JP2012214610A - Curable resin composition, film, laminate, and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition giving a cured product that excels in an electrical property, water resistance, heat resistance, and insulation reliability.SOLUTION: The curable resin composition includes: an alicyclic olefin polymer having at least one kind of a functional group chosen from the group consisting of a carboxyl group, a carboxylic acid anhydride group, and a hydroxyphenyl group (A); an epoxy compound having at least two epoxy groups condensed with a ring (B); and a photoacid generator (C).

Description

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

  Various display elements such as organic EL elements and liquid crystal display elements, semiconductor elements such as integrated circuit elements and solid-state imaging elements, protective films for preventing deterioration and damage, flattening for flattening the element surface and wiring A functional resin film such as an interlayer insulating film for maintaining electrical insulation between the films and the wirings arranged in layers is provided.

  Conventionally, thermosetting resins such as polyimide resins have been used as resin materials for forming these films because of their excellent heat resistance and excellent electrical and mechanical properties.

  However, when a polyimide resin is used, there is a problem that insulation reliability is not sufficient because migration occurs in the obtained resin film. Further, the polyimide resin has a high curing temperature of 300 ° C. or higher, and there is a problem that the wiring metal is oxidized during the curing reaction.

  In recent years, resin materials have excellent dielectric properties, especially low dielectric constants, in response to increased signal delay and increased power consumption due to higher integration and higher density of semiconductor elements. There is a need to be. As a material for achieving such a low dielectric constant, an alicyclic olefin polymer has been studied.

  For example, in Patent Document 1, as a material for providing a resin layer excellent in processability, low stress property, low water absorption, and electrical insulation, a cyclic olefin resin having an acidic group, a photoacid generator, and 130 A resin composition comprising a compound having a reactive group capable of binding to an acidic group of a cyclic olefin-based resin having an acidic group at a temperature of 0 ° C. or higher is disclosed.

JP 2006-98807 A

  However, when the present inventors examined, when the resin layer of a semiconductor element was formed using the resin composition of the above-mentioned patent document 1, the problem that a deformation | transformation of a laminated substrate will become large, heat resistance, etc. It became clear that there was a problem that the reliability of was insufficient.

  The objective of this invention provides the curable resin composition which gives the hardened | cured material excellent in the electrical property, water resistance, heat resistance, and insulation reliability, and the film, hardened | cured material, and laminated body obtained using this. That is.

  As a result of diligent research to achieve the above object, the present inventors contain an alicyclic olefin polymer having a specific functional group, a specific epoxy compound, a photoacid generator, and an inorganic filler. The present inventors have found that the curable resin composition can give a cured product excellent in electrical characteristics, water resistance, heat resistance and insulation reliability, and completed the present invention.

That is, according to the present invention,
[1] An alicyclic olefin polymer (A) having at least one functional group selected from the group consisting of a carboxyl group, a carboxylic acid anhydride group, and a hydroxyphenyl group, two or more epoxy groups condensed to a ring A curable resin composition comprising an epoxy compound (B) and a photoacid generator (C),
[2] The curable resin composition according to [1], further including an inorganic filler (D),
[3] The curable resin composition according to the above [1] or [2], wherein the epoxy compound (B) does not contain an ester bond,
[4] A film comprising the curable resin composition according to any one of [1] to [3],
[5] The curable resin composition according to any one of [1] to [3], or a cured product obtained by curing the film according to [4],
[6] A laminate formed by laminating the film according to [4] on a base material,
[7] A laminate comprising a glass substrate or a silicon wafer substrate and the cured product according to [5], and
[8] The laminate according to [7], wherein a metal plating layer is formed on the surface of the cured product,
Is provided.

  According to the present invention, a curable resin composition capable of giving a cured product excellent in electrical characteristics, water resistance, heat resistance and insulation reliability, and such a curable resin composition can be obtained, A cured product and a laminate excellent in electrical characteristics, water resistance, heat resistance, and insulation reliability can be provided.

  The curable resin composition of the present invention is an alicyclic olefin polymer (A) having at least one functional group selected from the group consisting of a carboxyl group, a carboxylic acid anhydride group, and a hydroxyphenyl group, condensed to a ring An epoxy compound (B) containing two or more epoxy groups and a photoacid generator (C).

(Alicyclic olefin polymer (A))
The alicyclic olefin polymer (A) having at least one functional group selected from the group consisting of a carboxyl group, a carboxylic acid anhydride group, and a hydroxyphenyl group used in the present invention (hereinafter referred to as “alicyclic olefin” as appropriate). Examples of the alicyclic structure constituting the polymer (A) ”include a cycloalkane structure and a cycloalkene structure, and a cycloalkane structure is preferable from the viewpoint of mechanical strength and heat resistance. Examples of the alicyclic structure include monocycles, polycycles, condensed polycycles, bridged rings, and polycycles formed by combining these. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually in the range of 4 to 30, preferably 5 to 20, more preferably 5 to 15, and the carbon 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 addition, the alicyclic olefin polymer (A) used in the present invention may have any of a carboxyl group, a carboxylic anhydride group, and a hydroxyphenyl group, but the effect of the present invention becomes more remarkable. From the standpoint, those having a carboxylic anhydride group are particularly preferred.

  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.

  At least one functional group selected from the group consisting of a carboxyl group, a carboxylic anhydride group and a hydroxyphenyl group contained in the alicyclic olefin polymer (A) (hereinafter referred to as “specific functional group” as appropriate). .) Is directly bonded to the atoms constituting the main chain of the polymer, but is bonded via another divalent group such as a methylene group, an oxy group, an oxycarbonyloxyalkylene group or a phenylene group. Also good. The content of the specific functional group in the alicyclic olefin polymer (A) is not particularly limited, but is usually 5 to 60 with respect to the number of moles of all repeating units constituting the alicyclic olefin polymer (A). It is 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) a method of polymerizing an alicyclic olefin having a specific functional group by adding another monomer as necessary, and (2) an alicyclic olefin having no specific functional group A method of copolymerizing with a monomer having a group; (3) an aromatic olefin having a specific functional group is polymerized by adding another monomer as required, and the aromatic ring of the polymer obtained thereby A method of hydrogenating a portion, (4) a method of copolymerizing an aromatic olefin having no specific functional group with a monomer having a specific functional group, and hydrogenating an aromatic ring portion of a polymer obtained thereby, Or (5) a method of introducing a compound having a specific functional group into an alicyclic olefin polymer having no specific functional group by a modification reaction, or (6) obtained as described in (1) to (5) above. Alicyclic olefins having carboxylic acid ester groups The carboxylic acid ester group of the down polymer can be obtained by a method of converting the carboxyl group by, for example, hydrolysis. Among these, a polymer obtained by the method (1) described above is preferable.
As the polymerization method for obtaining the alicyclic olefin polymer (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 specific functional group that can be used as a monomer having a specific functional group include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl- 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 9-hydroxycarbonyltetracyclo [6. 2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-carboxymethyl-9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 5-exo-6-endo-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 9-exo-10-endo-dihydroxycarbonyltetracyclo [6. 2.1.1 ^3,6 . Alicyclic olefin having a carboxyl group such as 0 ^2,7 ] dodec-4-ene; bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, tetracyclo [6.2 1.1 ^{3, 6} . 0 ^2,7] dodeca-4-ene-9,10-dicarboxylic anhydride, hexacyclo [10.2.1.1 ^{3, 10.} 1 ^5,8 . 0 ^2,11 . Alicyclic olefins having a carboxylic anhydride group such as 0 ^4,9 ] heptadeca-6-ene-13,14-dicarboxylic anhydride; 5- (4-hydroxyphenyl) bicyclo [2.2.1] hept 2-ene, 9- (4-hydroxyphenyl) tetracyclo [6.2.13, 6.02,7] dodec-4-ene, N- (4-hydroxyphenyl) bicyclo [2.2.1 ] An alicyclic olefin having a hydroxyphenyl group such as hept-5-ene-2,3-dicarboximide; These may be used individually by 1 type and may use 2 or more types together.

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 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. These may be used alone or in combination of two or more.

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

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

  Examples of the monomer having no specific functional group other than the alicyclic olefin that can be copolymerized with the alicyclic olefin or aromatic olefin 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- Ethylene or α-olefin having 2 to 20 carbon atoms such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; And the like; hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene nonconjugated dienes such. These may be used alone or in combination of two or more.

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

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

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

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

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

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

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

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

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

  As a polymerization catalyst for 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 in the polymerization reaction described above, from the viewpoint of not reacting during the hydrogenation reaction, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, an ether solvent, an aromatic solvent Aromatic ether solvents are preferred, and aromatic ether solvents are more preferred.

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

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

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

(Epoxy compound (B))
The epoxy compound (B) (hereinafter abbreviated as “epoxy compound (B)” as appropriate) containing two or more epoxy groups condensed to a ring, used in the present invention, is an epoxy existing on a cycloalkane ring. It is an alicyclic epoxy compound containing two groups in the molecule, and in the present invention, one containing two epoxy groups present on the cycloalkane ring in the molecule and not containing an ester bond is preferable. Moreover, it is more preferable that it does not contain the functional group which has hetero atoms, such as a nitrogen atom, an oxygen atom, and a sulfur atom other than an epoxy group.

（上記一般式（１）中、Ｒ^１〜Ｒ^１２は、互いに独立して、水素原子、ハロゲン原子、又は炭素数１〜２０の炭化水素基を表す。）

（上記一般式（２）中、Ｒ^１３〜Ｒ^３０は、互いに独立して、水素原子；ハロゲン原子；酸素原子もしくはハロゲン原子を含んでもよい、炭素数１〜２０の炭化水素基；又は置換基を有してもよい炭素数１〜２０のアルコキシ基を表す。）

（上記一般式（３）中、Ｒ^３１〜Ｒ^４１は、互いに独立して、水素原子、ハロゲン原子、又は炭素数１〜２０の炭化水素基を表す。） As specific examples of the epoxy compound (B), any of the compounds represented by the following general formulas (1) to (3) is preferable.

(In the general formula (1), R ^{1 to} R ¹² each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms.)

(In the general formula (2), R ^{13 to} R ³⁰ are each independently a hydrogen atom; a halogen atom; a hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom or a halogen atom; or a substituent. Represents an alkoxy group having 1 to 20 carbon atoms which may have

(In the general formula ^(3), R 31 ^{to R 41} independently of one another, represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms.)

In formula (1) to ^(3), the halogen atom constituting R 1 ^{to R 41,} a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
R ^{1 to} R ¹² , R ^{31 to} R ⁴¹ , a C 1-20 hydrocarbon group, and R ^{13 to} R ³⁰ , an oxygen atom or a halogen atom, which may contain a C 1-20 carbonization Examples of the hydrogen group include alkyl groups such as methyl group, ethyl group, and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aromatic groups such as phenyl group, naphthyl group, and anthracenyl group. In R ^{13 to} R ³⁰ , these hydrocarbon groups may contain an oxygen atom or a halogen atom.

Examples of the alkoxy group having 1 to 20 carbon atoms that may have a substituent constituting R ^{13 to} R ³⁰ include a methoxy group, an ethoxy group, an n-propoxy group, an iso group. A propoxy group, n-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, n-octyloxy group and the like can be mentioned. Examples of the substituent include halogen atoms such as chlorine atom and bromine atom; alkoxy groups such as methoxy group and ethoxy group;

  Among these, the epoxy compound (B) preferably has a molecular weight of 300 or less, more preferably a molecular weight of 100 to 300, since the effects of the present invention become more remarkable. Moreover, what is a liquid at the temperature of 25 degreeC is preferable. Furthermore, as an epoxy compound (B), what does not have polar groups other than an epoxy group from the point that the electrical property and water resistance of the hardened | cured material obtained can be improved.

As the epoxy compound (B), in particular, a compound represented by the following formula (4) (tetrahydroindene diepoxide), a compound represented by the following formula (5) ((3,3 ′, 4,4′-diepoxy) ) Bicyclohexyl) or a compound represented by the following formula (6) (dicyclopentadiene diepoxide) is preferable, and a compound represented by the following formula (5) is more preferable from the viewpoint of reactivity and liquid. .

  As the epoxy compound (B), in addition to the compounds represented by the above formulas (4) to (6), for example, known methods such as a method of epoxidizing the carbon-carbon double bond of the corresponding olefin (See, for example, Japanese Patent Application Laid-Open Nos. 2002-145872, 2008-189698, and 2008-189709). Moreover, a commercial item can also be used as it is.

  The blending ratio of the epoxy compound (B) in the curable resin composition of the present invention is a weight ratio of “alicyclic olefin polymer (A) / epoxy compound (B)”, preferably 1/99 to 50. / 50, more preferably in the range of 10/90 to 40/60, still more preferably in the range of 20/80 to 40/60. When there are too few compounding ratios of an epoxy compound (B), hardening will become inadequate and there exists a possibility that the mechanical strength of the hardened | cured material obtained may deteriorate. On the other hand, when there are too many compounding ratios of an epoxy compound (B), there exists a possibility that it may become weak.

(Photoacid generator (C))
The photoacid generator (C) used in the present invention is a substance that generates Bronsted acid or Lewis acid in response to light and acts as a curing agent. Examples of the photoacid generator (C) include onium salts, halogenated organic compounds, α, α-bis (sulfonyl) diazomethane compounds, α-carbonyl-α-sulfonyl-diazomethane compounds, sulfone compounds, organic acid ester compounds, It is selected from organic acid amide compounds and organic acid imide compounds. Of these, onium salts are preferred.

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

Examples of the photoacid generator (C) used in the present invention include arylsulfonium salt derivatives (for example, Cyracure (registered trademark, the same applies hereinafter) manufactured by Dow Chemical Co., Ltd., UVI-6990, Cyracure UVI-6992, and Cyracure. UVI-6974: ADEKA Adekaoptomer (registered trademark, hereinafter the same) SP-150, Adekaoptomer SP-152, Adekaoptomer SP-170, Adekaoptomer SP-172], allyl iodonium salt derivative (For example, PI-2074 manufactured by Rhodia), allene-ion complex derivatives (for example, Irgacure (registered trademark) 261 manufactured by Ciba Geigy), acid generators such as diazonium salt derivatives, triazine-based initiators and other halides Is mentioned.

  The blending amount of the photoacid generator (C) in the curable resin composition of the present invention is preferably based on 100 parts by weight of the total of the alicyclic olefin polymer (A) and the epoxy compound (B), It is 0.1-10 weight part, More preferably, it is 0.5-5 weight part, More preferably, it is 1-4 weight part. If the blending amount of the photoacid generator (C) is too small, curing may be insufficient. On the other hand, if it is too large, reliability may be deteriorated.

(Inorganic filler (D))
In addition to the above-described alicyclic olefin polymer (A), epoxy compound (B) and photoacid generator (C), the curable resin composition of the present invention contains an inorganic filler (D). It is preferable to do. The inorganic filler (D) 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 blending the inorganic filler, the linear expansion of the obtained cured product can be lowered.

  Among the inorganic fillers (D) 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 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 (D) 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 (D) is too small, the melt viscosity becomes high and the embedding flatness may not be ensured. On the other hand, if the average particle size is too large, a short circuit between 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 (D) in the curable resin composition of the present invention is 30 to 90% by weight, preferably 40 to 80% by weight, more preferably 50 to 70% by weight. If the blending ratio of the inorganic filler (D) is too low, it is difficult to obtain the effect of blending the inorganic filler (D). On the other hand, if the blending ratio is too high, the film or cured product made of the curable composition is brittle. There is a risk.

(Other ingredients)
Moreover, you may mix | blend a photosensitizer with the curable resin composition of this invention as needed. Examples of the photosensitizer (g) include photosensitizers such as thioxanthone, thioxanthone derivatives, anthraquinone, anthraquinone derivatives, anthracene, anthracene derivatives, perylene, perylene derivatives, benzophenone, and benzoin isopropyl ether. Can do. The effect of the photosensitizer is increased by containing 0.1 to 20 parts by weight when the curable resin composition is 100 parts by weight. By using a photosensitizer, photocurability and photoreactivity can be improved, and adhesive strength can be improved.
Moreover, you may mix | blend a solvent with the curable resin composition of this invention as needed. By blending a solvent, it is possible to suppress the progress of the curing reaction when the curable resin composition of the present invention is prepared. Thereby, a stable composition can be obtained and molded into a film shape. It is possible to improve the moldability in the process. The solvent is volatilized and removed by heating or the like when the curable resin composition of the present invention is formed into a film and formed into a film.

  The solvent preferably has a boiling point of 30 to 250 ° C, more preferably 50 to 200 ° C, from the viewpoint of volatilization and removal by heating or the like when forming into a film. Specific examples of such solvents include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, trimethylbenzene, and anisole; aliphatics such as n-pentane, n-hexane, n-heptane, methyl ethyl ketone, and methyl isobutyl ketone. Hydrocarbons; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclopentanone, and cyclohexanone; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene. Among these, from the viewpoint of compatibility with each component constituting the curable resin composition of the present invention, when the cyclic olefin polymer (A) is used in the form of a polymer solution, the polymer solution It is preferable to use the same solvent as used in the above.

  The mixing ratio of the solvent in the curable resin composition of the present invention is preferably 90% by weight or less, more preferably 80% by weight or less, and further preferably 70% by weight or less.

  Furthermore, in the curable resin composition of the present invention, a rubbery polymer and other thermoplastic resins other than the alicyclic olefin polymer (A) can be blended as necessary. The rubbery polymer is a polymer having a glass transition temperature of room temperature (25 ° C.) or lower, and includes general rubbery polymers and thermoplastic elastomers.

  The blending amount of the rubber-like polymer and other thermoplastic resins is appropriately selected within a range not impairing the object of the present invention, but a total of 100 parts by weight of the alicyclic olefin polymer (A) and the epoxy compound (B). On the other hand, the blending amount is preferably 30 parts by weight or less.

  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 in 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 or less, with respect to 100 parts by weight of the alicyclic olefin polymer. is there.

  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.

  It does not specifically limit as a manufacturing method of the curable resin composition of this invention, It can manufacture by mixing said each component. Moreover, when using a solvent, you may prepare the composition of the state which melt | dissolved or disperse | distributed a part of said each component in a solvent, and may mix the remaining components with the said composition.

(the film)
The film of this invention is a molded object formed by shape | molding the curable resin composition of this invention mentioned above in a sheet form or a film form.

  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 body 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 article of 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 150 ° C, preferably 30 to 100 ° 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 film of this invention obtained in this way is used in the state made to adhere on a support body, or peeling from a support body.

  The thickness of the sheet-like or film-like 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.

  And the film of this invention obtained in this way can be made into hardened | cured material by irradiating actinic radiation, thereby activating a photo-acid generator (C) and causing hardening reaction.

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

The irradiation condition of the active radiation is appropriately selected according to the active radiation to be used. For example, when using a light beam having a wavelength of 200 to 450 nm, the irradiation amount is usually 10 to 10,000 mJ / cm ² , preferably 50. It is in the range of ˜5,000 mJ / cm ² and is determined according to the irradiation time and illuminance. Thus, after irradiating actinic radiation, a film-shaped hardened material is heat-processed as needed. Examples of the heating method include a method of heating a film-like cured product in a hot plate or an oven. The temperature is usually in the range of 100 to 300 ° C, preferably 120 to 200 ° C.

(Laminate)
The laminate of the present invention is formed by laminating the above-described film of the present invention. The laminate of the present invention may be at least a laminate of the above-described film of the present invention, but a laminate of the glass substrate or silicone wafer substrate and the above-described film of the present invention. preferable.

  The laminate of the present invention is usually a molded product obtained by molding the above-described film of the present invention (that is, 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 molded article obtained by impregnating a fiber base material with the curable resin composition of the present invention can be produced by thermocompression bonding.

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

  The temperature of the thermocompression bonding operation is usually 30 to 150 ° C., preferably 70 to 120 ° 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 1 Time, preferably 1 to 30 minutes. 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.

  Moreover, about the laminated body obtained in this way, it can be set as hardened | cured material by irradiating actinic radiation, and also heat-processing a laminated body as needed, and performing the process which hardens the film of this invention. it can. In this case, the irradiation conditions of the active radiation may be the same as described above. Furthermore, in this invention, you may form a metal plating layer on the surface of the hardened | cured material formed by irradiating actinic radiation and hardening the film of this invention.

  One embodiment of the laminate of the present invention is a semiconductor device having a wafer level package structure. The semiconductor device includes a semiconductor element, an external connection terminal connected to an electrode on the surface of the semiconductor element, and a film that covers the surface of the semiconductor element excluding the external connection terminal. Such a film is made of the film of the present invention and functions as an insulating resin layer. As a method for manufacturing the semiconductor device, the step of adhering the film of the present invention so as to cover the surface of the semiconductor wafer, after the film is cured, an opening is formed in a portion of the cured film where the electrode position of the semiconductor element is located. The step of forming, the step of forming a conductive wiring on the surface of the cured film through the opening, and the step of connecting the electrodes of the semiconductor element and the external connection terminals by appropriately repeating the three steps. By cutting the wafer thus obtained into individual elements, a semiconductor device having a wafer level package structure can be obtained.

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

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

(2) Hydrogenation rate of alicyclic olefin polymer The ratio of the number of moles of unsaturated bonds hydrogenated to the number of moles of unsaturated bonds in the alicyclic olefin polymer before hydrogenation was determined as ¹ H of 400 MHz. -It calculated | required by NMR spectrum measurement and made this hydrogenation rate.

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

(4) Water absorption rate (weight change rate)
The cured film was immersed in boiling water at a temperature of 100 ° C. for 1 hour, and the water absorption rate was evaluated by measuring the weight change rate before and after that. The weight change rate is determined according to “weight change rate (%) = {(weight after immersion in boiling water−weight before immersion in boiling water) / weight before immersion in boiling water} × 100”, according to the following criteria: The water absorption was evaluated. In addition, since a water absorption rate is low and it can be judged that it is excellent in water resistance, the weight change rate is preferable.
A: Weight change rate is less than 0.5% B: Weight change rate is 0.5% or more and less than 1% C: Weight change rate is 1% or more

(5) Relative permittivity A small piece having a width of 2.6 mm, a length of 80 mm, and a thickness of 20 μm was cut out from the cured film, and the relative permittivity at 10 GHz was measured using a cavity resonator perturbation method permittivity measuring apparatus.
A: The relative dielectric constant is less than 3.0 C: The relative dielectric constant is 3.0 or more,

(6) Dielectric loss tangent A small piece having a width of 2.6 mm, a length of 80 mm, and a thickness of 20 μm was cut out from the cured film, and the dielectric loss tangent at 10 GHz was measured using a cavity resonator perturbation method dielectric constant measuring apparatus.
A: Dielectric loss tangent is less than 0.02 C: Dielectric loss tangent is 0.02 or more,

(7) Linear expansion coefficient A piece having a width of 5.95 mm, a length of 15.4 mm, and a thickness of 20 μm was cut out from the cured film, and was subjected to a thermomechanical analyzer (TMA) under the conditions of a distance between supporting points of 10 mm and a heating rate of 10 ° C./min. / SDTA840: manufactured by METTLER TOLEDO), the linear expansion coefficient was measured at 30 ° C. to 150 ° C. and evaluated according to the following criteria.
A: The value of the linear expansion coefficient is less than 40 ppm / ° C. B: The value of the linear expansion coefficient is 40 ppm / ° C. or more and less than 50 ppm / ° C. C: The value of the linear expansion coefficient is 50 ppm / ° C. or more.

(8) Insulation reliability The multilayer laminated substrate was treated for 200 hours under conditions of 130 ° C., 85% RH, and applied voltage of 5V. Subsequently, the insulation resistance between the electrical insulation layers of the multilayer laminated substrate after the treatment for 200 hours was measured, and the insulation reliability was evaluated according to the following criteria.
A: 1.0 × 10 ⁷ Ω or more C: Less than 1.0 × 10 ⁷ Ω

Production Example 1
Tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene 70 mol parts, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride 30 mol parts, 1-hexene 0 .9 mol part, 590 mol part of anisole and 4-acetoxybenzylidene (dichloro) (4,5-dibromo-1,3-dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium (ruthenium) 0.015 mol part (manufactured by Wako Pure Chemical Industries, Ltd.) was put into a pressure-resistant glass reactor substituted with nitrogen, and a polymerization reaction was carried out at 80 ° C. for 1 hour with stirring to obtain a ring-opening polymer solution. Subsequently, the solution of the obtained ring-opening polymer was put 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 conduct a hydrogenation reaction, whereby an alicyclic olefin polymer (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%.

Example 1
(Curable resin composition)
40 parts of anisole solution (10 parts as a polymer) of the alicyclic olefin polymer (A1) obtained in Synthesis Example 1 above (3,3 ′, 4,4′-diepoxy) as an epoxy compound (B) 90 parts of bicyclohexyl (B1), 2 parts of arylsulfonium salt derivative (C1) (Adekaoptomer (registered trademark) SP172, manufactured by ADEKA) as a photoacid generator (C), and 9, as a photosensitizer A curable resin composition was obtained by mixing 0.5 parts of 10-dibutoxyanthracene with anisole and mixing so that the concentration of the compounding agent was 60%.

(Film molded product)
Next, using a die coater, the curable resin composition obtained above was a polyethylene terephthalate film having a thickness of 38 μm and a surface average roughness Ra of 0.08 μm (support: Lumirror (registered trademark) T60 Toray. And then dried at 80 ° C. for 10 minutes in a nitrogen atmosphere to obtain a film molded body of a curable resin composition having a thickness of 20 μm on the support.

(Cured film)
The film molded body of the obtained curable resin composition was bonded onto a 9 μm thick copper foil placed on a substrate so that the surface of the curable resin composition was on the inner layer substrate side, and then a primary press Went. The primary press was performed by thermocompression bonding at a temperature of 60 ° C. and a pressure of 0.1 MPa for 90 seconds under a reduced pressure of 200 Pa using a vacuum laminator equipped with heat-resistant rubber press plates at the top and bottom. Furthermore, using a hydraulic press apparatus provided with metal press plates at the top and bottom, thermocompression bonding was performed for 90 seconds at a pressure bonding temperature of 60 ° C. and 1 MPa. Next, by peeling off the support, a laminate of the curable resin composition layer and the copper foil was obtained, and the light intensity at 365 nm was 3.57 mW / cm on the curable resin composition surface of the obtained laminate. ² was irradiated in the air for 400 seconds. Then, the hardened | cured material of the 20-micrometer-thick film molded object was obtained on copper foil by heat-processing in the air for 60 minutes at 180 degreeC. And the copper foil of the hardened | cured material of the obtained film forming body with a copper foil is melt | dissolved in 1 mol / liter ammonium persulfate aqueous solution, This is dried under reduced pressure, A cured film (film-like hardened | cured material) is obtained. It was.

(Multilayer laminated board)
Subsequently, the inner layer board | substrate which has the copper surface by which the surface of the epoxy double-sided copper clad board with which the thickness of 18 micrometers was stuck was made to contact with an organic acid was microetched was obtained.

The film molded body obtained above was bonded to one surface of the inner layer substrate so that the curable resin composition surface was on the inner layer substrate side, and then primary press was performed. The primary press was performed by using a vacuum laminator equipped with heat-resistant rubber press plates at the top and bottom, under a reduced pressure of 200 Pa, under conditions of a temperature of 50 ° C. and a pressure of 0.1 MPa for 60 seconds. Furthermore, it crimped | bonded for 60 second on the conditions of crimping | compression-bonding temperature 50 degreeC and 0.5 MPa using the hydraulic press apparatus provided with the metal press board up and down. Next, the support was peeled off to obtain a laminate of the curable resin composition layer and the inner layer substrate. The surface of the curable resin composition of the obtained laminate is irradiated with ultraviolet rays having a light intensity at 365 nm of 3.57 mW / cm ² in the air for 400 seconds and further heat-treated in the air at 180 ° C. for 60 minutes. Thus, the curable resin composition layer was cured to form an electrically insulating layer on the inner layer substrate.

  Next, the obtained laminate was subjected to electroless copper plating to form a metal thin film layer on the surface of the laminate, and annealed at 150 ° C. for 30 minutes in an air atmosphere.

  And the resist pattern was obtained using the commercially available photosensitive resist for the laminated body to which the annealing process was given. And the electrolytic copper plating was given to the resist non-formation part, and the electrolytic copper plating film | membrane with a thickness of 18 micrometers was formed. Thereafter, the resist pattern on the laminate was removed using a stripping solution, and a copper etching process was performed on the portion where the resist was removed with a mixed solution of cupric chloride and hydrochloric acid. Next, a multilayer laminated substrate with a wiring pattern in which a circuit is formed by a conductor layer made of a metal thin film layer and an electrolytic copper plating film on the laminated body is obtained by heating the laminated body subjected to the etching treatment at 180 ° C. for 60 minutes. It was.

  Then, using the cured film and multilayer laminated substrate obtained as described above, according to the above method, each measurement / evaluation of water absorption, relative dielectric constant, dielectric loss tangent, linear expansion coefficient, and insulation reliability was performed. . The results are shown in Table 1.

Example 2
The amount of the anisole solution of the alicyclic olefin polymer (A1) is changed from 40 parts to 120 parts (30 parts as the polymer), and (3,3 ′, 4,4′-diepoxy) as the epoxy compound (B). A curable resin composition, a film molded body, a cured film, and a multilayer laminated substrate were obtained in the same manner as in Example 1, except that the amount of bicyclohexyl (B1) was changed from 90 parts to 70 parts. The same evaluation was performed. The results are shown in Table 1.

Example 3
Silane coupling agent-treated silica (D1) as an inorganic filler (D) (trade name “Admafine Silica SC2500-SXJ”, manufactured by Admatechs) 198 parts was added in the same manner as in Example 2 except that 198 parts were further added. A curable resin composition, a film molded body, a cured film, and a multilayer laminated substrate were obtained and evaluated in the same manner. The results are shown in Table 1.

Example 4
The amount of the anisole solution of the alicyclic olefin polymer (A1) was changed from 40 parts to 80 parts (20 parts as a polymer), and as the epoxy compound (B), (3, 3 ′, 4, 4 ′ -Diepoxy) A curable resin composition, a film molded product, a cured film, and the same as in Example 1 except that 80 parts of dicyclopentadiene diepoxide (B2) was used instead of bicyclohexyl (B1), and A multilayer laminated substrate was obtained and evaluated in the same manner. The results are shown in Table 1.

Example 5
While changing the compounding quantity of the anisole solution of an alicyclic olefin polymer (A1) from 40 parts to 60 parts (15 parts as a polymer), as an epoxy compound (B), (3,3 ', 4,4' -Diepoxy) Curable resin composition, film molded article, cured film, and multilayer as in Example 1 except that 85 parts of tetrahydroindene diepoxide (B2) was used instead of bicyclohexyl (B1) A laminated substrate was obtained and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 1
The blending amount of (3,3 ′, 4,4′-diepoxy) bicyclohexyl (B1) as the epoxy compound (B) was changed from 90 parts to 100 parts without blending the alicyclic olefin polymer (A1). Except having done, it carried out similarly to Example 1, obtained the curable resin composition, the film molded object, the cured film, and the multilayer laminated substrate, and evaluated similarly. The results are shown in Table 1.

Comparative Example 2
Example 1 except that 90 parts of 1,2: 8,9 diepoxy limonene was used instead of (3,3 ′, 4,4′-diepoxy) bicyclohexyl (B1) as the epoxy compound (B). In the same manner as above, a curable resin composition, a film molded body, a cured film, and a multilayer laminated substrate were obtained and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 3
Except for using 90 parts of bisphenol A type epoxy resin (jER828EL, manufactured by Mitsubishi Chemical Corporation) instead of (3,3 ′, 4,4′-diepoxy) bicyclohexyl (B1) as the epoxy compound (B), In the same manner as in Example 1, a curable resin composition, a film molded body, a cured film, and a multilayer laminated substrate were obtained and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 4
A comparison was made except that instead of the arylsulfonium salt derivative (C1) as the photoacid generator (C), 1.4 parts of a 70% anisole solution of 2-phenyl-4-methylimidazole as the imidazole curing agent was used. In the same manner as in Example 3, a curable resin composition, a film molded body, a cured film, and a multilayer laminated substrate were obtained and evaluated in the same manner. The results are shown in Table 1.

As shown in Table 1, a curable resin composition containing an alicyclic olefin polymer (A), an epoxy compound (B) containing two or more epoxy groups condensed to a ring, and a photoacid generator (C). The product may be able to give a cured product excellent in water resistance (low water absorption), electrical characteristics (low dielectric constant and low dielectric loss tangent), heat resistance (low linear expansion coefficient), and insulation reliability. As can be seen (Examples 1-5).
On the other hand, when the alicyclic olefin polymer (A) is not blended, a good film cannot be obtained, and the obtained cured product has poor water absorption, linear expansion coefficient, and insulation reliability. Results were obtained (Comparative Example 1).
When 1,2: 8,9 diepoxy limonene is used instead of the epoxy compound (B) containing two or more epoxy groups condensed on the ring, the water absorption rate and the linear expansion coefficient are deteriorated. (Comparative Example 2).
In addition, when a bisphenol A type epoxy resin is used instead of the epoxy compound (B) containing two or more epoxy groups condensed on the ring, the curing is insufficient and the linear expansion coefficient and the glass transition temperature are low. A sample that could be measured could not be obtained (Comparative Example 3).
Furthermore, a bisphenol A type epoxy resin was used in place of the epoxy compound (B) containing two or more epoxy groups condensed on the ring, and an amine curing agent was used in place of the photoacid generator (C). In this case, the insulation reliability was inferior (Comparative Example 4).

Claims (8)

  An alicyclic olefin polymer (A) having at least one functional group selected from the group consisting of a carboxyl group, a carboxylic acid anhydride group, and a hydroxyphenyl group, an epoxy containing two or more epoxy groups condensed to a ring A curable resin composition comprising a compound (B) and a photoacid generator (C).   The curable resin composition according to claim 1, further comprising an inorganic filler (D).   The curable resin composition according to claim 1 or 2, wherein the epoxy compound (B) does not contain an ester bond.   The film which consists of a curable resin composition in any one of Claims 1-3.   Hardened | cured material formed by hardening | curing the curable resin composition in any one of Claims 1-3, or the film of Claim 4.   The laminated body formed by laminating | stacking the film of Claim 4 on a base material.   A laminate comprising a glass substrate or a silicon wafer substrate and the cured product according to claim 5.   The laminate according to claim 7, wherein a metal plating layer is formed on the surface of the cured product.