low linear expansion of the electrical insulating layer is required. Although it is generally effective to add an inorganic filler for reducing the linear expansion of the electrical insulating layer, the addition of the inorganic filler increases the surface roughness of the electrical insulating layer, and the surface of the electrical insulating layer In the case where a fine wiring is formed by forming a conductor layer and etching the conductor layer, there is a problem that a conductor remains between patterns due to an etching failure, or the conductor is lifted or peeled off.

  On the other hand, in Patent Document 1, in order to form an electrical insulating layer having a low surface roughness and excellent adhesion to a conductor layer, an insulating adhesive film for forming the electrical insulating layer is an alicyclic olefin. A plated layer containing a polymer, a curing agent and an untreated inorganic filler not subjected to surface treatment, and an adhesive layer containing an alicyclic olefin polymer, a curing agent and a surface treated inorganic filler subjected to a surface treatment A technique is disclosed which is formed in a two-layer structure consisting of

JP, 2013-77704, A

  However, when the present inventors examined, in the technique of this patent document 1, the surface roughness is obtained by roughening the surface of the layer to be plated using an oxidizing compound such as an aqueous solution of permanganate. To improve the adhesion to the conductor layer while keeping the low, but by changing the conditions of such surface roughening treatment, the surface roughness of the electrical insulating layer obtained and the adhesion to the conductor layer However, there is a problem that it is difficult to stably obtain an electrical insulating layer having desired characteristics. In particular, the conditions of such surface roughening treatment often fluctuate due to various factors, and therefore, even when the conditions of surface roughening treatment fluctuate, the surface roughness is low and the adhesion to the conductor layer is excellent. It has been desired to stably obtain an electrically insulating layer.

  An object of the present invention is to provide a curable resin composition capable of stably providing an electrical insulating layer having low surface roughness and excellent adhesion to a conductor layer even when the surface roughening treatment conditions are varied. It is to do.

  As a result of intensive studies to achieve the above object, the present inventors have found that phenol having a fused polycyclic structure having a weight average molecular weight in a specific range for an alicyclic olefin polymer having a specific functional group. Curable obtained by blending a novolac epoxy compound and an inorganic filler surface-treated with a silane coupling agent, and setting the blending amount of a phenol novolac epoxy compound having a condensed polycyclic structure to a specific range According to the resin composition, it has been found that an electrical insulating layer having low surface roughness and excellent adhesion to a conductor layer can be stably provided even when the surface roughening treatment conditions vary. It came to complete.

That is, according to the present invention,
[1] Alicyclic olefin polymer (A) having at least one functional group selected from a carboxyl group, a carboxylic acid anhydride group and a phenolic hydroxyl group, a phenol novolac epoxy compound (B) having a condensed polycyclic structure, And an inorganic filler (C) surface-treated with a silane coupling agent, wherein the epoxy equivalent of the epoxy compound (B) is 260 to 400, based on 100 parts by weight of the alicyclic olefin polymer (A), A curable resin composition in which the content ratio of the epoxy compound (B) is 10 to 100 parts by weight,
[2] The curable resin composition according to [1], wherein the content ratio of the inorganic filler (C) is 5 to 50% by weight.
[3] The curable aliphatic resin composition according to the above [1] or [2], wherein the content of the alicyclic olefin polymer (A) is larger than the content of the inorganic filler (C). Curable resin composition,
[4] A film comprising the curable resin composition according to any one of the above [1] to [3],
[5] A laminated film having a to-be-plated layer comprising the curable resin composition according to any one of the above [1] to [3] and an adhesive layer comprising the resin composition for adhesive layer,
[6] The laminated film according to the above [5], wherein the resin composition for an adhesive layer contains an epoxy compound and an active ester compound,
[7] A prepreg comprising a fibrous base material in the film of the above [4] or the laminated film of the above [5] or [6],
[8] A laminate obtained by laminating the film according to the above [4], the laminated film according to the above [5] or [6] or the prepreg according to the above [7] on a substrate,
[9] The curable resin composition according to any one of the above [1] to [3], the film as described in the above [4], the laminated film as described in the above [5] or [6], the above [7] Or the cured product obtained by curing the laminate of [8],
[10] A composite obtained by forming a conductor layer on the surface of the cured product according to the above [9], and
[11] A substrate for electronic material comprising the cured product according to the above [9] or the composite according to the above [10] as a constituent material,
Is provided.

  According to the present invention, a curable resin composition capable of stably providing an electrical insulating layer having low surface roughness and excellent adhesion to a conductor layer even when the surface roughening treatment conditions vary, and Provided are a film, a laminated film, a prepreg, a laminate, a cured product, and a composite obtained by using the same. In particular, according to the present invention, the margin of the surface roughening treatment conditions (specifically, the margin of the treatment time and the treatment temperature) is increased, so that the surface roughness is low, and the electricity is excellent in the adhesion to the conductor layer. The insulating layer can be stably obtained without strictly controlling the surface roughening treatment conditions.

(Curable resin composition)
The curable resin composition of the present invention comprises an alicyclic olefin polymer (A) having at least one functional group selected from a carboxyl group, a carboxylic acid anhydride group and a phenolic hydroxyl group, and a phenol novolac having a condensed polycyclic structure Type epoxy compound (B), and an inorganic filler (C) surface-treated with a silane coupling agent, and the epoxy equivalent of the epoxy compound (B) is 260 to 400, and the alicyclic olefin polymer ( A) The content of the epoxy compound (B) is 10 to 100 parts by weight with respect to 100 parts by weight.

(Alicyclic olefin polymer (A))
The alicyclic olefin polymer (A) used in the present invention is an alicyclic olefin polymer having at least one functional group selected from a carboxyl group, a carboxylic acid anhydride group and a phenolic hydroxyl group. As an alicyclic structure which comprises an alicyclic olefin polymer (A), although a cycloalkane structure, a cycloalkene structure, etc. are mentioned, a cycloalkane structure is preferable from viewpoints of mechanical strength, heat resistance, etc. In addition, as the alicyclic structure, a single ring, a multiple ring, a condensed multiple ring, a bridged ring, a multiple ring formed by combining these, and the like can be mentioned. 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 carbon constituting the alicyclic structure When the number of atoms is in this range, various properties of mechanical strength, heat resistance and moldability are highly balanced and suitable. The alicyclic olefin polymer (A) is usually thermoplastic.

  The alicyclic olefin polymer (A) used in the present invention is one having at least one functional group selected from a carboxyl group, a carboxylic acid anhydride group and a phenolic hydroxyl group. An organic group is more preferred. The alicyclic olefin polymer (A) may have two or more of such functional groups, and such functional groups are directly bonded to atoms constituting the main chain of the polymer. Or may be bonded via another divalent group such as a methylene group, an oxy group, an oxycarbonyloxyalkylene group, or a phenylene group. Although the content of the monomer unit having at least one functional group selected from a carboxyl group, a carboxylic acid anhydride group and a phenolic hydroxyl group in the alicyclic olefin polymer (A) is not particularly limited, it is an alicyclic It is 4-60 mol% normally, Preferably it is 8-50 mol% in 100 mol% of all the monomer units which comprise an olefin polymer (A).

The alicyclic olefin polymer (A) used in the present invention can be obtained, for example, by the following method. That is, (1) an alicyclic olefin having at least one functional group selected from a carboxyl group, a carboxylic acid anhydride group and a phenolic hydroxyl group (hereinafter, appropriately referred to as a "specific functional group"), if necessary (2) a method of copolymerizing a cycloaliphatic olefin having no specific functional group with a monomer having a specific functional group, (3) a specific functional group (4) an aromatic olefin having no specific functional group, a method of polymerizing the aromatic olefin having, optionally adding other monomers, and polymerizing it, thereby hydrogenating the aromatic ring portion of the polymer obtained Is copolymerized with a monomer having a specific functional group to hydrogenate the aromatic ring portion of the polymer thus obtained, or (5) specified as an alicyclic olefin polymer having no specific functional group Change compounds with functional groups It can be obtained by a method of introducing the reaction. Among these, the polymers obtained by the above-mentioned method (1) are preferable.
The polymerization method for obtaining the alicyclic olefin polymer (A) used in the present invention is ring-opening polymerization or addition polymerization, but in the case of ring-opening polymerization, it is preferable to hydrogenate the obtained ring-opening polymer .

5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo [2.2.1] hept as a specific example of the alicyclic olefin which has a specific functional group -2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-carboxymethyl-9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 5-exo-6-endo-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 9-exo-10-endo-dihydroxycarbonyltetracyclo [6. 2.1.1 ^3,6 . Alicyclic olefins having a carboxyl group such as 0 ^2,7 ] dodec-4-ene; bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, tetracyclo [6.2 .1.1 ^3,6 . 0 ^2,7] dodeca-4-ene-9,10-dicarboxylic anhydride, hexacyclo [10.2.1.1 ^{3, 10. 5,8} . 0 ^{2, 11} . 0 ^4,9] heptadec-6-ene-13,14-alicyclic olefin having a carboxylic acid anhydride group, such as a dicarboxylic acid anhydride; (5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 9- (4-hydroxyphenyl) tetracyclo ^[6.2.1.1 3,6 ^{.0 2,7]} dodeca-4-ene, N-(4-hydroxyphenyl) bicyclo [2. 2.1] Aliphatic olefins having a phenolic hydroxyl group such as hept-5-ene-2,3-dicarboximide, etc. These may be used alone or two or more of them may be used. You may use together.

Specific examples of alicyclic olefins having no specific functional group include bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethyl-bicyclo [2.2.1] hept- 2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2. 1] Hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene (common name: Dicyclopentadiene), tetracyclo [6.2.1.1 ^{3, 6} . 0 ^2,7 ] dodec-4-ene (common name: tetracyclododecene), 9-methyl-tetracyclo [6.2.1.1 ^{3, 6} . 0 ^2,7 ] dodec-4-ene, 9-ethyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methoxycarbonyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-vinyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-propenyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-phenyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7] dodeca-4-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene, cyclopentene, cyclopentadiene and the like. One of these may be used alone, or two or more may be used in combination.

  Examples of aromatic olefins having no specific functional group include styrene, α-methylstyrene, divinylbenzene and the like. In addition, when these compounds have the said specific functional group, they are mentioned as an example of the aromatic olefin which has a specific functional group. One of these may be used alone, or two or more may be used in combination.

  As a monomer having a specific functional group other than an alicyclic olefin having a specific functional group, which can be copolymerized with an alicyclic olefin or an aromatic olefin, an ethylenically unsaturated compound having a specific functional group is Specific examples thereof include unsaturated carboxylic acid compounds such as acrylic acid, methacrylic acid, α-ethyl acrylic acid, 2-hydroxyethyl (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, etc .; maleic anhydride And unsaturated carboxylic acid anhydrides such as butenyl succinic anhydride, tetrahydrophthalic anhydride, citraconic anhydride, and the like. One of these may be used alone, or two or more may be used in combination.

  Examples of monomers having no specific functional group other than alicyclic olefin that can be copolymerized with alicyclic olefins and aromatic olefins include ethylenically unsaturated compounds having no specific functional group, Specific examples thereof 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- C2-C20 ethylene or alpha-olefins such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; And the like; hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene nonconjugated dienes such. One of these may be used alone, or two or more may be used in combination.

  The molecular weight of the cycloaliphatic olefin polymer (A) used in the present invention is not particularly limited, but it is a weight average molecular weight in terms of polystyrene as measured by gel permeation chromatography using tetrohydrofuran as a solvent. It is preferably in the range of 000,000, more preferably in the range of 1,000 to 500,000, and particularly preferably in the range of 3,000 to 300,000. When the weight average molecular weight is too small, the mechanical strength of the cured product obtained by curing the curable resin composition is reduced, and when it is too large, the workability when forming into a sheet or film to form a molded product is deteriorated. There is a tendency to

  As a polymerization catalyst in the case of obtaining the alicyclic olefin polymer (A) used by this invention by the ring-opening polymerization method, the conventionally well-known metathesis polymerization catalyst can be used. Examples of the metathesis polymerization catalyst include transition metal compounds containing atoms such as Mo, W, Nb, Ta and Ru. Among them, compounds containing Mo, W or Ru are preferable because of high polymerization activity. Specific examples of particularly preferable metathesis polymerization catalysts include: (1) Molybdenum or tungsten compounds having as a ligand a halogen group, an imide group, an alkoxy group, an aryloxy group or a carbonyl group as a main catalyst, and an organometallic compound The catalyst used as a 2nd component and the metal carbene complex catalyst which makes (2) Ru a central metal can be mentioned.

Examples of compounds used as a main catalyst in the catalyst of the above (1) include halogenated molybdenum compounds such as MoCl ₅ and MoBr ₅ and halogenated compounds such as WCl ₆ , WOCl ₄ , tungsten (phenyl imide) tetrachloride / diethyl ether etc. Tungsten compounds can be mentioned. Moreover, as an organic metal compound used as a 2nd component by the catalyst of said (1), the organic metal compound of periodic table group 1, 2, 12, 13, or 14 group can be mentioned. Among them, organic lithium compounds, organic magnesium compounds, organic zinc compounds, organic aluminum compounds and organic tin compounds are preferable, and organic lithium compounds, organic aluminum compounds and organic tin compounds are particularly preferable. Examples of the organic lithium compound include n-butyllithium, methyllithium, phenyllithium, neopentyllithium, neophyllithium and the like. Examples of the organic magnesium include butylethyl magnesium, butyl octyl magnesium, dihexyl magnesium, ethyl magnesium chloride, n-butyl magnesium chloride, allyl magnesium bromide, neopentyl magnesium chloride, neophyl magnesium chloride and the like. Examples of organic zinc compounds include dimethyl zinc, diethyl zinc and diphenyl zinc. Examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum ethoxide, ethylaluminum diethoxide and the like, and further, An aluminoxane compound obtained by the reaction of an organoaluminum compound and water can also be used. Examples of the organotin compound include tetramethyltin, tetra (n-butyl) tin and tetraphenyltin. The amount of these organometallic compounds varies depending on the organometallic compound to be used, but the molar ratio is preferably 0.1 to 10,000 times, 0.2 to 5,000 times the central metal of the main catalyst. More preferably, 0.5 to 2,000 times is particularly preferable.

  Moreover, as a metal carbene complex catalyst which makes Ru the center metal of said (2), (1, 3- dimesityl imidazolidin 2-ylidene) (tricyclohexyl phosphine) benzylidene ruthenium dichloride, bis (tricyclohexyl phosphine) benzylidene Ruthenium dichloride, tricyclohexylphosphine- [1,3-bis (2,4,6-trimethylphenyl) -4,5-dibromoimidazole-2-ylidene]-[benzylidene] ruthenium dichloride, 4-acetoxybenzylidene (dichloro) ( 4,5-dibromo-1,3-dimesityl-4-imidazolin-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 as the molar ratio of (transition metal in the metathesis polymerization catalyst: monomer) to the monomer used for the polymerization. And preferably in the range of 1: 200 to 1: 1,000,000. When the amount of the catalyst is too large, the removal of the catalyst becomes difficult, and when it is too small, sufficient polymerization activity may not be obtained.

  The polymerization reaction is usually carried out in an organic solvent. The organic solvent to be used is not particularly limited as long as the polymer dissolves or disperses under predetermined conditions and does not affect the polymerization, but it is preferably industrially used widely. Specific examples of the organic solvent include aliphatic hydrocarbons such as pentane, hexane and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane Alicyclic hydrocarbons such as hexahydroindene cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogen-based aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; chlorobenzene and dichlorobenzene Halogen-containing aromatic hydrocarbons such as: Nitromethane, nitrobenzene, nitrogen-containing hydrocarbon solvents such as acetonitrile; diethyl ether, tetrahydrofuran etc Et - ether solvents; and the like; anisole, aromatic ether solvents such as phenetole. Among these, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ether solvents, and aromatic ether solvents which are widely used industrially are preferable.

  The amount of the organic solvent used is preferably such that the concentration of the monomer in the polymerization solution will be 1 to 50% by weight, more preferably 2 to 45% by weight, and 3 to 40. It is particularly preferred that the amount is in weight percent. 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 initiated by mixing the monomers used for the polymerization and the 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 consisting of a transition metal compound which is a main catalyst and an organic metal compound which is a second component, the reaction liquid 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.

  The polymerization temperature is not particularly limited, but is usually -30 ° C to 200 ° C, preferably 0 ° C to 180 ° C. The polymerization time is not particularly limited, but is usually 1 minute to 100 hours.

  As a method of adjusting the molecular weight of the obtained alicyclic olefin polymer (A), a method of adding an appropriate amount of a vinyl compound or a diene compound can be mentioned. 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, 1-octene and the like; styrene, vinyl toluene 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, and nitrogen-containing vinyl compounds such as acrylamide Can be mentioned. As a diene compound used for molecular weight adjustment, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl-1 Non-conjugated diene such as 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 the vinyl compound or the diene compound can be optionally selected between 0.1 and 10 mol% with respect to the monomer used for polymerization, depending on the target molecular weight.

  As a polymerization catalyst in the case of obtaining the alicyclic olefin polymer (A) used by this invention by the addition polymerization method, the catalyst which consists of titanium, a zirconium or a vanadium compound, and an organic aluminum compound is used suitably, for example. These polymerization catalysts can be used alone or in combination of two or more. The amount of the polymerization catalyst is usually in the range of 1: 100 to 1: 2,000,000 as a molar ratio of (metal compound in the polymerization catalyst: monomer used for polymerization).

  When a hydrogenated product of a ring-opening polymer is used as the alicyclic olefin polymer (A) used in the present invention, hydrogenation of the ring-opening polymer is usually carried out using a hydrogenation catalyst. The hydrogenation catalyst is not particularly limited, and one which is generally used in hydrogenation of an olefin compound may be appropriately adopted. Specific examples of the hydrogenation catalyst include, for example, cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, titanocene dichloride and n-butyllithium, zirconocene dichloride and sec-butyllithium, tetrabutoxytitanate and dimethylmagnesium, etc. 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. In addition, heterogeneous catalysts in which a metal such as nickel, palladium, platinum, rhodium, or ruthenium is supported on a carrier such as carbon, silica, diatomaceous earth, alumina, or titanium oxide; for example, nickel / silica, nickel / diatomaceous earth, nickel And alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like can also be used. Moreover, it is also possible to use the above-mentioned metathesis polymerization catalyst as it is as a hydrogenation catalyst.

  The hydrogenation reaction is usually carried out in an organic solvent. The organic solvent can be appropriately selected depending on the solubility of the generated hydrogenate, and the same organic solvent as the organic solvent used for the above-mentioned polymerization reaction can be used. Therefore, after the polymerization reaction, it is also possible to add the hydrogenation catalyst as it is to react without replacing the organic solvent. Furthermore, among the organic solvents used for the above-mentioned polymerization reaction, from the viewpoint of not reacting in the hydrogenation reaction, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ether solvents, aroma Group ether solvents are preferable, and aromatic ether solvents are more preferable.

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

  The time of the hydrogenation reaction is appropriately selected to control the hydrogenation rate. The reaction time is usually in the range of 0.1 to 50 hours, and 50 mol% or more, preferably 70 mol% or more, more preferably 100 mol% of carbon-carbon double bonds in the main chain in the polymer. 80 mol% or more, particularly preferably 90 mol% or more can be hydrogenated.

  After the hydrogenation reaction is performed, a treatment for removing the catalyst used for the hydrogenation reaction may be performed. The method of removing the catalyst is not particularly limited, and methods such as centrifugation and filtration may be mentioned. Furthermore, catalyst removal can be promoted by adding a catalyst deactivating agent such as water or alcohol, or adding an adsorbent such as activated clay, alumina, silicon earth or the like.

  The alicyclic olefin polymer (A) used in the present invention may be used either as a polymer solution after polymerization or hydrogenation reaction or after removal of the solvent. It is preferable to use as a polymer solution because the dissolution and dispersion of the additive become good and the process can be simplified when preparing.

(Phenol novolac epoxy compound (B) having condensed polycyclic structure)
The phenol novolac epoxy compound (B) having a condensed polycyclic structure used in the present invention (hereinafter, referred to as "phenol novolac epoxy compound (B)") may be abbreviated. ] Is a phenol novolak type epoxy compound having a condensed polycyclic structure and an epoxy equivalent in the range of 260 to 400. Here, the epoxy equivalent of the phenol novolac epoxy compound (B) is the number of grams of epoxy compound containing 1 gram equivalent of epoxy group (g / eq), which is calculated by measuring the amount of oxygen of oxirane in the compound. Ru.

  The fused polycyclic structure refers to a structure formed by condensation (ring condensation) of two or more single rings. The ring constituting the fused polycyclic structure may be alicyclic or aromatic and may contain a hetero atom. The number of condensed rings is not particularly limited, but from the viewpoint of enhancing the heat resistance and mechanical strength of the obtained electrical insulating layer, it is preferably 2 rings or more, and for practical purposes, the upper limit is about 10 rings. is there. As such a fused polycyclic structure, for example, a dicyclopentadiene structure, a naphthalene structure, a fluorene structure, an anthracene structure, a phenanthrene structure, a triphenylene structure, a pyrene structure, an ovalene structure and the like can be mentioned. The condensed polycyclic structure usually constitutes the main chain of the resin in the obtained cured resin, but may be present in the side chain.

  The phenol novolac epoxy compound (B) used in the present invention may have an epoxy equivalent in the range of 260 to 400, preferably in the range of 265 to 350, and more preferably in the range of 270 to 300. When the epoxy equivalent is too low or too high, the stability of the resulting cured product (particularly, the surface roughness and the adhesion with the conductor layer) is improved when the surface roughening treatment conditions are changed. The effect can not be obtained.

The phenol novolac epoxy compound (B) used in the present invention can be appropriately produced according to a known method, but is also available as a commercial product. For example, as a commercial product of a phenol novolac epoxy compound (B), it is a novolac epoxy compound having a dicyclopentadiene structure, for example, trade names "Epiclon HP 7200, Epiclon HP 7200H, Epiclon HP 7200HH, Epiclon HP 7200HHH" (more than Manufactured by DIC, "Epiclon" is a registered trademark, and trade name "Tactix 756" (manufactured by Huntsman Advanced Materials, "Tactix" is a registered trademark), and the like.
The above phenol novolak epoxy compounds (B) can be used alone or in combination of two or more.

  The content of the phenol novolac epoxy compound (B) in the curable resin composition of the present invention is 10 to 100 parts by weight, preferably 100 parts by weight of the alicyclic olefin polymer (A). It is 15 to 80 parts by weight, more preferably 20 to 60 parts by weight. If the content of the phenol novolac epoxy compound (B) is too small, the effect of improving the stability of the adhesion strength with the conductor layer can not be obtained when the surface roughening treatment conditions change, or the heat resistance and mounting reliability can not be obtained. It may be inferior to sex. On the other hand, when the content of the phenol novolac epoxy compound (B) is too large, the effect of improving the stability of the surface roughness of the obtained cured product can not be obtained when the surface roughening treatment conditions fluctuate, or the heat resistance can not be obtained. May be inferior to the

  Further, the equivalent ratio of the phenol novolac epoxy compound (B) to the alicyclic olefin polymer (A) in the cured resin composition of the present invention [the total number of epoxy groups of the phenol novolac epoxy compound (B)] The ratio of the total number of functional groups of the alicyclic olefin polymer (A) (epoxy group content / functional group content) is preferably 0.9 to 1.2, more preferably 0.95 to 1. It is 15.

[Inorganic filler (C) surface-treated with silane coupling agent]
The inorganic filler (C) surface-treated with a silane coupling agent used in the present invention [hereinafter, may be abbreviated as “surface-treated inorganic filler (C)”. The inorganic filler is not particularly limited as long as it has been pretreated with the silane coupling agent on the surface of the inorganic filler. In the present invention, “surface-treated with a silane coupling agent” indicates that the silane coupling agent is physically or chemically bonded to the surface of the inorganic filler particles.

  In the present invention, by using the surface-treated inorganic filler (C) together with the above-described alicyclic olefin polymer (A) and phenol novolac epoxy compound (B), it is possible to use an ordinary filter for surface roughening. The resistance to oxidizing compounds such as an aqueous solution of manganate can be enhanced, which allows the surface roughening treatment to proceed gently, and as a result, even if the surface roughening treatment conditions change, the surface It becomes possible to stably obtain an electrical insulating layer having a low degree of roughness and excellent adhesion to the conductor layer.

  As the inorganic filler, for example, 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 can be mentioned. Among these, those which do not decompose or dissolve due to an oxidizing compound such as an aqueous solution of permanganate used for surface roughening treatment of a cured product are preferable, and silica is particularly preferable.

  The silane coupling agent used for the surface treatment of the inorganic filler is not particularly limited, but is preferably one having at least one functional group selected from glycidyl group, amino group and mercapto group, It is preferable to have.

Examples of the silane coupling agent having a glycidyl group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. Be
As a silane coupling agent having an amino group, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-amino) Ethyl) -3-aminopropylmethyldimethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane and the like can be mentioned.
As a silane coupling agent having a mercapto group, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, etc. may be mentioned.

  The average particle size of the surface-treated inorganic filler (C) is preferably 0.1 to 0.5 μm, more preferably 0.15 to 0.4 μm. By setting the average particle diameter of the surface-treated inorganic filler (C) in the above range, the surface roughness of the obtained electrical insulating layer can be made more appropriate. The average particle size can be measured by a particle size distribution measuring apparatus.

  The content of the surface-treated inorganic filler (C) is preferably 5 to 50% by weight in the curable resin composition of the present invention (in the case of containing the organic solvent, in the curable resin composition excluding the organic solvent). More preferably, it is 10 to 45% by weight, and more preferably 15 to 40% by weight. In the curable resin composition of the present invention, the content of the surface-treated inorganic filler (C) may be in the above range, but is less than the content of the alicyclic olefin polymer (A) It is preferable to By setting the content of the surface-treated inorganic filler (C) in the above range, the variation in the surface roughness of the obtained electrical insulating layer is small even when the surface roughening treatment conditions vary, Adhesion strength can be made stable.

(Other ingredients)
Moreover, in the curable resin composition used by this invention, you may contain the hardening accelerator as needed. The curing accelerator is not particularly limited, and examples thereof include aliphatic polyamines, aromatic polyamines, secondary amines, tertiary amines, imidazole derivatives, organic acid hydrazide, dicyandiamide and derivatives thereof, urea derivatives and the like. Among these, imidazole derivatives are particularly preferable.

  The imidazole derivative may be any compound having an imidazole skeleton, and is not particularly limited. For example, 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, 1-methyl Alkyl substituted imidazole compounds such as 2-ethylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-heptadecylimidazole; 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2- And aryl groups such as methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, benzimidazole, 2-ethyl-4-methyl-1- (2'-cyanoethyl) imidazole, aralkyl groups, etc. ring Imidazole compounds substituted with a hydrocarbon group containing a granulation; and the like. These can be used singly or in combination of two or more.

  Although the compounding quantity in the case of mix | blending a hardening accelerator may be suitably selected according to the intended purpose, Preferably it is 0.1-20 weight parts with respect to 100 weight parts of alicyclic olefin polymers (A), More preferably, it is 0.1 to 10 parts by weight, still more preferably 0.1 to 5 parts by weight.

  Moreover, the curable resin composition of this invention may contain the hindered phenol compound and the hindered amine compound other than the said component. These hindered phenol compounds and hindered amine compounds act as anti-aging agents.

  The hindered phenol compound is a phenol compound having a hydroxyl group and having at least one hindered structure in the molecule that does not have a hydrogen atom at the carbon atom at the β-position of the hydroxyl group. Specific examples of the hindered phenol compound include 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and 4,4'-butylidene bis- (3-methyl-6-). tert-Butylphenol), 2,2-thiobis (4-methyl-6-tert-butylphenol), n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate, tetrakis -[Methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane and the like can be mentioned.

  The compounding amount of the hindered phenol compound in the curable resin composition of the present invention is not particularly limited, but preferably 0.04 to 10 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer (A) More preferably, it is in the range of 0.3 to 5 parts by weight, still more preferably 0.5 to 3 parts by weight. By making the compounding quantity of a hindered phenol compound into the said range, the mechanical strength of the electrical insulation layer obtained can be made favorable.

  The hindered amine compound is a compound having at least one 2,2,6,6-tetraalkylpiperidine group having a secondary amine or a tertiary amine at the 4-position in the molecule. The carbon number of the alkyl is usually 1 to 50. The hindered amine compound is preferably a compound having at least one 2,2,6,6-tetramethyl piperidyl group having a secondary amine or a tertiary amine in the 4-position in the molecule. In the present invention, it is preferable to use a hindered phenol compound and a hindered amine compound in combination.

  Specific examples of the hindered amine compound include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1 [2 -{3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-Tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,2,3-triazaspiro [4,5] undecane-2,4- And the like.

  The compounding amount of the hindered amine compound is not particularly limited, but generally 0.02 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably to 100 parts by weight of the alicyclic olefin polymer (A). Is 0.25 to 3 parts by weight. By making the compounding quantity of a hindered amine compound into the said range, the mechanical strength of the electrical insulation layer obtained can be made favorable.

  Furthermore, in the curable resin composition of the present invention, for the purpose of improving the flame retardancy of the obtained electrical insulating layer, for example, for forming a general electrical insulating film such as a halogen-based flame retardant or phosphate ester flame retardant The flame retardant blended in the resin composition of The blending amount in the case of blending the flame retardant 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 alicyclic olefin polymer (A).

  Further, the curable resin composition of the present invention may further contain, if necessary, a flame retardant auxiliary, a heat stabilizer, a weathering stabilizer, an antiaging agent, an ultraviolet absorber (laser processability improver), a leveling agent, Optional components such as an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a dye, a natural oil, a synthetic oil, a wax, an emulsion, a magnetic material, a dielectric property modifier, and a toughness agent may be blended. The blending ratio of these optional components may be appropriately selected as long as the object of the present invention is not impaired.

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

(the film)
The film of the present invention is a molded article obtained by forming the above-described curable resin composition of the present invention into a sheet or film.

  When the curable resin composition of the present invention is formed into a sheet or film to form a molded article, the resin composition of the present invention is optionally coated with an organic solvent and applied to a support Preferably, it is obtained by spraying or casting and then drying.

  As a support used at this time, a resin film, metal foil, etc. are mentioned. Examples of the resin film include polyethylene terephthalate film, polypropylene film, polyethylene film, polycarbonate film, polyethylene naphthalate film, polyarylate film, nylon film and the like. Among these films, polyethylene terephthalate film or polyethylene naphthalate film is preferable from the viewpoint of heat resistance, chemical resistance, peelability and the like. As metal foil, copper foil, aluminum foil, nickel foil, chromium foil, gold foil, silver foil etc. are mentioned.

  The thickness of the sheet-like or film-like molded article is not particularly limited, but is usually 1 to 150 μm, preferably 2 to 100 μm, and more preferably 5 to 80 μm from the viewpoint of workability and the like. The surface roughness Ra of the support is usually 300 nm or less, preferably 200 nm or less, more preferably 100 nm or less.

  Examples of the method for applying the curable resin composition of the present invention include dip coating, roll coating, curtain coating, die coating, slit coating, and gravure coating.

  In the present invention, as the sheet-like or film-like molded article, the curable resin composition of the present invention is preferably in an uncured or semi-cured state. Here, “uncured” means that substantially all of the alicyclic olefin polymer is dissolved when the molded body is immersed in a solvent capable of dissolving the alicyclic olefin polymer used for the preparation of the composition. State to In addition, semi-hardening is a state in which the resin is partially cured to such an extent that it can be cured by further heating, and preferably, the epoxy is contained in a solvent capable of dissolving the alicyclic olefin polymer used for preparation of the composition. Either a part of the compound is dissolved (specifically, an amount of 7% by weight or more and an amount such that a part remains), or after immersing the formed body in a solvent for 24 hours Volume of 200% or more (swelling rate) of the volume before immersion.

  Moreover, after apply | coating the curable resin composition of this invention on a support body, you may dry as needed. The drying temperature is preferably a temperature at which the curable resin composition of the present invention does not cure, and is usually 20 to 300 ° C., preferably 30 to 200 ° C. If the drying temperature is too high, the curing reaction may proceed too much and the resulting molded article may not be in an uncured or semi-cured state. The drying time is usually 30 seconds to 1 hour, preferably 1 minute to 30 minutes.

  Then, the film of the present invention obtained in this manner is used in the state of being deposited on the support or peeled off from the support.

(Laminated film)
The laminated film of the present invention has a to-be-plated layer composed of the above-described curable resin composition and an adhesive layer composed of the adhesive layer resin composition.

  The adhesive layer resin composition for forming the adhesive layer is not particularly limited, but from the viewpoint of improving the electric properties and heat resistance of the laminated film, it contains an epoxy compound and an active ester compound. preferable.

  The epoxy compound is not particularly limited. For example, phenol novolac epoxy compound, cresol novolac epoxy compound, cresol epoxy compound, bisphenol A epoxy compound, bisphenol F epoxy compound, polyphenol epoxy compound, brominated bisphenol A Ether type epoxy compounds, brominated bisphenol F type epoxy compounds, glycidyl ether type epoxy compounds such as hydrogenated bisphenol A type epoxy compounds, alicyclic epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, isocyanurate type epoxy compounds And epoxy resins having an alicyclic olefin structure or a fluorene structure. Among these, bisphenol A epoxy compounds and epoxy resins having an alicyclic olefin structure or a fluorene structure from the viewpoint that the mechanical properties of the obtained film, laminate and cured product can be made better. Is preferred.

  As the bisphenol A type epoxy compound, for example, trade names “jER 827, jER 828, jER 828 EL, jER 828 XA, jER 834” (above, manufactured by Mitsubishi Chemical Corporation), trade names “Epiclon 840, Epiclon 840-S, Epiclon 850, Epiclon 850-S Epiclon 850-LC "(above, manufactured by Dainippon Ink and Chemicals, Inc.," Epiclon "is a registered trademark), and the like. As an epoxy resin which has an alicyclic olefin structure or a fluorene structure, the thing similar to what was illustrated as a phenol novolak-type epoxy compound (B) mentioned above can be used.

  As the active ester compound, any compound having an active ester group may be used, but in the present invention, a compound having at least two active ester groups in the molecule is preferable. The active ester compound acts as a curing agent for the above-mentioned epoxy compound by the reaction between the ester site and the epoxy group upon heating.

  From the viewpoint of, for example, enhancing the heat resistance of the obtained electrical insulating layer, as an active ester compound, an active ester obtained from a reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. Preferred is a compound, and more preferred is an active ester compound obtained from a reaction of a carboxylic acid compound and one or more selected from the group consisting of a phenol compound, a naphthol compound and a thiol compound, and a carboxylic acid compound Particularly preferred is an aromatic compound obtained from the reaction of an aromatic compound having a phenolic hydroxyl group and having at least two active ester groups in the molecule. The active ester compound may be linear or multi-branched, and exemplified by the case where the active ester compound is derived from a compound having at least two carboxylic acids in the molecule, such at least two carboxylic acids In the case where the compound having in the molecule contains an aliphatic chain, the compatibility with the epoxy compound can be enhanced, and when it has an aromatic ring, the heat resistance can be enhanced.

  Specific examples of the carboxylic acid compound for forming the active ester compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. Among these, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable, and phthalic acid, isophthalic acid, and terephthalic acid are more preferable, from the viewpoint of improving the heat resistance of the obtained electrical insulation layer. Isophthalic acid and terephthalic acid are more preferred.

  Specific examples of the thiocarboxylic acid compound for forming the active ester compound include thioacetic acid, thiobenzoic acid and the like.

  Specific examples of the hydroxy compound for forming the active ester compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone Examples thereof include tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyldiphenol, phenol novolac and the like. Among them, from the viewpoint of improving the solubility of the active ester compound and enhancing the heat resistance of the obtained electrical insulating layer, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxy benzophenone, tetrahydroxy benzophenone, dicyclopentadienyl diphenol, phenol novolac is preferable, dihydroxy benzophenone, trihydroxy benzophenone, tetrahydroxy benzophenone, dicyclopentadienyl diphenol, phenol novolac is more preferable, dicyclopentadi Enyl diphenol and phenol novolac are more preferred.

  Specific examples of the thiol compound for forming the active ester compound include benzene dithiol, triazine dithiol and the like.

  The method for producing the active ester compound is not particularly limited, and the active ester compound can be produced by a known method. For example, it can be obtained by the condensation reaction of the above-mentioned carboxylic acid compound and / or thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound.

  In the present invention, as the active ester compound, for example, an aromatic compound having an active ester group disclosed in JP-A-2002-12650 and a polyfunctional polyester disclosed in JP-A-2004-277460 or And commercially available products can be used. As a commercial item, for example, trade names “EXB9451, EXB9460, EXB9460S, Epiclon HPC-8000-65T” (above, DIC Corporation, “Epiclon” is a registered trademark), trade name “DC808” (Japan Epoxy Resins Co., Ltd.) And trade name “YLH1026” (manufactured by Japan Epoxy Resins Co., Ltd.).

  The compounding amount of the active ester compound in the adhesive layer resin composition used in the present invention is preferably 10 to 150 parts by weight, more preferably 15 to 130 parts by weight, further preferably 100 parts by weight of the epoxy compound to be used. Is in the range of 20 to 120 parts by weight.

  Further, in the resin composition for an adhesive layer used in the present invention, if desired, a filler such as silica, a curing accelerator, a flame retardant, a flame retardant auxiliary, a heat resistant stabilizer, a weather resistant stabilizer, an antiaging agent, ultraviolet light Absorbent agent (laser processability improver), leveling agent, antistatic agent, slip agent, antiblocking agent, antifogging agent, lubricant, dye, natural oil, synthetic oil, wax, emulsion, magnetic material, dielectric property modifier, Known components such as a toughness agent may be appropriately blended.

  The method for producing the adhesive layer resin composition used in the present invention is not particularly limited, and the above-described components may be mixed as they are, or mixed in a state of being dissolved or dispersed in an organic solvent. The composition may be prepared by dissolving or dispersing some of the components in an organic solvent, and the remaining components may be mixed with the composition.

  The laminated film of the present invention is produced using such a resin composition for an adhesive layer and the above-mentioned curable resin composition of the present invention. Specifically, the laminated film of the present invention is prepared, for example, by coating, spraying or casting the above-described curable resin composition of the present invention on a support, and optionally drying it. And then further coating or casting the above-described resin composition for an adhesive layer and optionally drying it; (2) the above-mentioned curable resin composition of the present invention on a support Applied to the support, coated, dispersed or cast, and optionally molded into a sheet or film form obtained by optionally drying, and the above-described resin composition for adhesive layer is applied onto a support , Spraying or casting, optionally drying it, and molding it for an adhesive layer, which is formed into a sheet or film, and laminated, and manufactured by integrating these moldings. can do. Among these production methods, the production method of the above (1) is preferable because it is an easier process and excellent in productivity.

  When the curable resin composition of the present invention is applied, sprayed or cast on a support in the above-mentioned production method (1), and the resin for adhesive layer is applied to the applied, sprayed or cast curable resin composition When the composition is applied, dispersed or cast, or in the production method of the above (2), the curable resin composition and the resin composition for an adhesive layer are formed into a sheet or film to form a layer to be plated When forming a molded article for a body and an adhesive layer, it is preferable to apply, disperse or cast the curable resin composition or the resin composition for an adhesive layer on a support, optionally adding an organic solvent.

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

  The thicknesses of the curable resin composition and the resin composition for the adhesive layer in the above-mentioned production method of (1), or the thicknesses of the molded body for the layer to be plated and the molded article for the adhesive layer in the above-mentioned production method of (2) The thickness of the layer to be plated is preferably 1 to 10 μm, more preferably 1.5 to 8 μm, still more preferably 2 to 5 μm, and the thickness of the adhesive layer is not particularly limited. The thickness is preferably 10 to 100 μm, more preferably 10 to 80 μm, and still more preferably 15 to 60 μm. When the thickness of the layer to be plated is too thin, the formability of the conductor layer may be reduced when the conductor layer is formed by electroless plating on the cured product obtained by curing the laminated film, If the thickness of the layer to be plated is too thick, the linear expansion of the cured product obtained by curing the laminated film may be increased. In addition, when the thickness of the adhesive layer is too thin, the wiring embedding property of the laminated film may be reduced.

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

  In addition, after the curable resin composition is applied, dispersed or cast on the support in the production method of the above (1), or the resin composition for adhesive layer is applied, dispersed or applied onto the curable resin composition. After casting, or after the curable resin composition and the resin composition for an adhesive layer are applied on a support in the above-mentioned production method (2), drying may be performed if desired. The drying temperature is preferably a temperature at which the curable resin composition and the adhesive layer resin composition do not cure, 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 the laminated film of the present invention, it is preferable that the layer to be plated and the adhesive layer constituting the laminated film be in an uncured or semi-cured state. By making these uncured or semi-cured, the laminated film of the present invention can be made highly adhesive. Moreover, the laminated | multilayer film of this invention can exhibit the peeling strength of the plating more excellent by the to-be-plated layer.

(Prepreg)
The prepreg of the present invention comprises the above-described film of the present invention or the laminated film of the present invention and a fiber base.

  Examples of the fiber base include organic fibers such as polyamide fibers, polyaramid fibers and polyester fibers, and inorganic fibers such as glass fibers and carbon fibers. Moreover, as a form of a fiber base material, the form of textiles, such as plain weave or twill weave, or the form of a nonwoven fabric etc. are mentioned. 5-100 micrometers is preferable and, as for the thickness of a fiber base material, the range of 10-50 micrometers is preferable. If the thickness is too thin, the handling becomes difficult, and if the thickness is too thick, the resin layer may be relatively thin and the wiring burying property may be insufficient.

  In the case where the prepreg of the present invention comprises the above-mentioned film of the present invention including the fiber base, the prepreg of the present invention is to impregnate the curable resin composition of the present invention into the fiber base. Can be manufactured. In this case, the method for impregnating the curable resin composition of the present invention into the fiber base is not particularly limited, but an organic solvent is added to the curable resin composition of the present invention in order to adjust viscosity and the like. The method of immersing a fiber base material in the curable resin composition which added the organic solvent, the method of apply | coating and disperse | distributing the curable resin composition which added the organic solvent on a fiber base material etc. are mentioned. In the method of coating or spreading, a fiber base can be placed on a support, and a curable resin composition to which an organic solvent is added can be coated or spread thereon. In the present invention, as the sheet-like or film-like composite molded article, the curable resin composition of the present invention is uncured or semi-cured as in the sheet-like or film-like compact described above. It is preferable to contain.

  In addition, after the curable resin composition of the present invention is impregnated into the fiber substrate, drying may be performed if desired. The drying temperature is preferably a temperature at which the curable resin composition of the present invention does not cure, and is usually 20 to 300 ° C., preferably 30 to 200 ° C. If the drying temperature is too high, the curing reaction may proceed too much, and the resulting composite molded article may not be in an uncured or semi-cured state. The drying time is usually 30 seconds to 1 hour, preferably 1 minute to 30 minutes.

  Alternatively, when the prepreg of the present invention comprises the above-described laminated film of the present invention including a fiber base, the prepreg of the present invention has an adhesive layer on one side and a plating on the other side. The layer preferably has a fiber base inside, and the method for producing the layer is not limited. For example, the following method: (1) Resin composition film for adhesive layer with support and curable resin with support Method of manufacturing the composition film by laminating the resin layer side of each film so as to sandwich the fiber substrate and laminating it under conditions such as pressure, vacuum, heating and the like if desired; (2) adhesion Either a layer resin composition or a curable resin composition is impregnated into the fiber substrate and optionally dried to prepare a prepreg, and the other resin composition is applied, dispersed or cast onto this prepreg. By doing A method of producing by laminating the other support-attached resin composition film; (3) applying, scattering, casting, etc. either the resin composition for the adhesive layer or the curable resin composition on the support It can be manufactured by laminating by laminating the fiber base material on top of that, and further laminating the other resin composition from the top by coating, spreading or casting, and optionally drying. In any of the methods, an organic solvent is optionally added to the composition, and the viscosity of the composition is adjusted to improve the workability in impregnating a fiber substrate, coating on a support, scattering, or casting. It is preferable to control.

  Further, as a support used in this case, resin films such as polyethylene terephthalate film, polypropylene film, polyethylene film, polycarbonate film, polyethylene naphthalate film, polyarylate film, nylon film, copper foil, aluminum foil, nickel foil, Metal foils such as chromium foils, gold foils, silver foils, etc. may be mentioned, and these may be attached not only to one side of the prepreg but also to both sides.

  The thickness of the prepreg of the present invention is not particularly limited, but the thickness of the layer to be plated is preferably 1 to 10 μm, more preferably 1.5 to 8 μm, still more preferably 2 to 5 μm, and the thickness of the adhesive layer is The thickness is preferably 10 to 100 μm, more preferably 10 to 80 μm, and still more preferably 15 to 60 μm.

  When manufacturing the prepreg of the present invention, examples of the method for applying the resin composition for adhesive layer and the curable resin composition include dip coating, roll coating, curtain coating, die coating, slit coating, gravure coating and the like.

  Further, in the prepreg of the present invention, as in the case of the film and the laminated film of the present invention described above, it is preferable that the resin composition constituting the prepreg is in an uncured or semi-cured state.

  And the prepreg of this invention obtained in this way can be made into a hardened | cured material by heating and hardening this.

  The curing temperature is usually 30 to 400 ° C, preferably 70 to 300 ° C, and more preferably 100 to 200 ° C. The curing time is 0.1 to 5 hours, preferably 0.5 to 3 hours. The method of heating is not particularly limited, and may be performed using, for example, an electric oven or the like.

(Laminate)
The laminate of the present invention is obtained by laminating the above-described film, laminated film or prepreg of the present invention on a substrate. The laminate of the present invention may be at least a laminate of the above-described film, laminate film or prepreg of the present invention, but the film of the present invention described above, a substrate having a conductor layer on the surface, and laminate It is preferable to laminate an electric insulating layer made of a film or a prepreg.

  The substrate having the conductor layer on the surface is the one having the conductor layer on the surface of the electrically insulating substrate. The electrically insulating substrate is a resin containing a known electrically insulating material (eg, alicyclic olefin polymer, epoxy compound, maleimide resin, (meth) acrylic resin, diallyl phthalate resin, triazine resin, polyphenylene ether, glass, etc.) It is formed by curing the composition. The conductor layer is not particularly limited, but is usually a layer including a wiring formed of a conductor such as a conductive metal, and may further include various circuits. The configuration, thickness and the like of the wiring and circuit are not particularly limited. A printed wiring board, a silicon wafer board | substrate, etc. can be mentioned as a specific example of a board | substrate which has a conductor layer in the surface. The thickness of the substrate having a conductor layer on its surface is usually 10 μm to 10 mm, preferably 20 μm to 5 mm, more preferably 30 μm to 2 mm.

  In the substrate having a conductor layer on the surface used in the present invention, it is preferable that the surface of the conductor layer is pretreated in order to improve the adhesion to the electrical insulating layer. As a pre-treatment method, known techniques can be used without particular limitation. For example, if the conductor layer is made of copper, an oxidation treatment method in which a strong alkaline oxidizing solution is brought into contact with the surface of the conductor layer to form a layer of copper oxide on the surface of the conductor to roughen the surface; A method of oxidation by the following method followed by reduction with sodium borohydride, formalin, etc., a method of depositing plating on the conductor layer and roughening, a method of contacting an organic acid with the conductor layer to dissolve copper grain boundaries and roughening And a method of forming a primer layer on the conductor layer with a thiol compound or a silane compound. Among them, from the viewpoint of the ease of maintaining the shape of the fine wiring pattern, a method in which an organic acid is brought into contact with the conductor layer to elute and roughen the grain boundaries of copper, and a primer by a thiol compound or a silane compound The method of forming a layer is preferred.

  The laminate of the present invention usually comprises the film of the present invention described above on a substrate having a conductor layer on the surface (that is, a molded product obtained by forming the curable resin composition of the present invention into a sheet or film). A laminated film (that is, a sheet-like or film-like formed article comprising a layer to be plated comprising the curable resin composition of the present invention and an adhesive layer), or a prepreg (a film of the present invention Or a composite molded body comprising a fibrous base material on the laminated film of the present invention, and can be produced by thermocompression bonding.

  As a method of thermocompression bonding, a compact with a support or a composite compact is laminated so as to be in contact with the above-described conductor layer of the substrate, and pressure machines such as a pressure laminator, press, vacuum laminator, vacuum press, roll laminator, etc. The method of thermocompression bonding (lamination) using is mentioned. By heating and pressing, bonding can be performed so that a void does not substantially exist at the interface between the conductor layer on the substrate surface and the formed body or the composite formed body. The molded body or composite molded body is usually laminated to the conductor layer of the substrate in an uncured or semi-cured state.

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

(Cured product)
The cured product of the present invention is obtained by curing the curable resin composition of the present invention, and is produced by curing the film, the laminated film, the prepreg, and the laminate of the present invention, which are composed of the composition. All things are included. Curing can be carried out by appropriately heating the curable resin composition, film and the like of the present invention under the curing conditions described later.

  For example, about the laminated body of this invention, it can be set as hardened | cured material by performing the process which hardens the film, laminated film, or prepreg of this invention which comprises it. Curing is usually carried out by heating the entire substrate on which the film, laminated film or prepreg of the present invention is formed on the conductor layer. Curing can be performed simultaneously with the above-described heat and pressure bonding operation. Alternatively, the heat-pressing operation may be performed under conditions where curing does not occur, that is, at a relatively low temperature for a short time, and then curing may be performed.

  In addition, for the purpose of improving the flatness of the electrical insulating layer or for the purpose of increasing the thickness of the electrical insulating layer, two or more films, laminated films or prepregs of the present invention are contacted and laminated on the conductor layer of the substrate. It is also good.

  The curing temperature is usually 30 to 400 ° C, preferably 70 to 300 ° C, and more preferably 100 to 200 ° C. The curing time is usually 0.1 to 5 hours, preferably 0.5 to 3 hours. The method of heating is not particularly limited, and may be performed using, for example, an electric oven.

(Complex)
The composite of the present invention is obtained by forming a conductor layer on the surface of the cured product of the present invention described above.

  For example, when the laminate of the present invention forms a multilayer substrate, the composite of the present invention is obtained by forming another conductor layer on the electrical insulating layer of the laminate. As such a conductor layer, metal plating or metal foil can be used. Examples of the metal plating material include gold, silver, copper, rhodium, palladium, nickel, tin and the like, and examples of the metal foil include those used as a support of the above-mentioned film, laminated film or prepreg. In the present invention, the method of using metal plating as the conductor layer is preferable from the point that fine wiring is possible. Hereinafter, the method for producing a composite of the present invention will be described by exemplifying a multilayer circuit board using metal plating as a conductor layer as an example of the composite of the present invention.

  First, a via hole or a through hole which penetrates the electrical insulating layer is formed in the laminate. The via holes are formed to connect the conductor layers constituting the multilayer circuit board when the multilayer circuit board is used. The via holes and the through holes can be formed by a chemical process such as photolithography, or by a physical process such as a drill, a laser, or plasma etching. Among these methods, the laser method (carbon dioxide gas laser, excimer laser, UV-YAG laser, etc.) is preferable because finer via holes can be formed without deteriorating the characteristics of the electrical insulating layer.

Next, a surface roughening treatment is performed to roughen the surface of the electrical insulating layer (that is, the cured product of the present invention) of the laminate. The surface roughening treatment is performed to enhance the adhesion to the conductive layer formed on the electrical insulating layer.
Arithmetic mean roughness Ra of the surface of the electrically insulating layer is preferably 0.5 μm or less, more preferably 0.3 μm or less, and surface ten-point mean roughness Rzjis is preferably less than 5 μm, more preferably 3 μm or less It is. In the present 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.

  As the surface roughening method, in the present invention, a method of contacting the surface of the electrical insulating layer with the oxidizing compound may, for example, be mentioned. Examples of the oxidizing compound include known compounds having oxidizing ability such as inorganic oxidizing compounds and organic oxidizing compounds. It is particularly preferable to use an inorganic oxidizing compound or an organic oxidizing compound because of the ease of controlling the surface roughness of the electrical insulating layer. Inorganic oxidizing compounds include permanganate, chromic acid anhydride, bichromate, chromate, persulfate, activated manganese dioxide, osmium tetraoxide, hydrogen peroxide, periodate and the like . Examples of the organic oxidizing compound include dicumyl peroxide, octanoyl peroxide, m-chloroperbenzoic acid, peracetic acid, ozone and the like.

  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 above-mentioned 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, a dip method of immersing the electrical insulating layer in the oxidizing compound solution, using surface tension of the oxidizing compound solution Any method may be used, such as a method in which the oxidizing compound solution is placed on the electrical insulating layer, and a spraying method in which the oxidizing compound solution is sprayed on the electrical insulating layer. By performing the surface roughening treatment, the adhesion between the electrical insulating layer and another layer such as a conductor layer can be improved.

  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 oxidizing compounds, the method of contact, etc. The temperature is 95 ° C., preferably 30 to 85 ° C., and the time is usually 0.5 to 60 minutes, preferably 1 to 40 minutes.

  Note that after the surface roughening treatment, the surface of the electrical insulating layer after the surface roughening treatment is washed with water in order to remove the oxidizing compound. If a substance that can not be washed out with water alone is attached, the substance is further washed with a soluble washing solution or brought into contact with another compound to make the substance soluble in water. Wash with water. For example, when an aqueous alkaline 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, etc., for the purpose of removing the generated manganese dioxide film. It can be washed with water after neutralization reduction treatment with an acidic aqueous solution of

  Next, the surface of the electrical insulation layer of the laminate is roughened, and then a conductor layer is formed on the surface of the electrical insulation layer and the inner wall surfaces of the via holes and through holes. It is preferable to carry out the formation method of a conductor layer by the electroless-plating method from a viewpoint that the conductor layer which is excellent in adhesiveness can be formed.

  For example, when forming a conductor layer by electroless plating, first, before forming a metal thin film on the surface of the electrical insulation layer, catalyst nuclei of silver, palladium, zinc, cobalt, etc. are formed on the electrical insulation layer. It is common to make it adhere. The method of attaching the catalyst nucleus to the electrical insulating layer is not particularly limited, and, for example, metal compounds such as silver, palladium, zinc and cobalt or salts or complexes thereof with water or an organic solvent such as alcohol or chloroform may be used. After immersing in a solution (containing an acid, an alkali, a complexing agent, a reducing agent, etc., if necessary) dissolved at a concentration of 10% by weight, a method of reducing metal, etc. may be mentioned.

  As the electroless plating solution used for the electroless plating method, a known autocatalytic electroless plating solution may be used, and metal species, reducing agent species, complexing agent species, hydrogen ion concentration, and the like contained in the plating solution, The dissolved oxygen concentration and the like are not particularly limited. For example, an electroless copper plating solution containing ammonium hypophosphite, hypophosphorous acid, ammonium borohydride, hydrazine, formalin or the like as a reducing agent; an electroless nickel-phosphorus 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-phosphorus plating solution using sodium hypophosphite as a reducing agent can be used.

  After forming the metal thin film, the surface of the substrate can be brought into contact with an antirust agent to carry out an antirust treatment. In addition, after the metal thin film is formed, the metal thin film can also be heated to improve adhesion and the like. The heating temperature is usually 50 to 250 ° C, preferably 80 to 200 ° C.

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

  The multilayer circuit substrate obtained as described above is used as a substrate for producing the above-described laminate, and this is subjected to heat and pressure bonding with the above-described molded body or composite molded body to form an electrical insulating layer. Further, on this, the formation of the conductive layer is performed according to the above-mentioned method, and by repeating these, further multi-layering can be performed, whereby a desired multilayer circuit board can be obtained.

  The composite of the present invention (and the multilayer circuit board as an example of the composite of the present invention) thus obtained has an electrical insulating layer (the cured product of the present invention) composed of the curable resin composition of the present invention. The curable resin composition of the present invention can stably provide an electrical insulating layer having low surface roughness and excellent adhesion to a conductor layer even when the surface roughening treatment conditions are changed. As it is possible, the composite of the present invention (and the multilayer circuit board as an example of the composite of the present invention) can be suitably used for various applications.

(Substrate for electronic materials)
The substrate for electronic materials of the present invention comprises the above-mentioned cured product or composite of the present invention. The substrate for electronic materials of the present invention comprising the cured product or composite of the present invention is a mobile phone, PHS, laptop computer, PDA (portable information terminal), mobile television phone, personal computer, super computer, server, Router, LCD projector, engineering workstation (EWS), pager, word processor, television, viewfinder or monitor direct view video tape recorder, electronic organizer, electronic desktop computer, car navigation device, POS terminal, device with touch panel And other electronic devices.

  Hereinafter, the present invention will be more specifically described by way of examples and comparative examples. In the examples, "parts" and "%" are on a weight basis unless otherwise noted. Various physical properties were evaluated according to the following method.

(1) Number average molecular weight (Mn), weight average molecular weight (Mw) of alicyclic olefin polymer
It measured by gel permeation chromatography (GPC) by using tetrahydrofuran as a developing solvent, and it calculated | required as polystyrene conversion value.

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

(3) Content of Monomer Unit Having Carboxylic Anhydride Group in Alicyclic Olefin Polymer The number of moles of monomer unit having a carboxylic anhydride group relative to the total number of monomer units in the polymer The ratio of H was determined by 400 MHz ¹ H-NMR spectrum measurement, and this was taken as the content of monomer units having a carboxylic acid anhydride group of the polymer.

(4) Surface roughness (arithmetic mean roughness Ra) of electrical insulating layer (to-be-plated layer)
The surface roughness of the to-be-plated layer obtained by dissolving the copper on the surface of the multilayer printed wiring board with an ammonium persulfate solution was measured using a surface shape measuring device (WYKO NT1100, manufactured by Becoin Instruments) in a measuring range of 91 μm × 120 μm. The (arithmetic mean roughness Ra) was measured.
In the present embodiment, two types of multilayer printed wiring boards having different treatment times (surface roughening treatment time) in the oxidation treatment process described later (80.degree. C. for 15 minutes, and 80.degree. C. for 30 minutes) The surface roughness was measured for each of these two types of multilayer printed wiring boards.
○: surface roughness Ra is less than 200 μm Δ: surface roughness Ra is 200 μm or more and less than 300 μm ×: surface roughness Ra is 300 μm or more

(5) Adhesion (peel strength) between the electrically insulating layer (the layer to be plated) and the conductor layer
The peel strength (peel strength) of the layer to be plated and the copper plating layer in a multilayer printed wiring board was measured in accordance with JIS C6481-1996.
In the present embodiment, two types of multilayer printed wiring boards having different treatment times (surface roughening treatment time) in the oxidation treatment process described later (80.degree. C. for 15 minutes, and 80.degree. C. for 30 minutes) The peel strength was measured for each of these two types of multilayer printed wiring boards.
○: Peel strength is 6 N / cm or more Δ: Peel strength is 4 N cm or more and less than 6 N / cm ×: Peel strength is less than 4 N cm

Synthesis example 1
As the first stage of polymerization, 35 molar parts of 5-ethylidene-bicyclo [2.2.1] hept-2-ene (EdNB), 0.9 molar parts of 1-hexene, 340 molar parts of anisole and 4-acetoxybenzylidene (dichloro) In a pressure-resistant glass reactor in which 0.005 part of (4,5-dibromo-1,3-dimesityl-4-imidazolin-2-ylidene) (tricyclohexylphosphine) ruthenium (C1063, manufactured by Wako Pure Chemical Industries, Ltd.) is replaced with nitrogen. The mixture was charged, and a polymerization reaction was performed at 80 ° C. for 30 minutes under stirring to obtain a solution of a norbornene ring-opening polymer.
Then, tetracyclo ^{[9.2.1.0 2,10} in the solution obtained in the polymerization the first stage as the polymerization second stage. 0 ^3,8 ] Tetradeca-3,5,7,12-tetraene (MTF) 35 mol parts, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride (NDCA) 30 mol A part, 250 mol parts of anisole and 0.01 part of C1063 were added, and a polymerization reaction was carried out at 80 ° C. for 1.5 hours under stirring to obtain a solution of a norbornene ring-opening polymer. The solution was subjected to gas chromatography measurement to confirm that substantially no monomer remained, and the polymerization conversion was 99% or more.
Subsequently, the solution of the obtained ring-opened polymer is charged into a nitrogen-substituted autoclave with a stirrer, 0.03 parts of C1063 is added, and stirring is performed for 5 hours at 150 ° C. and hydrogen pressure 7 MPa to carry out a hydrogenation reaction A solution of an alicyclic olefin polymer (A-1) which is a hydrogenated product of a norbornene ring-opening polymer was obtained. The weight average molecular weight of the obtained polymer (A-1) was 60,000, the number average molecular weight was 30,000, and the molecular weight distribution was 2. The hydrogenation rate was 95%, and the content of the monomer unit having a carboxylic acid anhydride group was 30 mol%. The solid content concentration of the solution of the polymer (A-1) was 22%.

Example 1
(Preparation of a curable resin composition)
455 parts (100 parts by weight of the alicyclic olefin polymer (A-1)) of the solution of the alicyclic olefin polymer (A-1) obtained in Synthesis Example 1, phenol novolac epoxy compound (B) 31 parts of novolac type epoxy compound (Epiclon HP 7200H, manufactured by DIC, epoxy equivalent 278) having a dicyclopentadiene structure as a surface-treated inorganic filler (C), spherical silica (Admafine (registered trademark) SO-C1, Ad An amino group formed by treating Matex (volume average particle diameter 0.25 μm) with N-phenyl-3-aminopropyltrimethoxysilane (KBM-573, Shin-Etsu Chemical Co., Ltd., amino group-containing silane coupling agent) 60 parts of treated silane coupling agent treated silica, tetrakis (1,2,2,6,6-pentamethyl as anti-aging agent 4-piperidyl) 1,2,3,4-butanetetracarboxylate (Adekastab (registered trademark) LA 52, manufactured by ADEKA Corporation) 1.3 parts, tris- (3,5-di-t-butyl-) as an antioxidant 1 part of 4-hydroxybenzyl) -isocyanurate (IRGANOX (registered trademark) 3114, manufactured by BASF Corp.), 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl as a laser processability improver 1 part of 2 H-benzotriazole (TINUVIN 234, manufactured by BASF) and 335 parts of anisole were mixed, and stirred with a planetary stirrer for 3 minutes.
Further, 1 part (0.5 parts in terms of 1-benzyl-2-phenylimidazole) of a solution in which 50% of 1-benzyl-2-phenylimidazole is dissolved in anisole as a curing accelerator is mixed therewith, and the planetary system is used. It stirred for 5 minutes with a stirrer, and obtained the varnish of the curable resin composition for to-be-plated layers.

(Resin composition for adhesive layer)
80 parts of phenol novolac epoxy compound (Epiclon HP 7200H, manufactured by DIC, epoxy equivalent 278) having a dicyclopentadiene structure, 20 parts of tetrakis hydroxyphenylethane epoxy compound (jER 1031S, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 200), activity 90 parts of ester compound (Epiclon HPC-8000-65T, toluene solution with nonvolatile content of 65%, active ester group equivalent weight 223, manufactured by DIC, 350 parts of silica (trade name "SC2500-SXJ", manufactured by Admatex Co., Ltd.), aging As an inhibitor, 0.95 parts of tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate (IRGANOX® 3114, manufactured by BASF Corp.) and 97 parts of anisole are mixed, and a planet is formed. Stirred for 3 minutes with a mechanical stirrer
Further, 9 parts (4.5 parts in terms of 1-benzyl-2-phenylimidazole) of a solution in which 50% of 1-benzyl-2-phenylimidazole is dissolved in anisole as a curing accelerator is mixed, and a planetary type The mixture was stirred for 5 minutes with a stirrer to obtain a varnish of the resin composition for an adhesive layer.

(Preparation of laminated film)
The varnish of the curable resin composition for a layer to be plated obtained above is applied on a polyethylene terephthalate film (support) having a thickness of 100 μm using a wire bar, and then at 85 ° C. in a nitrogen atmosphere. The film was dried for 5 minutes to obtain a film with a support having a thickness of 3 μm formed of a non-cured curable resin composition.

  Next, a varnish of the resin composition for an adhesive layer obtained above is formed on a surface of a film to be plated comprising a curable resin composition of a film with a support, a doctor blade (manufactured by Tester Sangyo Co., Ltd.) and an auto film. The laminated film with a support on which a plating layer having a total thickness of 40 μm and an adhesive layer were formed by applying using an applicator (manufactured by Tester Sangyo Co., Ltd.) and then drying under nitrogen atmosphere at 80 ° C. for 10 minutes Obtained. The obtained laminated film with a support was formed in the order of a support, a to-be-plated layer composed of a curable resin composition, and an adhesive layer composed of a resin composition for an adhesive layer.

(Preparation of laminate)
Next, separately from the above, copper having a thickness of 35 μm is stuck on the surface of a core material obtained by impregnating glass fiber and a varnish containing a halogen-free epoxy resin into glass fiber and having a thickness of 0.8 mm X A double-sided copper-clad laminate substrate (inner layer substrate) was obtained in which the copper surface of a 150 mm long x 150 mm wide double-sided copper-clad laminate substrate was microetched by contact with an organic acid.

  The above-obtained adhesive film with a support cut into 150 mm squares is attached to both surfaces of this inner layer substrate so that the surface on the resin composition side for the adhesive layer is the inner side, and then the primary press Did. The primary press is a thermocompression bonding with a temperature of 110 ° C. and a pressure of 0.1 MPa for 90 seconds under a reduced pressure of 200 Pa with a vacuum laminator equipped with heat resistant rubber press plates at the top and bottom. Furthermore, heat pressing was carried out at a pressing temperature of 110 ° C. and 1 MPa for 90 seconds using a hydraulic pressing device provided with metal pressing plates at the top and bottom. Subsequently, the support was peeled off to obtain a laminate of a resin layer composed of a curable resin composition and a resin composition for an adhesive layer and an inner layer substrate. Further, the laminate was left to stand at 180 ° C. for 60 minutes in an air atmosphere to cure the resin layer and form an electrical insulating layer on the inner layer substrate.

(Swelling process)
The resulting laminate was prepared at a temperature of 60 ° C. so as to be 500 mL / L of swelling liquid (“Swelling Dip Securigant P”, manufactured by Atotech Co., Ltd., “Securigant” is a registered trademark) and 3 g / L of sodium hydroxide. The plate was shaken and immersed in an aqueous solution for 15 minutes and then washed with water.

(Oxidation treatment process)
Subsequently, it is subjected to rocking immersion in an aqueous solution of 80 ° C. prepared to have an aqueous solution of permanganate (“Concentrate Compact CP”, manufactured by Atotech Co., Ltd.) 640 mL / L and a sodium hydroxide concentration of 40 g / L. did.
In addition, in the present Example, the laminated body which made rocking immersion time in the aqueous solution of 80 degreeC 15 minutes for 15 minutes, and the laminated body made 30 minutes were obtained. That is, laminates different in oxidation treatment time (surface roughening treatment time) were obtained, and each of the following steps was performed on each of the laminates different in oxidation treatment time.

(Neutralization reduction treatment process)
Subsequently, the aqueous solution of hydroxyamine sulfate ("Reduction Security G 500", manufactured by Atotech, "Security G") is 100 mL / L, sulfuric acid 35 mL / L prepared at 40 ° C. aqueous solution, laminated body The film was immersed for 5 minutes, subjected to neutralization reduction treatment, and then washed with water.

(Cleaner-conditioner process)
Next, the laminate is immersed for 5 minutes in a 50 ° C. aqueous solution adjusted to a concentration of 50 ml / L with a cleaner / conditioner aqueous solution ("Al cup MCC-6-A", manufactured by Uemura Kogyo Co., Ltd., "Al cup" is a registered trademark) , Cleaner-conditioner treatment. Subsequently, after immersing a laminated body in 40 degreeC wash water for 1 minute, it washed with water.

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

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

(Catalyst application process)
Then, 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 (trade name, manufactured by Mura Kogyo Co., Ltd., "Alcupe" The laminate was immersed for 5 minutes in a 60 ° C. Pd salt-containing plating catalyst aqueous solution prepared to have a registered trademark of 30 mL / L and sodium hydroxide of 0.35 g / L, and then washed with water.

(Activation process)
Subsequently, 20 mL / L of Alcup Red Reuser MAB-4-A (trade name, manufactured by Uemura Kogyo Co., Ltd., "Alcup" is a registered trademark), Alcup Red Reusser MAB-4-B (trade name, manufactured by Kamimura Kogyo Co., Ltd.), The laminate 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)
Then, the laminate was immersed at 25 ° C. for 1 minute 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) is 50 mL / L. .

(Electroless plating process)
Thus, the laminate obtained in this manner is Sulcup PEA-6-A (trade name, manufactured by Kamimura Kogyo Co., Ltd., "Sulcup" is a registered trademark) 100 mL / L, Sulcup PEA-6-B-2X (trade name, Kamimura) Made by Industrial Co., Ltd.) 50 mL / L, Sul cup PEA-6-C (trade name, manufactured by Kamimura Kogyo Co., Ltd.) 14 mL / L, Sul cup PEA-6-D (trade name, manufactured by Kamimura Kogyo) 15 mL / L, Sul cup PEA-6 No immersing for 20 minutes at a temperature of 36 ° C while blowing air into the electroless copper plating solution prepared to be 50 mL / L of E (trade name, manufactured by Kamimura Kogyo Co., Ltd.) and 5 mL / L of a 37% formalin aqueous solution The electroless copper plating process was performed and the electroless-plating film | membrane was formed in the laminated body surface (surface of the to-be-plated layer which consists of a resin composition for to-be-plated layers). Next, annealing was performed at 150 ° C. for 30 minutes in an air atmosphere.

  The laminate subjected to the annealing treatment was subjected to electrolytic copper plating to form an electrolytic copper plating film having a thickness of 30 μm. Then, the laminate was subjected to heat treatment at 180 ° C. for 60 minutes to obtain a double-sided multilayer printed wiring board in which a circuit was formed on the laminate by the conductor layer comprising the metal thin film layer and the electrolytic copper plating film. And the surface roughness (arithmetic mean roughness Ra) of a to-be-plated layer and the adhesiveness (peel strength) of a to-be-plated layer and a metal layer were evaluated according to the said method about the obtained multilayer printed wiring board. In the present embodiment, the multilayer printed wiring board obtained with the treatment time (surface roughening treatment time) in the above-mentioned oxidation treatment step being 15 minutes, and the multilayer printed wiring board obtained with the treatment time being 30 minutes, respectively. The above evaluations were made for The results are shown in Table 1.

Examples 2, 3 and Comparative Examples 1, 2
A varnish of a curable resin composition and a multilayer print in the same manner as in Example 1 except that the composition is changed according to the composition of the curable resin composition in Examples 2 and 3 and Comparative Examples 1 and 2 in Table 1. The wiring board was obtained and similarly measured and evaluated. The results are shown in Table 1.
In addition, in Table 1, each compound shown in Table 1 is as follows.
The “dicyclopentadiene structure-containing phenol novolac epoxy compound (HP7200HH)” is a phenol novolac epoxy compound having a dicyclopentadiene structure (Epiclon HP7200HH, manufactured by DIC, epoxy equivalent: 282).
-"Bisphenol A type epoxy compound (jER 828 EL)" is a bisphenol A type epoxy compound (jER 828 EL, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 186).
"Untreated silica" is a non-treated spherical silica (Admafine (registered trademark) SO-C1, manufactured by Admatex, volume average particle diameter 0.25 μm).

As shown in Table 1, according to the curable resin composition of the present invention, when the treatment time (surface roughening treatment time) in the oxidation treatment step is 80 ° C., 15 minutes, it is 80 ° C., 30 minutes In any of the cases, it can be seen that an electrical insulating layer (layer to be plated) having low surface roughness and excellent adhesion to the conductor layer can be formed (Examples 1 to 3). Therefore, according to the curable resin composition of the present invention, an electrical insulating layer having a large margin for surface roughening treatment conditions, a low surface roughness, and excellent adhesion to a conductor layer is subjected to the surface roughening treatment conditions. It can be seen that stable acquisition is possible without strict control.
On the other hand, when it does not contain a phenol novolak type epoxy compound (B), or when using an inorganic filler which is not treated with a silane coupling agent, the treatment time (surface roughening treatment time) in the oxidation treatment step is The surface roughness of the resulting electrical insulating layer and the adhesion to the conductor layer were inferior (comparative examples 1 and 2).

Claims (11)

Carboxyl group, an alicyclic olefin polymer having at least one functional group selected from carboxylic acid anhydride group and a phenolic hydroxyl group and (A),
Include phenol novolak type epoxy compound having a condensed polycyclic structure (B), and surface-treated inorganic filler with a silane coupling agent and (C),
The epoxy equivalent of the phenol novolac epoxy compound (B) is 265 to 400,
The alicyclic olefin polymer (A) with respect to 100 parts by weight, Ri 100 parts by weight of Der content from 10 of the phenol novolak type epoxy compound (B),
The phenol novolac epoxy compound (B) has a dicyclopentadiene structure,
Curable resin composition. The curable resin composition according to claim 1, wherein the content ratio of the inorganic filler (C) is 5 to 50% by weight. The curable resin composition according to claim 1, wherein the content of the alicyclic olefin polymer (A) in the curable resin composition is larger than the content of the inorganic filler (C). Film made of a curable resin composition according to any one of claims 1 to 3. And the object to be plated layer made of a curable resin composition according to any one of claims 1 to 3,
And an adhesive layer comprising the resin composition for adhesive layer. The laminated film according to claim 5, wherein the adhesive layer resin composition contains an epoxy compound and an active ester compound. The film according to claim 4 , or the laminated film according to claim 5 or 6,
A prepreg comprising a fibrous base material. A film according to claim 4, or a laminated film according to claim 5 or 6 , or a prepreg according to claim 7.
A laminate formed by laminating on a substrate. The curable resin composition according to any one of claims 1 to 3, or film according to claim 4, or laminate film according to claim 5 or 6, or prepreg according to claim 7, or A cured product obtained by curing the laminate according to claim 8. A composite formed by forming a conductor layer on the surface of the cured product according to claim 9. A substrate for electronic material comprising the cured product according to claim 9 or the composite according to claim 10 as a constituent material.