JP2012136646A - Curing resin composition, cured material, laminate body, multilayer circuit board, and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curing resin composition providing a cured material having low linear expansion, being excellent in heat resistance, wire burying flatness and resin strength.SOLUTION: The curing resin composition includes an alicyclic olefin polymer (A) having a carboxyl group and/or a carboxylic anhydride group, a curing agent (B) having at least two functional group, and an alicyclic olefin structure or a fluorene structure, and an inorganic filler (C), wherein the blend amount of the inorganic filler (C) is 30 to 90 wt.%.

Description

  The present invention relates to a curable resin composition, a cured product, a laminate, a multilayer circuit board, and an electronic device.

  With the pursuit of downsizing, multi-functionalization, high-speed communication, etc. of electronic devices, there is a need for higher density circuit boards used in electronic devices. To meet such demands for higher density, Circuit boards are being made multilayered. In such a multilayer circuit board, for example, an electrical insulation layer is laminated on an inner layer substrate composed of an electrical insulation layer and a conductor layer formed on the surface thereof, and a conductor layer is formed on the electrical insulation layer. Further, it is formed by repeatedly stacking these electrical insulating layers and forming the conductor layer. When the conductor layer of such a multilayer circuit board has a high-density pattern, the insulating film used to form the electrical insulating layer has good electrical characteristics such as low dielectric constant and excellent embedded flatness. Desired.

  As a material for forming an insulating film used for forming such an electric insulating layer, an alicyclic olefin polymer has been studied.

  For example, Patent Document 1 discloses norbornene as a norbornene-based resin composition that provides a material having sufficient mechanical strength even at high temperatures, low linear expansion, excellent heat resistance, low moisture absorption, and dielectric properties. 90% by weight of a norbornene polymer having a glass transition temperature of 180 ° C. or higher by DSC measurement and a filler of 10% to 99% by weight. And a norbornene-based resin composition comprising:

  By the way, when a filler is blended in a resin composition such as a norbornene-based resin composition, the filler aggregates and settles during storage, the viscosity of the resin composition increases, and the handleability deteriorates. Furthermore, when a molded body is obtained using such a resin composition, there may be a problem that the filler does not aggregate and become homogeneous in the molded body.

  On the other hand, as a method for producing a varnish having excellent dispersion stability of the filler and having a small viscosity change during storage, for example, Patent Document 2 discloses a polymer having a predetermined polar group, a filler, When producing a varnish containing an epoxy compound and an organic solvent, a polymer solution and a filler slurry are prepared in advance, the filler slurry is added to the polymer solution, and then the viscosity of the resulting mixture is changed for 10 minutes. After stirring until the rate becomes 2% or less, a method of adding an epoxy compound and then stirring until the rate of change in viscosity of the mixed solution obtained here for 10 minutes becomes 2% or less is disclosed.

JP 11-43566 A JP 2008-1871 A

However, as a result of studies by the present inventors, it is possible to obtain a molded article having low linear expansion and excellent heat resistance and mechanical strength by the technique described in Patent Document 1 above. When the molded body is used as the insulating layer of the circuit board, the embedded flatness of the wiring constituting the circuit is still insufficient. The reason for this is considered to be that the norbornene-based resin composition described in Patent Document 1 has a high melt viscosity. Moreover, the cured product using the varnish obtained by the technique described in Patent Document 2 has a problem that it does not sufficiently satisfy the balance between wiring embedding flatness, low linear expansion coefficient, and heat resistance.
An object of the present invention is a curable resin composition that provides a cured product having low linear expansion, excellent heat resistance and wiring embedding flatness, and excellent resin strength, as well as a cured product obtained by using this, and a laminate It is to provide a body, a multilayer circuit board, and an electronic device.

  As a result of intensive studies to achieve the above object, the present inventors have found that an alicyclic olefin polymer having a carboxyl group and / or a carboxylic anhydride group, at least two functional groups, and an alicyclic olefin structure or A curable resin composition containing a curing agent having a fluorene structure and an inorganic filler has a low melt viscosity even when the blending amount of the inorganic filler is increased to 30 to 90% by weight. The cured product obtained by using a simple curable resin composition is found to have low linear expansion, excellent heat resistance and wiring embedding flatness, and excellent resin strength, and complete the present invention. It came to.

That is, according to the present invention,
[1] An alicyclic olefin polymer (A) having a carboxyl group and / or a carboxylic anhydride group, a curing agent (B) having at least two functional groups, and an alicyclic olefin structure or a fluorene structure, and A curable resin composition comprising an inorganic filler (C), wherein a blending amount of the inorganic filler (C) is 30 to 90% by weight;
[2] The alicyclic olefin polymer (A) having the carboxyl group and / or carboxylic acid anhydride group has a weight average molecular weight of 20,000 or more and 100,000 or less. An alicyclic olefin polymer (A1) having a group, and an alicyclic olefin polymer (A2) having a carboxyl group and / or a carboxylic anhydride group having a weight average molecular weight of 5,000 or more and less than 20,000 The blend ratio of the alicyclic olefin polymer (A1) and the alicyclic olefin polymer (A2) is 5/95 in a weight ratio of “polymer (A1) / polymer (A2)”. The curable resin composition according to [1], which is 70/30,
[3] The curing agent (B) is an epoxy resin (B1) having at least two functional groups and an alicyclic olefin structure or fluorene structure, at least two functional groups, and an alicyclic olefin structure or fluorene. The curable resin composition according to the above [1] or [2], comprising a phenol resin (B2) having a structure;
[4] The curable resin composition according to any one of [1] to [3], wherein the inorganic filler (C) is silica obtained by treating the surface with a silane coupling agent.
[5] A cured product obtained by curing the curable resin composition according to any one of [1] to [4],
[6] A laminate formed by laminating a substrate having a conductor layer on the surface and an electrical insulating layer made of the cured product according to [5],
[7] A multilayer circuit board obtained by further forming a conductor layer on the electrical insulating layer of the laminate according to [6], and
[8] An electronic device including the multilayer circuit board according to [7],
Is provided.

  According to the present invention, a curable resin composition that provides a cured product that has low linear expansion, excellent heat resistance and wiring embedding flatness, and excellent resin strength, and a cured product, laminate, multilayer circuit board, In addition, an electronic device can be provided. In particular, since the curable resin composition of the present invention has a low melt viscosity, when used as a cured product, the linear expansion is small, and the wiring embedded flatness is improved while maintaining good heat resistance and resin strength. It is something that can be done.

  The curable resin composition of the present invention has an alicyclic olefin polymer (A) having a carboxyl group and / or a carboxylic anhydride group, at least two functional groups, and an alicyclic olefin structure or a fluorene structure. It contains a curing agent (B) and an inorganic filler (C), and the blending amount of the inorganic filler (C) is 30 to 90% by weight.

(Alicyclic olefin polymer having carboxyl group and / or carboxylic anhydride group (A))
The fat constituting the alicyclic olefin polymer (A) having a carboxyl group and / or a carboxylic acid anhydride group used in the present invention (hereinafter abbreviated as “alicyclic olefin polymer (A)” as appropriate). Examples of the ring structure include a cycloalkane structure and a cycloalkene structure, and a cycloalkane structure is preferable from the viewpoint of mechanical strength, heat resistance, and the like. Examples of the alicyclic structure include monocycles, polycycles, condensed polycycles, bridged rings, and polycycles formed by combining these. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually in the range of 4 to 30, preferably 5 to 20, more preferably 5 to 15, and the carbon atoms constituting the cyclic structure. When the number is in this range, the mechanical strength, heat resistance, and moldability are highly balanced and suitable. The alicyclic olefin polymer (A) is usually thermoplastic. In the present specification, the “carboxylic anhydride group” refers to an atomic group represented by —CO—O—CO—.

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

  Even if the carboxyl group and / or carboxylic anhydride group contained in the alicyclic olefin polymer (A) is directly bonded to the atoms constituting the main chain of the polymer, it is a methylene group, an oxy group, an oxycarbonyl group. You may couple | bond together through other bivalent groups, such as an oxyalkylene group and a phenylene group. Although the content rate of the carboxyl group and / or carboxylic anhydride group in the alicyclic olefin polymer (A) is not particularly limited, it depends on the number of moles of all repeating units constituting the alicyclic olefin polymer (A). On the other hand, it is usually 5 to 60 mol%, preferably 10 to 50 mol%.

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 a carboxyl group and / or a carboxylic anhydride group (hereinafter referred to as “carboxyl group or the like” as appropriate) is added with other monomers as necessary, A method of polymerizing, (2) a method of copolymerizing an alicyclic olefin having no carboxyl group or the like with a monomer having a carboxyl group or the like, and (3) an aromatic olefin having a carboxyl group or the like, if necessary. A method of polymerizing by adding another monomer and hydrogenating the aromatic ring portion of the polymer obtained thereby, (4) a monomer having a carboxyl group or the like, an aromatic olefin having no carboxyl group or the like Or a method of hydrogenating the aromatic ring portion of the polymer obtained by this, or (5) a compound having a carboxyl group or the like in an alicyclic olefin polymer having no carboxyl group or the like Or (6) hydrolyzing, for example, a carboxylic acid ester group of an alicyclic olefin polymer having a carboxylic acid ester group obtained as described in (1) to (5) above. It can obtain by the method etc. which convert to a carboxyl group by etc. Among these, a polymer obtained by the method (1) described above is preferable.
As the polymerization method for obtaining the alicyclic olefin polymer (A) used in the present invention, ring-opening polymerization or addition polymerization is used. In the case of ring-opening polymerization, it is preferable to hydrogenate the obtained ring-opening polymer. .

Specific examples of the alicyclic olefin having a carboxyl group and / or a carboxylic anhydride group include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 9-hydroxycarbonyltetracyclo [6.2.1.1 ^{3 , 6} . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-carboxymethyl-9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 5-exo-6-endo-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 9-exo-10-endo-dihydroxycarbonyltetracyclo [6. 2.1.1 ^3,6 . Alicyclic olefin having a carboxyl group such as 0 ^2,7 ] dodec-4-ene; bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, tetracyclo [6.2. 1.1 ^{3, 6} . 0 ^2,7] dodeca-4-ene-9,10-dicarboxylic anhydride, hexacyclo [10.2.1.1 ^{3, 10.} 1 ^5,8 . 0 ^2,11 . And the like; 0 ^4,9] heptadec-6-ene-13,14-alicyclic olefin having a carboxylic acid anhydride group, such as a dicarboxylic acid anhydride. These may be used alone or in combination of two or more.

In addition, examples of the alicyclic olefin having a carboxylic acid ester group include 9-methyl-9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2 -Ene and the like.

Specific examples of the alicyclic olefin having no carboxyl group and / or carboxylic anhydride 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. These may be used alone or in combination of two or more.

  Examples of the aromatic olefin having no carboxyl group and / or carboxylic anhydride group include styrene, α-methylstyrene, divinylbenzene and the like. These may be used alone or in combination of two or more.

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

  As a monomer having no carboxyl group and / or carboxylic anhydride group other than the alicyclic olefin, which can be copolymerized with an alicyclic olefin or an aromatic olefin, a carboxyl group and / or a carboxylic anhydride Examples thereof include ethylenically unsaturated compounds having no physical group, and specific examples thereof include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, and 3-methyl-1- Pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl- 1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, -Ethylene or α-olefin having 2 to 20 carbon atoms such as eicosene; non-such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene Conjugated dienes; and the like. These may be used alone or in combination of two or more.

  In the present invention, as the alicyclic olefin polymer (A) having a carboxyl group and / or a carboxylic acid anhydride group, a polymer having a weight average molecular weight of 20,000 or more and 100,000 or less (hereinafter referred to as appropriate). , “High molecular weight alicyclic olefin polymer (A1)”) and a polymer having a weight average molecular weight of 5,000 or more and less than 20,000 (hereinafter referred to as “low molecular weight alicyclic olefin polymer as appropriate”). (A2) ”) is preferably used. By using the high molecular weight alicyclic olefin polymer (A1) and the low molecular weight alicyclic olefin polymer (A2) having different molecular weights in combination, the melt viscosity of the curable resin composition can be obtained. The resin strength of the cured product can be highly balanced.

  The blending ratio of the high molecular weight alicyclic olefin polymer (A1) and the low molecular weight alicyclic olefin polymer (A2) is “high molecular weight alicyclic olefin polymer (A1) / low molecular weight alicyclic olefin polymer”. The weight ratio of (A2) ”is preferably 5/95 to 70/30, more preferably 8/92 to 50/50, and still more preferably 12/88 to 30/70. If the amount of the high molecular weight alicyclic olefin polymer (A1) is too small, the resin strength in the case of a cured product may be lowered. On the other hand, if the amount of the low molecular weight alicyclic olefin polymer (A2) is too small, When the viscosity is increased and the cured product is used, the wiring embedding flatness may be lowered.

  The weight average molecular weight of the high molecular weight alicyclic olefin polymer (A1) is from 20,000 to 100,000, preferably from 30,000 to 80,000, more preferably from 40,000 to 60,000. 000 or less. If the molecular weight of the high molecular weight alicyclic olefin polymer (A1) is too low, the resin strength of the resulting cured product may be reduced.

  The weight average molecular weight of the low molecular weight alicyclic olefin polymer (A2) is 5,000 or more and less than 20,000, preferably 7,000 or more and 17,000 or less, more preferably 9,000 or more and 15, 000 or less. If the molecular weight of the low molecular weight alicyclic olefin polymer (A2) is too high, it may be difficult to obtain the effect of reducing the melt viscosity of the curable resin composition.

  The weight average molecular weights of the high molecular weight alicyclic olefin polymer (A1) and the low molecular weight alicyclic olefin polymer (A2) are, for example, converted to polystyrene by gel permeation chromatography using tetrohydrofuran as a solvent. Can be measured.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

After the hydrogenation reaction, a treatment for removing the catalyst used in the hydrogenation reaction may be performed. The method for removing the catalyst is not particularly limited, and examples thereof include centrifugation and filtration. Furthermore, the catalyst removal can be promoted by adding a catalyst deactivator such as water or alcohol, or by adding an adsorbent such as activated clay, alumina, or silicon earth.
The alicyclic olefin polymer (A) used in the present invention may be used as a polymer solution after polymerization or hydrogenation reaction or may be used after removing the solvent. When preparing a product, the additive is preferably dissolved and dispersed, and the process can be simplified, so that it is preferably used as a polymer solution.

(Curing agent (B))
The curable resin composition of the present invention has a curing agent (B) having at least two functional groups and an alicyclic olefin structure or a fluorene structure (hereinafter abbreviated as “curing agent (B)” as appropriate). Containing.
Here, as the at least two functional groups of the curing agent (B), groups capable of reacting with the carboxyl group and / or carboxylic anhydride group of the alicyclic olefin polymer (A) to form a bond. There is no particular limitation as long as it is sufficient. Examples of the functional group include an epoxy group, an amino group, a hydroxyl group, and an isocyanate group.

  The curing agent (B) used in the present invention is an epoxy resin (B1) having at least two functional groups and an alicyclic olefin structure or a fluorene structure (hereinafter abbreviated as “epoxy resin (B1)” as appropriate). Or a phenol resin (B2) having at least two functional groups and an alicyclic olefin structure or a fluorene structure (hereinafter abbreviated as “phenol resin (B2)” as appropriate), and a curing agent. (B) is more preferably a combination of the epoxy resin (B1) and the phenol resin (B2) from the viewpoint of increasing the crosslink density and improving the resin strength.

  In the curing agent (B) used in the present invention, the “alicyclic olefin structure” is preferably an alicyclic structure having at least one carbon-carbon double bond in the alicyclic ring. The alicyclic structure may be a monocyclic structure or a polycyclic structure. The “fluorene structure” refers to the following structure.

  As an epoxy resin (B1) having at least two functional groups and an alicyclic olefin structure or a fluorene structure, an epoxy resin having a dicyclopentadiene skeleton [for example, trade names “Epicron (registered trademark) HP7200L, Epicron (registered) Trademark) HP7200, Epicron (registered trademark) HP7200H, Epicron (registered trademark) HP7200HH "(manufactured by Dainippon Ink & Chemicals, Inc.); Trade name" Tactix (registered trademark) 558 "(manufactured by Huntsman Advanced Materials) Trade names “XD-1000-1L, XD-1000-2L” (manufactured by Nippon Kayaku Co., Ltd.)] and epoxy resins having a fluorene skeleton [for example, trade names “Oncoat EX-1010, Oncoat EX-1011” , On coat EX-1012, on coat E -1020, ONCOAT EX-1030, ONCOAT EX-1040, ONCOAT EX-1050, ONCOAT EX-1051 (above, manufactured by Nagase Sangyo Co., Ltd.); EG-250) "(manufactured by Osaka Gas Chemical Co., Ltd.)] and the like.

  Further, as the phenol resin (B2) having at least two functional groups and an alicyclic olefin structure or a fluorene structure, a phenol resin having a dicyclopentadiene skeleton [for example, trade names “Resitop GDP-6085, ResidtopGDP- 6095LR, Residtop GDP-6095HR, Residtop GDP-6115L, Residtop GDP-6115H, Residtop GDP-6140 (manufactured by Gunei Chemical Industry Co., Ltd.); Trade names "J-DPP-95, J-DPP-115" (JFE Chemical Co., Ltd.) Product)] and phenol resins having a fluorene skeleton [for example, trade names “CP-001, CP-002, NV-203-R4” (manufactured by Osaka Gas Chemical Co., Ltd.); trade names “S-TPM-113, S- TPM-130 "(manufactured by JFE Chemical Co., Ltd.)] It is.

  The blending ratio of the epoxy resin (B1) and the phenol resin (B2) is preferably a weight ratio of “epoxy resin (B1) / phenol resin (B2)”, preferably 80/20 to 40/60, more preferably 70 / 30-50 / 50.

  Moreover, the compounding quantity of the hardening | curing agent (B) in the curable resin composition of this invention is based on 100 weight part of alicyclic olefin polymers (A) which have a carboxyl group and / or a carboxylic anhydride group. The amount is preferably 300 to 1800 parts by weight, more preferably 350 to 1500 parts by weight, and still more preferably 400 to 1200 parts by weight. If the blending amount of the curing agent (B) is too small, the melt viscosity becomes high and the wiring embedding flatness may not be ensured. On the other hand, if it is too large, the desmear resistance may be deteriorated.

(Inorganic filler (C))
The inorganic filler (C) is not particularly limited as long as it is generally used industrially. For example, calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, silica Calcium acid, zirconium silicate, hydrated alumina, magnesium hydroxide, aluminum hydroxide, barium sulfate, silica, talc, clay and the like can be mentioned. By mix | blending an inorganic filler (C), the linear expansion of the hardened | cured material obtained can be made low.

  Among the inorganic fillers (C) described above, silica is preferable because it is excellent in heat resistance, low water absorption, dielectric properties, low impurity properties, heat dissipation, and the like. In particular, the surface is treated with a silane coupling agent. Silica is more preferable. In particular, by using silica obtained by treating the surface with a silane coupling agent, it is possible to improve desmear resistance of the obtained cured product (resistance to desmear treatment with an aqueous permanganate solution). In addition, it does not specifically limit as a silane coupling agent, A well-known thing can be used.

  The average particle diameter of the inorganic filler (C) used in the present invention is preferably 0.05 to 1.5 μm, more preferably 0.1 to 1 μm. If the average particle size of the inorganic filler (C) is too small, the melt viscosity increases and the embedded flatness may not be ensured. On the other hand, if the average particle size is too large, a short circuit between the wirings occurs when a fine wiring pattern is embedded. May cause. The average particle diameter can be measured with a particle size distribution measuring device.

  The compounding ratio of the inorganic filler (C) in the curable resin composition of the present invention is 30 to 90% by weight, preferably 40 to 80% by weight, and more preferably 50 to 70% by weight. The curable resin composition of the present invention includes an alicyclic olefin polymer (A) having a carboxyl group and / or a carboxylic acid anhydride group as described above, at least two functional groups, and an alicyclic olefin structure or a fluorene structure. Since the curing agent (B) and the inorganic filler (C) are blended, the curable resin is used even when the blending amount of the inorganic filler (C) is increased to 30% by weight or more. An increase in the melt viscosity of the composition can be suppressed. And the resin intensity | strength of the hardened | cured material obtained can be kept favorable, and by this, the hardened | cured material obtained can be made into the thing with low linear expansion and excellent wiring embedding flatness. Moreover, the reduction effect of the linear expansion of the hardened | cured material obtained can be improved by mix | blending many inorganic fillers (C). When there are too few compounding quantities of an inorganic filler (C), the linear expansion coefficient of the hardened | cured material obtained may become high. On the other hand, if the amount is too large, the melt viscosity becomes high and the embedded flatness may not be ensured.

  Moreover, you may mix | blend a hardening accelerator and a hardening adjuvant with the curable resin composition of this invention other than the said component. As the curing accelerator, a curing accelerator blended in a general curable resin composition for forming an electrical insulating film may be used. For example, a tertiary amine compound or a boron trifluoride complex compound is cured. It is suitably used as an accelerator. Of these, the use of a tertiary amine compound is preferable because the effect of improving the insulation resistance, heat resistance, and chemical resistance of the resulting cured product is high.

  Specific examples of the tertiary amine compound include, for example, chain tertiary amine compounds such as benzyldimethylamine, triethanolamine, triethylamine, tributylamine, tribenzylamine, dimethylformamide; pyrazoles, pyridines, pyrazines , Pyrimidines, indazoles, quinolines, isoquinolines, imidazoles, triazoles and the like. Among these, imidazoles, particularly substituted imidazole compounds having a substituent are preferable.

  Specific examples of the substituted imidazole compound include, for example, 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, 1-methyl-2-ethylimidazole, 2-isopropylimidazole, Alkyl-substituted imidazole compounds such as 2,4-dimethylimidazole and 2-heptadecylimidazole; 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole 1-benzyl-2-phenylimidazole, benzimidazole, 2-ethyl-4-methyl-1- (2′-cyanoethyl) imidazole, 2-ethyl-4-methyl-1- [2 ′-(3 ″, 5 ″ -Diaminotriazinyl) ethyl] imi Tetrazole and the like imidazole compounds substituted with a hydrocarbon group containing a ring structure, such as an aryl group or an aralkyl group such as. Among these, imidazole having a ring structure-containing substituent is preferable from the viewpoint of compatibility with the alicyclic olefin polymer (A) having a functional group, and 1-benzyl-2-phenylimidazole is particularly preferable.

  These curing accelerators can be used alone or in combination of two or more. The blending amount of the curing accelerator may be appropriately selected according to the purpose of use, but is usually based on 100 parts by weight of the alicyclic olefin polymer (A) having a carboxyl group and / or a carboxylic anhydride group. It is 0.001-30 weight part, Preferably it is 0.01-10 weight part, More preferably, it is 0.03-5 weight part.

  As the curing aid, a curing aid blended in a general curable resin composition for forming an electrical insulating film may be used. Specific examples thereof include quinone dioxime, benzoquinone dioxime, and p-nitrosophenol. Oxime / nitroso curing aids such as: N, Nm-phenylene bismaleimide and other maleimide curing aids; diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and other allyl curing aids; ethylene glycol di And methacrylate-based curing aids such as methacrylate and trimethylolpropane trimethacrylate; vinyl-based curing aids such as vinyltoluene, ethylvinylbenzene, and divinylbenzene; These curing aids can be used alone or in combination of two or more. The blending ratio of the curing aid is usually in the range of 1 to 1000 parts by weight, preferably 10 to 500 parts by weight with respect to 100 parts by weight of the curing agent (B).

In addition, the curable resin composition of the present invention may contain a rubbery polymer and other thermoplastic resins other than the above-described alicyclic olefin polymer (A) as necessary. The rubbery polymer is a polymer having a glass transition temperature of room temperature (25 ° C.) or lower, and includes general rubbery polymers and thermoplastic elastomers. By adding a rubbery polymer or other thermoplastic resin to the curable resin composition of the present invention, the flexibility of the resulting cured product can be improved. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the rubber polymer to be used may be appropriately selected, but is usually 5 to 200.

  Specific examples of rubber-like polymers include ethylene-α-olefin rubber-like polymers; ethylene-α-olefin-polyene copolymer rubbers; ethylene and unsaturated carboxylic acids such as ethylene-methyl methacrylate and etherene-butyl acrylate. Copolymers with esters; copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate; alkyl acrylates such as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate Polybutadiene, polyisoprene, styrene-butadiene or styrene-isoprene random copolymer, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene- (meth) acrylic acid alkyl ester copolymer, pig Diene rubber such as diene- (meth) acrylic acid alkyl ester-acrylonitrile copolymer, butadiene- (meth) acrylic acid alkyl ester-acrylonitrile-styrene copolymer; modified diene rubber such as epoxidized polybutadiene; butylene-isoprene A copolymer; and the like.

  Specific examples of the thermoplastic elastomer include aromatic vinyl such as styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer, etc. Examples thereof include conjugated diene block copolymers, low crystalline polybutadiene resins, ethylene-propylene elastomers, styrene grafted ethylene-propylene elastomers, thermoplastic polyester elastomers, and ethylene ionomer resins. Of these thermoplastic elastomers, a hydrogenated styrene-butadiene block copolymer and a hydrogenated styrene-isoprene block copolymer are preferable, and specifically, JP-A-2-133406 and JP-A-2-305814. Those described in JP-A-3-72512 and JP-A-3-74409 are preferably used.

  Other thermoplastic resins include, for example, low density polyethylene, high density polyethylene, linear low density polyethylene, ultra low density polyethylene, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, polystyrene, polyphenylene sulfide. , Polyphenylene ether, polyamide, polyester, polycarbonate, cellulose triacetate and the like.

  The above-mentioned rubber-like polymer and other thermoplastic resins can be used alone or in combination of two or more, and the blending amount thereof is appropriately selected within a range not impairing the object of the present invention. The blending amount is preferably 30 parts by weight or less with respect to 100 parts by weight of the alicyclic olefin polymer (A).

  In the curable resin composition of the present invention, for the purpose of improving flame retardancy when cured, for example, curing for forming a general electric insulation film such as a halogen-based flame retardant or a phosphate ester-based flame retardant. You may mix | blend the flame retardant mix | blended with an adhesive resin composition. When the flame retardant is blended with the curable resin composition of the present invention, the blending amount is preferably 100 parts by weight or less, more preferably 60 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer (A). Or less.

Further, the curable resin composition of the present invention further includes a flame retardant aid, a heat resistance stabilizer, a weather resistance stabilizer, an anti-aging agent, an ultraviolet absorber (laser processability improver), a leveling agent, if necessary. You may mix | blend arbitrary 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 body, a dielectric property modifier, and a toughening agent. What is necessary is just to select suitably the mixture ratio of these arbitrary components in the range which does not impair the objective of this invention.
The method for producing the curable resin composition of the present invention is not particularly limited, and the above components may be mixed as they are, or may be mixed in a state dissolved or dispersed in an organic solvent. Then, a composition in a state where a part of each of the above components is dissolved or dispersed in an organic solvent may be prepared, and the remaining components may be mixed with the composition.

(Cured product)
The cured product of the present invention is obtained by curing the above-described curable resin composition of the present invention. When obtaining the cured product of the present invention, the curable resin composition of the present invention is molded into a sheet or film to form a molded body, or the curable resin composition of the present invention is applied to a fiber substrate. It is preferably obtained by impregnating it into a sheet-like or film-like composite molded body and heating the resulting molded body or composite molded body.

  When the curable resin composition of the present invention is molded into a sheet shape or a film shape to obtain a molded body, the curable resin composition of the present invention is added to an organic solvent as necessary, and a support. It is preferably obtained by applying, spraying or casting to the substrate and then drying.

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

  The thickness of the sheet-like or film-like molded product is not particularly limited, but is usually 1 to 150 μm, preferably 2 to 100 μm, more preferably 5 to 80 μm from the viewpoint of workability and the like. The surface average roughness Ra of the support is usually 300 nm or less, preferably 150 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 molded product used in the present invention, the curable resin composition of the present invention is preferably in an uncured or semi-cured state. Here, uncured means a state where substantially all of the alicyclic olefin polymer (A) is dissolved when the molded body is immersed in a solvent capable of dissolving the alicyclic olefin polymer (A). Say. Semi-cured is a state where the resin is cured to the middle so that it can be further cured by heating. Preferably, the alicyclic olefin polymer (A) is dissolved in a solvent capable of dissolving the alicyclic olefin polymer (A). A part of A) (specifically, 7% by weight or more) is in a dissolved state, or the volume after the molded body is immersed in the solvent for 24 hours is 200% or more of the volume before the immersion (swelling) Rate).

  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 is not cured, and is usually 20 to 300 ° C, preferably 30 to 200 ° C. If the drying temperature is too high, the curing reaction proceeds 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.

  And the molded object obtained in this way is used in the state made to adhere on a support body, or peeling from a support body.

  Alternatively, instead of a sheet-shaped or film-shaped molded body, the fiber base material is impregnated with the curable resin composition of the present invention to form a sheet-shaped or film-shaped molded body, and the obtained composite molded body is obtained. The cured product may be obtained by heating.

  Examples of the fiber base material used in this case include woven and non-woven fabrics such as roving cloth, chopped mat, and surfacing mat; and bundles and lumps of fibers. Among these fiber base materials, a woven fabric is preferable from the viewpoint of dimensional stability, and a nonwoven fabric is preferable from the viewpoint of workability.

  The thickness of the sheet-shaped or film-shaped composite molded body 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. The amount of the fiber base in the composite molded body is usually 20 to 90% by weight, preferably 30 to 85% by weight.

  The method for impregnating the fiber base material with the curable resin composition of the present invention is not particularly limited, but an organic solvent is added to the curable resin composition of the present invention to adjust the viscosity and the like. The method of immersing a fiber base material in the added curable resin composition, the method of apply | coating or spraying the curable resin composition which added the organic solvent to a fiber base material, etc. are mentioned. In the method of coating or spreading, a curable resin composition to which an organic solvent is added can be applied or spread on a fiber base material placed on a support. In addition, in the composite molded object used by this invention, it is preferable that the curable resin composition of this invention is contained in the uncured or semi-hardened state similarly to the molded object mentioned above.

  Moreover, after impregnating the fiber base material with the curable resin composition of this invention, you may dry as needed. The drying temperature is preferably a temperature at which the curable resin composition of the present invention is not cured, and is usually 20 to 300 ° C, preferably 30 to 200 ° C. If the drying temperature is too high, the curing reaction proceeds 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.

  And the hardened | cured material of this invention can be obtained by heating and hardening the molded object or composite molded object mentioned above.

  The curing conditions are appropriately selected according to the type of the curing agent (B), but the curing temperature is usually 30 to 400 ° C, preferably 70 to 300 ° C, more preferably 100 to 200 ° C. The curing time is 0.1 to 5 hours, preferably 0.5 to 3 hours. The heating method is not particularly limited, and may be performed using, for example, an electric oven.

(Laminate)
The laminate of the present invention is formed by laminating a substrate having a conductor layer on the surface and an electrical insulating layer made of the cured product of the present invention described above.

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

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

  The laminate of the present invention is usually a molded body (a molded body formed by molding the curable resin composition of the present invention into a sheet or film) on a substrate having a conductor layer on the surface, or a composite. Electrical insulation comprising a molded product (composite molded product obtained by impregnating a fiber base material with the curable resin composition of the present invention) by thermocompression bonding, curing the molded product or the composite molded product, and the cured product of the present invention. It can be manufactured by forming a layer.

  As a method of thermocompression bonding, a molded body with a support or a composite molded body is superposed so as to be in contact with the conductor layer of the substrate described above, and a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator or the like is used. The method of carrying out thermocompression bonding (lamination) using is mentioned. By heating and pressurizing, bonding can be performed so that there is substantially no void at the interface between the conductor layer on the substrate surface and the molded body or composite molded body.

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

  And the laminated body of this invention is manufactured by hardening the molded object or composite molded object which is thermocompression-bonded, and forming an electrical-insulation layer. Curing is usually performed by heating the entire substrate on which a molded body or a composite molded body is formed on the conductor layer. Curing can be performed simultaneously with the above-described thermocompression bonding operation. Alternatively, the thermocompression may be performed after the thermocompression operation is performed under conditions that do not cause curing, that is, at a relatively low temperature for a short time.

  Further, for the purpose of improving the flatness of the electrical insulation layer or for the purpose of increasing the thickness of the electrical insulation layer, two or more molded bodies or composite molded bodies may be bonded and laminated on the conductor layer of the substrate.

(Multilayer circuit board)
The multilayer circuit board of the present invention is obtained by forming another conductor layer on the above-described electrical insulating layer of the laminate of the present invention. Hereinafter, the manufacturing method of the multilayer circuit board of this invention is demonstrated.

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

Next, 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 with an aqueous solution of permanganate. The surface roughening treatment is performed in order to improve the adhesiveness with the conductive layer formed on the electrical insulating layer.
The surface average roughness Ra of the electrical insulating layer is preferably 0.05 μm or more and less than 0.3 μm, more preferably 0.06 μm or more and 0.2 μm or less, and the surface 10-point average roughness Rzjis is preferably 0.00. They are 3 micrometers or more and less than 4 micrometers, More preferably, they are 0.5 micrometers or more and 2 micrometers or less. In this specification, Ra is the center line average roughness shown in JIS B0601-2001, and the surface ten-point average roughness Rzjis is the ten-point average roughness shown in JIS B0601-2001 appendix 1. .

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

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

  The temperature and time for bringing these oxidizing compound solutions into contact with the surface of the electrical insulating layer may be set arbitrarily in consideration of the concentration and type of the oxidizing compound, the contact method, etc. It is 250 degreeC, Preferably it is 20-180 degreeC, and time is 0.5 to 60 minutes normally, Preferably it is 1 to 40 minutes.

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

Next, after surface roughening treatment is performed on the electrical insulating layer of the laminate, a conductor layer is formed on the surface of the electrical insulating layer and on the inner wall surface of the via hole or the through hole.
Although the formation method of a conductor layer is not specifically limited, The plating method is preferable from a viewpoint of forming the conductor layer excellent in adhesiveness.

  The method for forming the conductor layer by plating is not particularly limited. For example, a method of forming a metal thin film on the electrical insulating layer by plating or the like and then growing the metal layer by thick plating can be employed.

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

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

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

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

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

  The multilayer circuit board of the present invention thus obtained has an electrical insulation layer (cured product of the present invention) made of the curable resin composition of the present invention, and the electrical insulation layer has a low linear expansion. In addition, since it is excellent in heat resistance, wiring embedding flatness, and resin strength, the multilayer circuit board of the present invention can be suitably used for various applications.

(Electronics)
The electronic device of the present invention comprises the multilayer circuit board of the present invention described above.
The electronic device of the present invention is not particularly limited, and for example, a mobile phone, a PHS, a notebook computer, a PDA (personal digital assistant), a mobile video phone, a personal computer, a supercomputer, a server, a router, a liquid crystal projector, an engineering Examples include a workstation (EWS), a pager, a word processor, a television, a viewfinder type or a monitor direct-view type video tape recorder, an electronic notebook, an electronic desk calculator, a car navigation device, a POS terminal, and a device equipped with a touch panel. According to the present invention, the electronic device of the present invention is provided with the multilayer circuit board of the present invention, so that it is possible to achieve high performance and high quality.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. Parts and% in each example are based on weight unless otherwise specified.
In addition, the definition and evaluation method of each characteristic are as follows.

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

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

(3) Content ratio of repeating unit having carboxylic acid anhydride group of alicyclic olefin polymer Number of moles of repeating unit having carboxylic acid anhydride group to total number of moles of monomer units in alicyclic olefin polymer The ratio was obtained by 1H-NMR spectrum measurement at 400 MHz.

(4) Melt viscosity 15 film molded bodies of the curable resin composition were overlapped to produce a plate-like sample having a thickness of 600 μm. This dynamic viscoelasticity measurement was measured using a VAR100 VISCOANALYSER ETC-3 manufactured by Jusco International at a rate of temperature increase of 5 ° C./min, a starting temperature of 50 ° C., a measurement temperature interval of 2.5 ° C., and a vibration of 1 Hz / deg. The minimum melt viscosity at 100 ° C to 130 ° C was evaluated according to the following criteria.
◎: Less than 50 Pa · s ○: 50 Pa · s or more, less than 100 Pa · s Δ: 100 Pa · s or more, less than 500 Pa · s ×: 500 Pa · s or more

(5) Linear expansion coefficient A 10 μm-thick copper foil is placed on a copper-clad laminate, and a film molded body of the curable resin composition is placed thereon, with the support attached, Using a vacuum laminator equipped with heat-resistant rubber press plates at the top and bottom so as to be on the inside, the pressure was reduced to 200 Pa, thermocompression bonded at a temperature of 110 ° C. and a pressure of 0.1 MPa for 60 seconds, and then 120 ° C. at 120 ° C. Heat cured in air for minutes. After curing, a cured resin with a copper foil was cut out and the copper foil was dissolved in a 1 mol / L ammonium persulfate aqueous solution to obtain a film-like cured product. A piece having a width of 5.95 mm, a length of 15.4 mm, and a thickness of 30 μm was cut out from the obtained film-like cured product, and thermogravimetric / differential heat was simultaneously obtained under the conditions of a distance between fulcrums of 10 mm and a heating rate of 10 ° C./min. The linear expansion coefficient was measured with a measuring device (TMA / SDTA840: manufactured by METTLER TOLEDO) and evaluated according to the following criteria.
◎: The value of the linear expansion coefficient is less than 25 ppm / ° C. ○: The value of the linear expansion coefficient is 25 ppm / ° C. or more and less than 40 ppm / ° C. Δ: The value of the linear expansion coefficient is 40 ppm / ° C. or more and less than 55 ppm / ° C. : The value of linear expansion coefficient is 55 ppm / ° C or more

(6) Glass transition temperature (Tg)
A film-like cured product was obtained in the same manner as in (5) above. The glass transition temperature (Tg) of the obtained cured film was determined from the peak temperature of loss tangent of dynamic viscoelasticity analysis (DMA method), and the glass transition temperature (Tg) was evaluated according to the following criteria.
A: Glass transition temperature is 170 ° C. or higher. ○: Glass transition temperature is 160 ° C. or higher and lower than 170 ° C. Δ: Glass transition temperature is 150 ° C. or higher and lower than 160 ° C. ×: Glass transition temperature is lower than 150 ° C.

(7) Desmear resistance The laminated body which has a via hole was immersed in the 80 degreeC permanganate aqueous solution for 30 minutes, and the desmear process was performed. And the via hole after a desmear process was observed with the optical microscope (magnification: 2000 times), and the desmear tolerance was evaluated on the following references | standards.
◎: Change rate of via hole top diameter is less than 10% ○: Change rate of via hole top diameter is 10% or more and less than 15% △: Change rate of via hole top diameter is 15% or more and less than 20% ×: Via hole The change rate of the top diameter of 20% or more

(8) Resin Strength A laminate having via holes was immersed in an aqueous permanganate solution at 80 ° C. for 30 minutes, and desmeared. And the via hole after a desmear process was observed with the optical microscope, and the resin intensity | strength was evaluated on the following references | standards.
◎: No crack around the via hole ○: One crack is generated in 1000 holes of the via hole △: 2 or more cracks are generated in 1000 holes of the via hole 1000: 11 or more cracks are generated in 1000 holes of the via hole

(9) Wiring embedding flatness A copper-clad laminated substrate on which a wiring pattern with a copper thickness of 35 μm, L / S = 50/50, 100/100, or 200/200 μm was formed. A curable resin composition film having a resin thickness of 40 μm was laminated thereon using a vacuum laminator and cured at 180 ° C. for 60 minutes. After curing, the step between the portion with the pattern and the portion without the pattern was measured with a stylus type step thickness meter (P-10 manufactured by Tencor Instruments), and the wiring embedding flatness was evaluated according to the following criteria.
A: Step is less than 1 μm ○: Step is 1 μm or more and less than 2 μm Δ: Step is 2 μm or more and less than 3 μm ×: Step is 3 μm or more

Production Example 1
Tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (methanotetrahydrofluorene, hereinafter abbreviated as “MTF”) 70 mole parts, bicyclo [2.2.1] hept-2-ene-5 , 6-dicarboxylic anhydride (hereinafter abbreviated as “NDCA”) 30 mol part, 1-hexene 0.9 mol part, anisole 590 mol part and 4-acetoxybenzylidene (dichloro) (4 5-Dibromo-1,3-dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium (manufactured by Wako Pure Chemical Industries, Ltd.) in an amount of 0.015 mol in a nitrogen-substituted pressure glass reactor and stirred. The polymer was subjected to a polymerization reaction at 80 ° C. for 1 hour to obtain a ring-opened polymer solution. Next, the solution of the obtained ring-opening polymer was charged into an autoclave equipped with a stirrer purged with nitrogen, and the mixture was stirred at 150 ° C. and a hydrogen pressure of 7 MPa for 5 hours to carry out a hydrogenation reaction, whereby a high molecular weight alicyclic olefin polymer was obtained. A solution of (A1) was obtained. The resulting alicyclic olefin polymer (A1) had a weight average molecular weight of 50,000, a number average molecular weight of 26,000, and a molecular weight distribution of 1.9. The hydrogenation rate was 97%, and the content of repeating units having a carboxylic anhydride group was 30 mol%. The solid content concentration of the alicyclic olefin polymer (A1) solution was 25%.

Production Example 2
MTF 70 mol part, NDCA 30 mol part, 1-hexene 6 mol part, anisole 590 mol part and 4-acetoxybenzylidene (dichloro) (4,5-dibromo-1,3-dimesityl-4-imidazoline) as ruthenium-based polymerization catalyst 2-ylidene) (tricyclohexylphosphine) ruthenium (manufactured by Wako Pure Chemical Industries, Ltd.) in an amount of 0.015 mol was charged in a pressure-resistant glass reactor substituted with nitrogen, and the polymerization reaction was carried out at 80 ° C. for 1 hour with stirring. A solution of a ring polymer was obtained. Next, the nitrogen-substituted autoclave equipped with a stirrer was charged with the obtained ring-opening polymer solution, and the mixture was stirred at 150 ° C. and a hydrogen pressure of 7 MPa for 5 hours to conduct a hydrogenation reaction. A low molecular weight alicyclic olefin polymer A solution of (A2) was obtained. The resulting low molecular weight alicyclic olefin polymer (A2) had a weight average molecular weight of 10,000, a number average molecular weight of 5,000, and a molecular weight distribution of 2. The hydrogenation rate was 97%, and the content of repeating units having a carboxylic anhydride group was 30 mol%. Anisole was distilled off from the solution under reduced pressure to make the solid concentration 50%.

Example 1
(Curable resin composition)
10 parts of the high molecular weight alicyclic olefin polymer (A1) obtained in Production Example 1, 50 parts of the low molecular weight alicyclic olefin polymer (A2) obtained in Production Example 2, and diester as an epoxy resin (B1) Epoxy resin having a cyclopentadiene skeleton (trade name “Epicron HP7200L”, manufactured by Dainippon Ink and Chemicals, Inc.) 28 parts, Epoxy resin having a fluorene skeleton as an epoxy resin (B1) (trade name “Ogsol PG100”, Osaka Gas Chemical) 106 parts, phenol resin having a dicyclopentadiene skeleton as a phenol resin (B2) (trade name “Resitop GDP-6095LR”, Gunei Chemical Industry Co., Ltd.) 79 parts, a fluorene skeleton as a phenol resin (B2) Phenol resin (trade name “CP-001”, manufactured by Osaka Gas Chemical Co., Ltd.) 35 parts As other curing agents, bisphenol A type epoxy resin (jER828EL, manufactured by Mitsubishi Chemical Corporation) 28 parts, polyfunctional epoxy resin (jER1032H60, manufactured by Mitsubishi Chemical Corporation) 23 parts, silane coupling agent treated silica as inorganic filler (C) (Trade name “Admafine Silica SC2500-SXJ”, manufactured by Admatechs) 660 parts, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] as a laser processability improver 1 part of benzotriazole, 1 part of tris (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate as an anti-aging agent, and 1-benzyl-2-phenylimidazole as a curing accelerator 1 part was mixed with 343 parts of anisole to obtain a curable resin composition. In addition, the content rate of the silane coupling agent process silica in the obtained curable resin composition was 65 weight%. And about the obtained curable resin composition, the melt viscosity was evaluated according to the said method. The results are shown in Table 1.

(Film molded product)
Next, using a die coater, the curable resin composition obtained above was a polyethylene terephthalate film having a size of length 300 mm × width 300 mm, thickness 38 μm, and surface average roughness Ra 0.08 μm (support) Body: Lumirror (registered trademark) T60 manufactured by Toray Industries, Inc.) and then dried in a nitrogen atmosphere at 80 ° C. for 10 minutes to form a 40 μm-thick curable resin composition film molding on the support. Obtained. Each evaluation of a linear expansion coefficient, a glass transition temperature (Tg), and wiring embedding flatness was performed according to the said method using the film molding of the obtained curable resin composition. The results are shown in Table 1.

(Laminated body with via hole)
Both sides of 0.8 mm thick × 150 mm long × 150 mm wide, with 35 μm thick copper pasted on the surface of the core material obtained by impregnating glass fiber with varnish containing glass filler and halogen-free epoxy resin A wiring pattern of L / S = 50/50, 100/100, or 200/200 μm was formed on the surface of the copper-clad laminate. Subsequently, the copper surface was microetched by contact with an organic acid to obtain a double-sided copper-clad laminate (inner layer substrate) having a wiring pattern on the surface.

  Then, the film molded body of the curable resin composition obtained above is cut into a size of 150 mm in length and 150 mm in width with the support attached, and the film molded body is on the inside and the support is on the outside. In this manner, the inner layer substrate obtained above was superposed on both surfaces. The atmosphere was decompressed to 200 Pa using a vacuum laminator equipped with heat-resistant rubber press plates at the top and bottom, and thermocompression bonded at a temperature of 110 ° C. and a pressure bonding pressure of 0.1 MPa for 60 seconds (primary press). Furthermore, using a vacuum laminator provided with metal press plates at the top and bottom, thermocompression bonding was performed at a temperature of 110 ° C. and a pressure bonding pressure of 1.0 MPa for 90 seconds (secondary press). Next, the support was peeled off, and the cured substrate was laminated by heating and curing in air at 180 ° C. for 60 minutes to obtain a laminated substrate.

  And in this hardened | cured material layer, the via hole used as top diameter / bottom diameter = 55 / 44micrometer was formed using CO2 laser, and the laminated body which has a via hole was obtained. And evaluation of desmear tolerance and resin strength was performed using the obtained laminated body which has a via hole. The results are shown in Table 1.

Example 2
Epoxy resin having a dicyclopentadiene skeleton as an epoxy resin (B1) (trade name “Epicron (registered trademark) HP7200L”, manufactured by Dainippon Ink & Chemicals, Inc.) 90 parts, an epoxy having a fluorene skeleton as an epoxy resin (B1) Resin (trade name “Ogsol PG100”, manufactured by Osaka Gas Chemical Co., Ltd.) 28 parts, phenol resin having a fluorene skeleton as the phenol resin (B2) (trade name “CP-001”, manufactured by Osaka Gas Chemical Co., Ltd.), dicyclo Example 1 except that the phenolic resin having a dicyclopentadiene skeleton (trade name “Resitop GDP-6140”) instead of the phenolic resin having a pentadiene skeleton (trade name “Resitop GDP-6095LR”) is 124 parts. Similarly, curable resin composition, film molding , And to obtain a laminate having a via hole was subjected to each evaluation. The results are shown in Table 1.

Example 3
The same as Example 1 except that the amount of the high molecular weight alicyclic olefin polymer (A1) was changed to 5 parts and the amount of the low molecular weight alicyclic olefin polymer (A2) was changed to 55 parts. Then, a curable resin composition, a film molded body, and a laminate having a via hole were obtained, and each evaluation was performed. The results are shown in Table 1.

Example 4
Example 1 except that the amount of the high molecular weight alicyclic olefin polymer (A1) was changed to 20 parts and the amount of the low molecular weight alicyclic olefin polymer (A2) was changed to 40 parts, respectively. Then, a curable resin composition, a film molded body, and a laminate having a via hole were obtained, and each evaluation was performed. The results are shown in Table 1.

Examples 5 and 6
The curable resin composition and film molding were carried out in the same manner as in Example 1, except that the amount of the silane coupling agent-treated silica was changed to 192 parts (Example 5) and 2016 parts (Example 6), respectively. The laminated body which has a body and a via hole was obtained, and each evaluation was performed. The results are shown in Table 1. In addition, the content rate of the silane coupling agent process silica in the obtained curable resin composition was 35 weight% (Example 5) and 85 weight% (Example 6), respectively.

Example 7
In place of silane coupling agent-treated silica, curing was performed in the same manner as in Example 1 except that silica not treated with a silane coupling agent (trade name “Admafine Silica SC2500”, manufactured by Admatechs) was used. The laminated body which has a conductive resin composition, a film molded object, and a via hole was obtained, and each evaluation was performed. The results are shown in Table 1.

Example 8
A curable resin was prepared in the same manner as in Example 1 except that the high molecular weight alicyclic olefin polymer (A1) was not added and the amount of the low molecular weight alicyclic olefin polymer (A2) was changed to 60 parts. A laminate having a composition, a film molded body, and a via hole was obtained, and each evaluation was performed. The results are shown in Table 1.

Example 9
The curability was the same as in Example 1 except that the blending amount of the high molecular weight alicyclic olefin polymer (A1) was changed to 60 parts and the low molecular weight alicyclic olefin polymer (A2) was not blended. A laminate having a resin composition, a film molded body, and a via hole was obtained, and each evaluation was performed. The results are shown in Table 1.

Comparative Example 1
Instead of the epoxy resin (B1) as the curing agent (B), 45 parts of a bisphenol A type epoxy compound (trade name “jER828EL”, manufactured by Mitsubishi Chemical Corporation), 100 parts of a polyfunctional epoxy resin (jER1032H60, manufactured by Mitsubishi Chemical Corporation) And 45 parts of a phenol novolac type epoxy compound (trade name “jER152”, manufactured by Mitsubishi Chemical Corporation), instead of the phenol resin (B2) as the curing agent (B), a novolac type phenol resin (trade name “TD-2131”) “A product made by DIC Co., Ltd.) Except for changing to 100 parts, a curable resin composition, a film molded body, and a laminate having a via hole were obtained in the same manner as in Example 1, and each evaluation was performed. The results are shown in Table 1.

  From Table 1, when the alicyclic olefin polymer (A) having a carboxyl group is blended with a curing agent (B) having at least two functional groups and an alicyclic olefin structure or a fluorene structure, it is inorganic. Even when a relatively large amount of silica as the filler (C) is added, the melt viscosity can be lowered, low linear expansion is achieved, and a cured product having excellent heat resistance, wiring embedding flatness, and resin strength is obtained. (Examples 1-9). Moreover, it turns out that it can be set as the thing excellent in desmear tolerance, when it is set as a laminated body by using the silica by which the surface was processed with the silane coupling agent as an inorganic filler (C) ( Examples other than Example 7).

  On the other hand, when a curing agent having no alicyclic olefin structure or fluorene structure is used as the curing agent, the melt viscosity becomes high, and the obtained cured product is inferior in resin strength and wiring embedding flatness. (Comparative Example 1).

Claims (8)

  Alicyclic olefin polymer (A) having carboxyl group and / or carboxylic anhydride group, curing agent (B) having at least two functional groups and alicyclic olefin structure or fluorene structure, and inorganic filler A curable resin composition comprising (C), wherein the blending amount of the inorganic filler (C) is 30 to 90% by weight.   The alicyclic olefin polymer (A) having a carboxyl group and / or a carboxylic acid anhydride group has a carboxyl group and / or a carboxylic acid anhydride group having a weight average molecular weight of 20,000 or more and 100,000 or less. An alicyclic olefin polymer (A1) and an alicyclic olefin polymer (A2) having a carboxyl group and / or a carboxylic anhydride group having a weight average molecular weight of 5,000 or more and less than 20,000, The blending ratio of the alicyclic olefin polymer (A1) and the alicyclic olefin polymer (A2) is 5/95 to 70 / in a weight ratio of “polymer (A1) / polymer (A2)”. The curable resin composition according to claim 1, which is 30.   The curing agent (B) comprises at least two functional groups, an epoxy resin (B1) having an alicyclic olefin structure or a fluorene structure, at least two functional groups, and an alicyclic olefin structure or a fluorene structure. The curable resin composition according to claim 1, comprising a phenol resin (B2) having the resin.   The curable resin composition according to any one of claims 1 to 3, wherein the inorganic filler (C) is silica obtained by treating the surface with a silane coupling agent.   Hardened | cured material formed by hardening | curing the curable resin composition in any one of Claims 1-4.   The laminated body formed by laminating | stacking the board | substrate which has a conductor layer on the surface, and the electrically insulating layer which consists of hardened | cured material of Claim 5.   A multilayer circuit board obtained by further forming a conductor layer on the electrically insulating layer of the laminate according to claim 6.   An electronic device comprising the multilayer circuit board according to claim 7.