JP2010084026A - Curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition which has excellent flame retardancy and with which an insulating film facilitating placement of a conductive layer including a fine wiring pattern produced by plating, and excellent in adhesive properties of the conductive layer, is obtained. <P>SOLUTION: The curable resin composition is formed by compounding an alicyclic olefin polymer (A) of which the weight average molecular weight is 10,000-250,000 and which has a carboxyl group or an acid anhydride group with a curing agent (B), and a phosphazene compound (C) including phenols with a content of ≤20 μg/g included as impurities and having a predetermined structure including an aryloxy group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  In particular, the present invention relates to a curable resin composition suitably used for an insulating film of a circuit board. More specifically, the present invention is excellent in flame retardancy and can easily provide a conductor layer having a fine circuit pattern by plating. The present invention relates to a curable resin composition that provides an insulating film having excellent adhesion of the conductor layer.

  With the pursuit of downsizing, multi-functionalization, high-speed communication, etc. of electronic devices, higher density of circuit boards used in electronic devices is required, and therefore circuit boards are being made multilayered. Multi-layer circuit boards usually require an electrical insulation layer stacked on an inner layer board consisting of an electrical insulation layer and a conductor layer formed on the surface, and a conductor layer is formed on the electrical insulation layer. In response to this, a plurality of sets of electrical insulating layers and conductor layers are further laminated thereon. When the conductor layer of such a multilayer circuit board has a high-density pattern, there is often a problem that the conductor layer or the board generates heat. Therefore, the improvement of the flame retardance of the insulating film used for forming an electrical insulating layer is calculated | required. In addition, used multilayer circuit boards are often incinerated. Conventionally, since halogen-based flame retardants are blended in the electrical insulating layer (see, for example, Patent Document 1), halogen-based harmful substances are generated during incineration. To do is also a problem. Therefore, there is a demand for a multilayer circuit board having a flame-retardant insulating film that does not generate halogen-based harmful substances during incineration.

  As a material for forming a flame-retardant insulating film that meets such demands, Patent Document 2 discloses a polymer and a curing agent having a weight average molecular weight of 10,000 to 250,000 and having a carboxyl group or an acid anhydride group. And a curable resin composition containing a phosphazene compound. This curable resin composition is suitable for obtaining a multilayer circuit board capable of orderly forming fine wiring patterns with high density, and is excellent in flame retardancy, insulation and crack resistance, and at the time of incineration. It provides an insulating film that is less likely to generate harmful substances.

  By the way, Patent Document 2 discloses a phosphazene compound in which an aryloxy group is bonded to a phosphorus atom forming the skeleton of a phosphazene compound as a specific example of the phosphazene compound to be blended in the curable resin composition. Such a phosphazene compound can provide good flame retardancy to a resin composition, among other phosphazene compounds.

JP-A-2-255848 Japanese Patent Laid-Open No. 2005-248069

  However, according to the study of the present inventors, when a phosphazene compound in which an aryloxy group is bonded to a phosphorus atom constituting the phosphazene compound skeleton is added to the curable resin composition, when the cured product is metal-plated, It has been clarified that so-called plating blisters are likely to occur, and that the plating layer is easily peeled off. Since a conductive layer having a fine circuit pattern is usually provided on the insulating film for a circuit board by plating, it is necessary to prevent such plating blistering and peeling of the plating layer.

  Therefore, an object of the present invention is to provide a curable resin composition that is excellent in flame retardancy and that can easily provide a conductor layer having a fine circuit pattern by plating and provides an insulating film with excellent adhesion of the conductor layer. To provide things.

  As a result of diligent research to achieve the above object, the present inventors have found that plating in a cured product of a curable resin composition containing a phosphazene compound in which an aryloxy group is bonded to a phosphorus atom constituting a skeleton of a phosphazene compound. It was found that the problem of blistering and peeling of the plating layer was caused by phenols contained in the phosphazene compound as impurities. And after performing the process which removes phenols from the phosphazene compound containing such phenols, the conductor layer provided with a fine circuit pattern by plating is provided by mix | blending it with a specific curable resin composition. It was found that a curable resin composition that provides an insulating film that is easy to handle and has excellent adhesion of the conductor layer can be obtained. The present invention has been completed based on this finding.

  Thus, according to the present invention, the alicyclic olefin polymer (A) having a carboxyl group or an acid anhydride group having a weight average molecular weight of 10,000 to 250,000 is added to the curing agent (B) as an impurity. Curable resin composition formed by blending at least one phosphazene compound (C) selected from the following general formula (1) and the following general formula (2), wherein the content of phenols contained is 20 μg / g or less. Things are provided.

（一般式（１）中、Ｘ^１は任意の一価の基であり、Ｙは−Ｎ＝Ｐ（Ｒ^２）_３または−Ｎ＝Ｐ（＝Ｏ）Ｒ^２を表し、Ｙは−Ｐ（＝Ｏ）Ｒ^３または−Ｐ（Ｒ^３）_３を表す。Ｒ^１〜Ｒ^３は独立に炭素数１〜８のアルキル基、アルケニル基、シクロアルキル基、アリール基、アラルキル基、アルケニルアリール基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アリールオキシ基、アラルキルオキシ基、アシルオキシアルコキシ基、アリールメルカプト基、アルキルアミノ基、アリールアミノ基、アリールグリシジルオキシ基、または、アミノ基もしくはハロゲン原子である。ｍは１〜１５００の整数である。）

(In General Formula (1), X ¹ is an arbitrary monovalent group, Y represents —N═P (R ² ) ₃ or —N═P (═O) R ² , and Y represents —P ( ═O) represents R ³ or —P (R ³ ) _3. R ^{1 to} R ³ independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenylaryl group, A haloalkyl group, an alkoxy group, a haloalkoxy group, an aryloxy group, an aralkyloxy group, an acyloxyalkoxy group, an arylmercapto group, an alkylamino group, an arylamino group, an arylglycidyloxy group, or an amino group or a halogen atom. Is an integer from 1 to 1500.)

（一般式（２）中、Ｘ^２は任意の一価の基であり、Ｒ^４は炭素数１〜８のアルキル基、アルケニル基、シクロアルキル基、アリール基、アラルキル基、アルケニルアリール基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アリールオキシ基、アラルキルオキシ基、アシルオキシアルコキシ基、アリールメルカプト基、アルキルアミノ基、アリールアミノ基、アリールグリシジルオキシ基、または、アミノ基もしくはハロゲン原子である。ｎは１〜１５００の整数である。）

(In the general formula (2), X ² is an arbitrary monovalent group, and R ⁴ is an alkyl group having 1 to 8 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenylaryl group, a haloalkyl group. A group, an alkoxy group, a haloalkoxy group, an aryloxy group, an aralkyloxy group, an acyloxyalkoxy group, an arylmercapto group, an alkylamino group, an arylamino group, an arylglycidyloxy group, or an amino group or a halogen atom. (It is an integer of 1-1500.)

  The curable resin composition is preferably used for an insulating film of a circuit board.

  Further, according to the present invention, there is provided a circuit board insulating film obtained by curing the above curable resin composition, and further comprising the above circuit board insulating film having a conductor layer formed on the surface by plating. A circuit board is provided.

  According to the present invention, there is provided a curable resin composition that is excellent in flame retardancy and that is easy to provide a conductor layer having a fine circuit pattern by plating and that provides an insulating film having excellent adhesion of the conductor layer. Provided.

  The curable resin composition of the present invention is obtained by blending a specific alicyclic olefin polymer (A) with a curing agent (B) and a specific phosphazene compound (C).

  The alicyclic olefin polymer (A) used in the present invention has a weight average molecular weight of 10,000 to 250,000 and a carboxyl group or an acid anhydride group (hereinafter, both are collectively referred to as “carboxyl group etc.”). Is an alicyclic olefin polymer. The weight average molecular weight (Mw) of the alicyclic olefin polymer (A) used in the present invention is preferably 15,000 to 150,000, more preferably 20,000 to 100,000. When Mw of an alicyclic olefin polymer (A) is too small, the intensity | strength of the obtained hardened | cured material will become inadequate and there exists a possibility that electrical insulation may fall. On the other hand, when Mw is too large, the compatibility between the alicyclic olefin polymer (A) and the curing agent (B) is reduced, and the surface roughness of the cured product is increased, which is used as an insulating film of a circuit board. There is a possibility that the accuracy of the circuit pattern formed on the substrate will deteriorate.

The alicyclic olefin polymer (A) is not particularly limited as long as it has the above-described molecular weight and functional group, but the volume specific resistance (according to ATSM D257) of the alicyclic olefin polymer (A) is preferably 1 × 10 ¹² Ω · cm or more, more preferably 1 × 10 ¹³ Ω · cm or more, and particularly preferably 1 × 10 ¹⁴ Ω · cm or more.

  An alicyclic olefin polymer is a polymer of an unsaturated hydrocarbon having an alicyclic structure. Specific examples of the alicyclic olefin polymer include a ring-opening polymer of a norbornene monomer and a hydrogenated product thereof, an addition polymer of a norbornene monomer, an addition weight of a norbornene monomer and a vinyl compound. Polymer, monocyclic cycloalkene polymer, alicyclic conjugated diene polymer, vinyl alicyclic hydrocarbon polymer and hydrogenated product thereof, and further polymerization of aromatic olefin polymer such as aromatic ring hydrogenated product. A polymer in which an alicyclic structure is formed by subsequent hydrogenation to form the same alicyclic structure as the alicyclic olefin polymer may be used. Among these, ring-opening polymers of norbornene monomers and hydrogenated products thereof, addition polymers of norbornene monomers, addition polymers of norbornene monomers and vinyl compounds, aromatic olefin polymers An aromatic ring hydride is preferable, and a hydride of a ring-opening polymer of a norbornene monomer is particularly preferable.

  The method for adjusting the weight average molecular weight (Mw) of the alicyclic olefin polymer (A) to the above range may be in accordance with a conventional method. For example, the ring-opening polymerization of the alicyclic olefin is titanium-based, tungsten-based or ruthenium. When performing using a system catalyst, the method of adding about 0.1-10 mol% of molecular weight modifiers, such as a vinyl compound and a diene compound, with respect to the monomer whole quantity is mentioned. When a large amount of the molecular weight modifier is used, a polymer having a low Mw is obtained. Examples of such molecular weight modifiers include vinyl compounds such as α-olefin compounds such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrene compounds such as styrene and vinyltoluene; ethyl vinyl ether, isobutyl vinyl ether, Ether compounds such as allyl glycidyl ether; halogen-containing vinyl compounds such as allyl chloride; other vinyl compounds such as allyl acetate, allyl alcohol, glycidyl methacrylate, and acrylamide; In the diene compound, non-conjugated dienes such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl-1,5-hexadiene, etc. Compounds; conjugated diene compounds such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene; It is done.

  The carboxyl group of the alicyclic olefin polymer (A) may be directly bonded to the carbon atom of the alicyclic olefin monomer unit, or may be a methylene group, an oxy group, an oxycarbonyloxyalkylene group, a phenylene group, etc. And may be bonded via a divalent group. As a method for producing an alicyclic olefin polymer having a carboxyl group or the like, (i) a monomer in which a carboxyl group or the like is previously bonded to a carbon atom of an alicyclic olefin monomer, ethylene, if necessary , A method of polymerizing with a copolymerizable monomer such as 1-hexene, 1,4-hexadiene, (b) an alicyclic olefin polymer having no carboxyl group, etc., in the presence of a radical initiator A method of graft-modifying a carbon-carbon unsaturated bond-containing compound having, for example, a polymer, and (c) a norbornene-based monomer having a precursor group that can be converted into a carboxyl group such as a carboxylate group Thereafter, a method of converting a precursor group into a carboxyl group or the like by hydrolysis or the like is mentioned.

As the carboxyl group-containing alicyclic olefin monomer used in the method (a), 8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] dodec-3-ene, 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, 8-methyl-8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-carboxymethyl-8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5-exo-6-endo-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 8-exo-9-endo-dihydroxycarbonyltetracyclo [4. 4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.

Examples of the acid anhydride group-containing alicyclic olefin monomer used in the method (a) include bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec- ³ -ene-8,9-dicarboxylic anhydride, hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] etc. heptadec-4-ene-11,12-dicarboxylic acid anhydride.

On the other hand, specific examples of the monomer for obtaining the alicyclic olefin polymer having no carboxyl group and the like used in the method (b) 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 [ 4.3.0.1 ^2,5] deca-3,7-diene (common name: dicyclopentadiene), tetracyclo ^{[8.4.0.1 11,14.} 0 ^2,8 ] tetradeca-3,5,7,12,11-tetraene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dec-3-ene (common name: tetracyclododecene), 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, pentacyclo [7.4.0.1 ^3,6. 1 ^10,13 . 0 ^2,7 ] pentadeca-4,11-diene, cyclopentene, cyclopentadiene, 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene, 8-phenyl-tetracyclo [4.4. 0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 7,10-methano-6b, 7,10,10a-tetrahydrofluoranthene and the like.

  Examples of the carbon-carbon unsaturated bond-containing compound having a carboxyl group and the like used in the method (b) include acrylic acid, methacrylic acid, α-ethylacrylic acid, 2-hydroxyethyl (meth) acrylic acid, Maleic acid, fumaric acid, itaconic acid, endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid, methyl-endocis-bicyclo [2.2.1] hept-5-ene- And unsaturated carboxylic acid compounds such as 2,3-dicarboxylic acid; unsaturated carboxylic acid anhydrides such as maleic anhydride, chloromaleic anhydride, butenyl succinic anhydride, tetrahydrophthalic anhydride, and citraconic anhydride;

As the monomer containing a precursor group that can be converted into a carboxyl group or the like used in the method (c) above, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] dodec-3-ene, 5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2 -Ene and the like.

  The content of the alicyclic olefin polymer (A) used in the present invention is not particularly limited as long as it has a carboxyl group or the like, but all of the repeating units constituting the alicyclic olefin polymer (A) are used. It is 5-60 mol% normally with respect to the number of moles, Preferably it is 10-50 mol%.

  Moreover, the alicyclic olefin polymer (A) used in the present invention may have a functional group other than a carboxyl group (hereinafter sometimes referred to as other functional group). Examples of other functional groups include an alkoxycarbonyl group, a cyano group, a phenyl group, a hydroxyphenyl group, an epoxy group, an alkoxyl group, an amide group, and an imide group. These other functional groups are preferably 30 mol% or less, more preferably 10 mol% or less, and particularly preferably 1 mol% or less with respect to the carboxyl group or the like.

  The proportion of the repeating unit derived from the alicyclic olefin in the alicyclic olefin polymer (A) used in the present invention is not particularly limited, but is usually 30 to 100% by weight, preferably 50 to 100% by weight, more preferably 70. ~ 100% by weight. When the ratio of the repeating unit derived from the alicyclic olefin is too small, the heat resistance of the resulting cured product 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.

  The molecular weight distribution of the alicyclic olefin polymer (A) used in the present invention is not particularly limited, but the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using cyclohexane or toluene as a solvent. And the number average molecular weight (Mn) (Mw / Mn), usually 5 or less, preferably 4 or less, more preferably 3 or less.

  The glass transition temperature (Tg) of the alicyclic olefin polymer (A) is preferably 120 to 300 ° C. When the Tg is too low, when the cured product of the curable resin composition is used as an insulating film, sufficient electrical insulation cannot be maintained at a high temperature, and when the Tg is too high, the insulating film receives a strong impact. There is a possibility that the conductor layer may be broken due to cracks.

  Moreover, when forming an insulating film with the hardening | curing agent (B) and phosphazene compound (C) which are mentioned later, an alicyclic olefin polymer (A) melt | dissolves in an organic solvent and makes it a varnish of curable resin composition. When used, it is preferably soluble at room temperature in an organic solvent described later.

  The polymerization method for obtaining the alicyclic olefin polymer (A) and the hydrogenation method performed as necessary are not particularly limited and can be performed according to a known method.

  The curing agent (B) used in the present invention is not limited as long as it is generally blended with a curable resin composition for forming an insulating film and forms a crosslinked structure by heating. Especially, the compound which can be bridge | crosslinked to the carboxyl group or acid anhydride group of an alicyclic olefin polymer (A) is preferable. Examples of the crosslinking agent include polyvalent epoxy compounds, polyvalent isocyanate compounds, polyvalent amine compounds, polyvalent hydrazide compounds, aziridine compounds, basic metal oxides, and organometallic halides. Moreover, you may use a peroxide together.

  Examples of the polyvalent epoxy compound include a glycidyl ether type such as a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, a cresol type epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, and a hydrogenated bisphenol A type epoxy compound. Epoxy compound; polycyclic epoxy compound such as alicyclic epoxy compound, glycidyl ester type epoxy compound, glycidyl amine type epoxy compound, isocyanurate type epoxy compound, phosphorus-containing epoxy compound; etc. having two or more epoxy groups in the molecule Compounds. These may be used alone or in combination of two or more.

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

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

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

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

  Among these curing agents, a polyvalent epoxy compound is preferable from the viewpoint that the reactivity with the alicyclic olefin polymer (A) having a carboxyl group or the like is moderate and the resulting resin composition is easy to process. However, bisphenol A glycidyl ether type epoxy compounds are preferred. The amount of the curing agent (B) used is usually 1 to 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer (A). It is a range. Moreover, it is preferable to add a curing accelerator in addition to the curing agent (B) because a cured product having high heat resistance can be easily obtained. For example, when a polyvalent epoxy compound is used as the curing agent (B), it is preferable to use a curing accelerator such as a triazole compound or an imidazole compound.

  The phosphazene compound (C) used in the present invention has at least one phosphazene compound selected from the following general formula (1) and the following general formula (2), wherein the content of phenols contained as impurities is 20 μg / g or less. It is.

（一般式（１）中、Ｘ^１は任意の一価の基であり、Ｙは−Ｎ＝Ｐ（Ｒ^２）_３または−Ｎ＝Ｐ（＝Ｏ）Ｒ^２を表し、Ｙは−Ｐ（＝Ｏ）Ｒ^３または−Ｐ（Ｒ^３）_３を表す。Ｒ^１〜Ｒ^３は独立に炭素数１〜８のアルキル基、アルケニル基、シクロアルキル基、アリール基、アラルキル基、アルケニルアリール基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アリールオキシ基、アラルキルオキシ基、アシルオキシアルコキシ基、アリールメルカプト基、アルキルアミノ基、アリールアミノ基、アリールグリシジルオキシ基、または、アミノ基もしくはハロゲン原子である。ｍは１〜１５００の整数である。）

(In General Formula (1), X ¹ is an arbitrary monovalent group, Y represents —N═P (R ² ) ₃ or —N═P (═O) R ² , and Y represents —P ( ═O) represents R ³ or —P (R ³ ) _3. R ^{1 to} R ³ independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenylaryl group, A haloalkyl group, an alkoxy group, a haloalkoxy group, an aryloxy group, an aralkyloxy group, an acyloxyalkoxy group, an arylmercapto group, an alkylamino group, an arylamino group, an arylglycidyloxy group, or an amino group or a halogen atom. Is an integer from 1 to 1500.)

（一般式（２）中、Ｘ^２は任意の一価の基であり、Ｒ^４は炭素数１〜８のアルキル基、アルケニル基、シクロアルキル基、アリール基、アラルキル基、アルケニルアリール基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アリールオキシ基、アラルキルオキシ基、アシルオキシアルコキシ基、アリールメルカプト基、アルキルアミノ基、アリールアミノ基、アリールグリシジルオキシ基、または、アミノ基もしくはハロゲン原子である。ｎは１〜１５００の整数である。）

(In the general formula (2), X ² is an arbitrary monovalent group, and R ⁴ is an alkyl group having 1 to 8 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenylaryl group, a haloalkyl group. A group, an alkoxy group, a haloalkoxy group, an aryloxy group, an aralkyloxy group, an acyloxyalkoxy group, an arylmercapto group, an alkylamino group, an arylamino group, an arylglycidyloxy group, or an amino group or a halogen atom. (It is an integer of 1-1500.)

  The phosphazene compound in which an aryloxy group is bonded to the phosphorus atom forming the skeleton of the phosphazene compound represented by the above general formula (1) or general formula (2) is particularly chemically stable among phosphazene compounds. Since the effect of imparting high flame retardancy is high, the cured product of the curable resin composition obtained by blending it exhibits excellent flame retardancy. The phosphazene compound represented by the general formula (1) or the general formula (2) can be obtained by reacting a metal phenolate with dichlorophosphazene as described in, for example, JP-A-2001-31639. It is also possible to obtain a commercial product. However, when the phosphazene compound is obtained by a method of reacting metal phenolates with dichlorophosphazene, the phosphazene compounds usually contain phenols generated by hydrolysis of the metal phenolates. Therefore, the phosphazene compounds represented by the general formula (1) and the general formula (2) that are generally commercially available contain phenols in an amount of several hundred μg / g. When a phosphazene compound containing phenols at a relatively high concentration is added to the curable resin composition, problems such as plating blisters and peeling of the plating layer occur when the cured product is plated.

  Therefore, in the present invention, the content of phenols (compound having a hydroxyl group directly bonded to an aromatic ring) contained as impurities (μg number of phenols contained in 1 g of phosphazene compound containing impurities to be measured) is A phosphazene compound (C) of 20 μg / g or less is used. By using such a phosphazene compound (C) with a low content of phenols, the problem of plating blisters and peeling of the plating layer when the cured product of the curable resin composition is plated is prevented. It is easy to provide a conductor layer having a fine circuit pattern by plating, and a curable resin composition that provides an insulating film having excellent adhesion of the conductor layer can be obtained.

  The method for obtaining the phosphazene compound (C) having a low content of phenols used in the present invention is not particularly limited. For example, for phosphazene compounds obtained by reacting metal phenolates with dichlorophosphazene or commercially available phosphazene compounds, The method of performing the process for reducing content of phenols is mentioned. As an example of the treatment for reducing the content of phenols in the phosphazene compound, a method for treating the phosphazene compound with an adsorbent as described in JP-A-2001-31639 and a reactive agent are used. And a method of treating a phosphazene compound.

  In order to treat the phosphazene compound with the adsorbent, the phosphazene compound and the adsorbent may be brought into contact with each other by a conventionally known method. For example, a method of mixing the phosphazene compound and the adsorbent in a solvent, A method can be used in which the agent is packed in a column and the phosphazene compound is passed through the column.

  As the adsorbent to be used, a known adsorbent may be used. For example, activated carbon, silica gel, activated alumina, activated clay, synthetic zeolite, polymer adsorbent and the like can be used.

  In the case of mixing the phosphazene compound and the adsorbent in the solvent, the solvent to be used is not particularly limited, but it is preferable that the phosphazene compound can be dissolved and does not inhibit the action of the adsorbent. Examples of such solvents include aromatic hydrocarbons such as benzene, toluene and xylene, halogenated aromatic hydrocarbons such as monochlorobenzene and dichlorobenzene, halogenated hydrocarbons such as chloroform, carbon tetrachloride and chloroethane, Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, methyl formate, ethyl formate, propyl formate, formic acid Esters such as butyl, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethers such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, trioxane Acetonitrile, benzonitrile, and other nitrogen-containing hydrocarbons such as pyridine and the like, which may be used alone, or in combination of two or more. The amount of the solvent used is not particularly limited, but is usually in the range where the concentration of the phosphazene compound is 1 to 90% by weight, and preferably in the range of 5 to 80% by weight. Further, the amount of the adsorbent used in this case is not particularly limited, but is usually 1 to 100 parts by weight, preferably 2 to 50 parts by weight with respect to 100 parts by weight of the phosphazene compound.

  Although the temperature and time for mixing the phosphazene compound and the adsorbent are not particularly limited, the temperature is usually 0 ° C. to 200 ° C., and the time is 5 minutes to 12 hours. Moreover, you may stir using a magnetic stirrer etc. as needed.

  In the method of treating a phosphazene compound with a reactant, the phosphazene compound may be brought into contact with a conventionally known reactant having reactivity with a hydroxyl group of phenols. Examples of such a reactant include hypochlorite, thiosulfate, dialkylsulfuric acid, orthoester, diazoalkane, lactone, alkane sultone, epoxy compound, hydrogen peroxide solution and the like.

  The content of phenols in the phosphazene compound treated as described above can be easily measured by, for example, liquid chromatography. Therefore, the content of phenols contained as impurities in the phosphazene compound can be easily reduced to 20 μg / g or less by performing the treatment as described above while confirming the content of phenols.

  The phosphazene compound (C) used in the present invention is particularly limited as long as the content of phenols contained as impurities is 20 μg / g or less and is represented by the general formula (1) or the general formula (2). However, a phosphazene compound in which two aryloxy groups are bonded to one phosphorus atom constituting the phosphazene compound skeleton is particularly preferably used. That is, the phosphazene compound (C) used in the present invention is particularly preferably at least one phosphazene compound selected from the following general formula (3) and the following general formula (4).

（一般式（３）中、Ｘ^１およびＸ^３は独立に任意の一価の基を表す。Ｙは−Ｎ＝Ｐ（Ｒ^２）_３または−Ｎ＝Ｐ（＝Ｏ）Ｒ^２を表し、Ｙは−Ｐ（＝Ｏ）Ｒ^３または−Ｐ（Ｒ^３）_３を表す。Ｒ^２およびＲ^３は独立に炭素数１〜８のアルキル基、アルケニル基、シクロアルキル基、アリール基、アラルキル基、アルケニルアリール基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アリールオキシ基、アラルキルオキシ基、アシルオキシアルコキシ基、アリールメルカプト基、アルキルアミノ基、アリールアミノ基、アリールグリシジルオキシ基、または、アミノ基もしくはハロゲン原子である。ｍは１〜１５００の整数である。）

(In General Formula (3), X ¹ and X ³ independently represent any monovalent group. Y represents —N═P (R ² ) ₃ or —N═P (═O) R ² , Y represents —P (═O) R ³ or —P (R ³ ) _3. R ² and R ³ independently represent an alkyl group, alkenyl group, cycloalkyl group, aryl group, aralkyl group having 1 to 8 carbon atoms. , Alkenylaryl group, haloalkyl group, alkoxy group, haloalkoxy group, aryloxy group, aralkyloxy group, acyloxyalkoxy group, arylmercapto group, alkylamino group, arylamino group, arylglycidyloxy group, amino group or halogen (M is an integer of 1 to 1500)

（一般式（４）中、Ｘ^２およびＸ^４は独立に任意の一価の基を表す。ｎは１〜１５００の整数である。）

(In General Formula (4), X ² and X ⁴ independently represent any monovalent group. N is an integer of 1 to 1500.)

  Further, the phosphazene compound (C) used in the present invention reacts with the functional group (carboxyl group or acid anhydride group) of the alicyclic olefin polymer (A) or the functional group of the curing agent (B) and is shared. It is preferable to have a functional group that generates a bond (hereinafter sometimes simply referred to as “reactive functional group”). By using such a phosphazene compound, it is possible to prevent the phosphazene compound from bleeding out from the cured product of the curable resin composition.

The reactive functional group that the phosphazene compound (C) can contain is not particularly limited, and examples thereof include a hydroxyl group, a carboxyl group, an epoxy group, an amino group, and a mercapto group. Among these, a hydroxyl group, a carboxyl group, an epoxy group, and a mercapto group are preferable from the viewpoint that gelation of the curable resin composition hardly occurs. These reactive functional groups may be directly bonded to the phosphorus atom forming the phosphazene compound skeleton or indirectly bonded, but from the viewpoint of flame retardancy and reactivity, It is preferably located at the para position of the aryloxy group of the phosphazene compound (C). That is, as the phosphazene compound (C) used in the present invention, at least a part of the monovalent groups represented by X ^{1 to} X ⁴ in the above general formulas (1) to (4) is alicyclic olefin heavy. What is the functional group which reacts with the functional group which a compound (A) has, and the functional group which a hardening | curing agent (B) has, and produces | generates a covalent bond is preferable, From a hydroxyl group, a carboxyl group, an epoxy group, an amino group, and a mercapto group Those which are at least one group selected are more preferable, and those which are at least one group selected from a hydroxyl group, a carboxyl group, an epoxy group and a mercapto group are particularly preferable. In the above general formulas (1) to (4), the monovalent group represented by X ^{1 to} X ⁴ may not be reactive with a functional group. , A hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, a cycloalkyl group, and an aryl group.

The phosphazene compound (C) used in the present invention has a vinyl group (CH ₂ ═CH—) in its molecule from the viewpoint of preventing a decrease in electrical properties in the cured product of the curable resin composition due to oxidative degradation. It is preferable that it does not have. Further, the phosphazene compound (C) used in the present invention may be a chain or a cyclic one, but from the viewpoint of obtaining a cured product having higher heat resistance, a cyclic one (ie, And those represented by the general formula (2) or (4)). Further, among the cyclic phosphazene compounds (C), those in the general formula (2) or (4) are preferably 3 to 10, more preferably 3 to 5, and particularly preferably 3. .

  Preferable specific examples of the phosphazene compound (C) used in the present invention include cyclic phosphazene compounds represented by the following chemical formula, wherein n is usually 3 to 10, preferably 3 to 5, more preferably 3. Can be mentioned.

  Among the phosphazene compounds exemplified above, phosphazene compounds represented by the formulas (5) to (8) are particularly preferably used from the viewpoint of flame retardancy and heat resistance of the obtained cured product.

  In the curable resin composition of the present invention, the phosphazene compound (C) may be used alone or in combination of two or more. The amount of the phosphazene compound (C) is not particularly limited, but is usually 1 to 40 parts by weight, preferably 5 to 35 parts by weight, per 100 parts by weight of the alicyclic olefin polymer (A). . If the amount of the phosphazene compound (C) is too small, the flame retardancy of the resulting cured product is insufficient. Conversely, if the amount is too large, the solder heat resistance is lowered, so that neither is preferable.

You may mix | blend a filler with the curable resin composition of this invention. The filler to be added is preferably non-conductive that does not deteriorate the dielectric properties of the insulating film and has a particle size of less than 1 μm. The shape of the filler is not particularly limited and may be spherical, fibrous, plate-like, or the like, but is preferably a fine powder to obtain a fine rough surface shape. By blending the filler, flame retardancy and linear expansion coefficient are improved. Specific examples of such fillers include silica, talc, clay, calcium carbonate, magnesium carbonate, barium zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, hydrated alumina, water Examples include magnesium oxide, aluminum hydroxide, barium sulfate, polyamide particles, liquid crystal polymer particles, polysulfide particles, pigments, and clay minerals such as montmorillonite. Of these fillers, silica, clay, polyamide particles, liquid crystal polymer particles, and montmorillonite are particularly preferable from the viewpoint of linear expansion coefficient and electrical characteristics. Furthermore, the inorganic filler such as silica and clay may be treated with a silane coupling agent or an organic acid such as stearic acid.

The curable resin composition may further contain a compound having a phosphorus atom in the molecule (hereinafter sometimes referred to as “phosphorus-containing compound”). The flame retardancy of the cured product obtained by blending a compound having a phosphorus atom in the molecule is improved. Such a compound having a phosphorus atom in the molecule includes a cyclic phosphorus compound, an organic phosphate, an inorganic phosphate, a normal phosphate, a condensed phosphate. Examples thereof include esters and aromatic organic phosphorus compounds. Among these, cyclic phosphorus compounds, organic phosphates, and condensed phosphates are particularly preferable from the viewpoint of flame retardancy, water resistance, difficulty in deteriorating linear expansion coefficient, and difficulty in bleeding out.

  To the curable resin composition of the present invention, a non-halogen flame retardant may be added as a flame retardant aid for the purpose of enhancing flame retardancy. Examples of such flame retardant aids include antimony compounds such as antimony trioxide, antimony pentoxide, sodium antimonate; aluminum hydroxide, magnesium hydroxide, zinc borate, guanidine sulfamate, zirconium compounds, molybdenum compounds, tin compounds, etc. Inorganic flame retardants; and the like. Of these, magnesium hydroxide and aluminum hydroxide are preferable, and magnesium hydroxide is particularly preferable from the viewpoint of excellent heat resistance, moisture resistance, and flame retardancy.

  The curable resin composition of the present invention may further include a soft polymer, a heat stabilizer, a weather stabilizer, an anti-aging agent, a leveling agent, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, if necessary. Optional components such as a lubricant, a dye, a natural oil, a synthetic oil, a wax, an emulsion, a magnetic material, a dielectric property adjusting agent, a toughening agent, and a laser processability improving agent are blended. The blending ratio of the optional components is appropriately selected within a range that does not impair the object of the present invention.

  The curable resin composition of the present invention is generally mixed with an organic solvent and used as a varnish. The organic solvent for preparing the varnish has a boiling point of preferably 30 to 250 ° C., more preferably 50 to 200 ° C. for the convenience of later heating and volatilization. Examples of such organic solvents include aromatic hydrocarbons such as toluene, xylene, ethylbenzene and trimethylbenzene; aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane; alicyclics such as cyclopentane and cyclohexane Hydrocarbons; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene; methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and the like.

  There is no special restriction | limiting in the preparation method of a varnish, For example, what is necessary is just to mix each component and organic solvent which comprise curable resin composition in accordance with a conventional method. For example, it can be carried out by a method using a magnetic stirrer, a high-speed homogenizer, a dispersion, a planetary stirrer, a twin-screw stirrer, a ball mill, or a three-roll. The mixing temperature is preferably within the boiling point of the organic solvent as long as the reaction by the curing agent does not occur. The amount of the organic solvent used is appropriately selected according to the demand for the thickness of the electrical insulating layer and the surface flatness, but the solid content concentration of the varnish is usually 5 to 70% by weight, preferably 10 to 65% by weight. Preferably it is the range which becomes 20 to 60 weight%.

  Next, after impregnating and / or laminating the prepared varnish on a base material, the organic solvent constituting the varnish is removed by drying to obtain a molded body of the curable resin composition. Usually, the obtained molded body is laminated on a substrate having a conductor layer on at least the surface (hereinafter sometimes referred to as “inner layer substrate”), and then the curable resin in the molded body is cured. Then, an insulating film is formed on the inner layer substrate to obtain a circuit board. This insulating film functions as an electrical insulating layer of the circuit board, and a conductor layer can be further formed thereon to make the circuit board multilayer. At this time, the insulating film formed on the inner layer substrate becomes a so-called interlayer insulating layer.

The base material used as described above is not particularly limited, but is preferably a molded body having an electrical insulating property that is made of an organic polymer and has excellent flame retardancy, and more specifically, conforms to the UL94 standard. It is preferable that the molded body is V-0, V-1, VTM-0 or VTM-1. Moreover, the organic polymer used as the material for forming the molded body used as the base material has a linear expansion coefficient of 10 × 10 ⁻⁶ / ° C. or less at 30 ° C. to 120 ° C. and a weight average molecular weight of 1,000 to 500, 000 organic polymers are preferred.

Specific examples of the substrate include nonwoven fabric, woven fabric, and resin film. In addition, examples of the organic polymer that is the material include polyacrylate, aramid, liquid crystal polymer, polyethylene terephthalate, polycarbonate, polypropylene, polyethylene, polyethylene naphthalate, polyimide, nylon, and the like. From the viewpoint of electrical characteristics. Further, the substrate is a molded body that can be impregnated or coated with the varnish described above, and from the viewpoint of insulating film formation, the film thickness is usually 20 μm or less, preferably 15 μm or less, more preferably 10 μm or less, Usually, it is 0.05 μm or more, preferably 0.1 μm or more. If the film thickness is too small, the strength cannot be obtained, and the linear expansion coefficient of the film cannot be improved when combined.
On the other hand, if the film thickness is too large, the laser processability deteriorates. Moreover, as for the surface average roughness of a base material, Ra is 300 nm or less normally, Preferably it is 150 nm or less, More preferably, it is 100 nm or less. When the surface average roughness Ra of the support film is too large, the surface average roughness Ra of the insulating film formed by curing becomes large, and it becomes difficult to form a fine circuit pattern.

Examples of the nonwoven fabric include an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, a polyethylene terephthalate nonwoven fabric, a polycarbonate nonwoven fabric, and a nylon nonwoven fabric. Among these nonwoven fabrics, an aramid nonwoven fabric and a liquid crystal polymer nonwoven fabric are preferable. Examples of the woven fabric include aramid woven fabric, liquid crystal polymer woven fabric, polyethylene terephthalate woven fabric, polycarbonate woven fabric, and nylon woven fabric. Among these woven fabrics, an aramid woven fabric and a liquid crystal polymer woven fabric are preferable. Examples of the resin film include polyamide film, liquid crystal polymer film, polyethylene terephthalate film, polypropylene film, polyethylene film, polycarbonate film, polyethylene naphthalate film, polyarylate film, polyimide film, and nylon film. Of these resin films, polyamide films and liquid crystal polymer films are preferred from the viewpoints of heat resistance, chemical resistance, linear expansion coefficient, and the like.

  Examples of the method for impregnating and / or applying the varnish of the curable resin composition to the substrate include dipping, roll coating, curtain coating, die coating, and slit coating.

  Drying conditions for removing the organic solvent are appropriately selected depending on the type of the organic solvent. The heating temperature is usually 20 to 300 ° C., preferably 30 to 200 ° C., and the heating time is usually 30 seconds to 1 hour, preferably 1 minute to 30 minutes.

  Although there is no particular limitation on the method of laminating the molded body made of the curable resin composition on the inner layer substrate, for example, the molded body is overlapped so as to be in contact with the conductor layer of the inner layer substrate, a pressure laminator, a press, Using a pressurizer such as a vacuum laminator, vacuum press, roll laminator, etc., thermocompression bonding (lamination) is performed so that there is substantially no void at the interface between the conductor layer on the inner substrate surface and the resin molding layer. A method is mentioned. The thermocompression bonding is preferably performed under vacuum in order to improve the embedding property of the circuit pattern and suppress the generation of bubbles. The temperature of the thermocompression bonding operation is usually 30 to 250 ° C., preferably 70 to 200 ° C., the applied pressure is usually 10 kPa to 20 MPa, preferably 100 kPa to 10 MPa, and the time is usually 30 seconds to 5 hours, preferably Is 1 minute to 3 hours. The atmospheric pressure is usually 100 kPa to 1 Pa, preferably 40 kPa to 10 Pa under reduced pressure.

  Curing of the molded body made of the curable resin composition of the present invention is usually performed by heating the layer of the molded body together with the inner layer substrate. The curing conditions are appropriately selected according to the type of curing agent, but the temperature is usually 30 to 400 ° C., preferably 70 to 300 ° C., more preferably 100 to 200 ° C., and the time is usually 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. The insulating film generated by curing is laminated on the conductor layer of the inner substrate to constitute an electric insulating layer.

  In addition, before bonding the uncured or semi-cured molded body made of the curable resin composition to the conductor layer on the outer surface of the inner layer substrate, the conductor layer is subjected to pretreatment for surface roughening in order to improve adhesion. It is preferable to apply. As a pretreatment method, a known technique is not particularly limited and can be used. For example, if the conductor layer is made of copper, an oxidation treatment method in which a strongly alkaline oxidizing solution is brought into contact with the surface of the conductor layer to form a tufted copper oxide layer on the conductor surface and roughened, the conductor layer After oxidizing the surface with the previous method, reducing with sodium borohydride, formalin, etc., depositing the plating on the conductor layer and roughening, bringing the organic acid into contact with the conductor layer and eluting the copper grain boundaries 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 circuit pattern, a method in which an organic acid is brought into contact with the conductor layer to elute and roughen the grain boundaries of copper, and a primer layer using a thiol compound or a silane compound The method of forming is preferred.

  Further, for the purpose of improving the flatness of the insulating film or increasing the thickness of the insulating film, two or more molded bodies made of the curable resin composition of the present invention are bonded and bonded onto the conductor layer of the inner substrate. You may laminate.

  When manufacturing a multilayer circuit board using the laminate as described above, a via hole penetrating the laminate is usually first provided in order to connect the conductor layers in the laminate. This via 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 (a carbon dioxide laser, an excimer laser, a UV-YAG laser, or the like) is preferable because a fine via hole can be formed without deteriorating the characteristics of the insulating film.

  Next, in order to improve the adhesiveness with the conductor layer, the surface of the insulating film is brought into contact with an oxidizing compound such as a peroxide, and is oxidized and roughened to adjust to a desired surface average roughness. The average surface roughness Ra of the insulating film is preferably 0.05 μm or more and less than 0.2 μm, and more preferably 0.06 μm or more and 0.1 μm or less. Further, the surface ten-point average roughness Rzjis of the insulating film is preferably 0.3 μm or more and less than 4 μm, and more preferably 0.5 μm or more and 2 μm or less. Here, Ra is the center line average roughness shown in JIS B 0601-2001, and the surface 10-point average roughness Rzjis is the 10-point average roughness shown in JIS B 0601-2001 Annex 1.

  Although there is no particular limitation on the method of forming the conductor layer on the surface of the insulating film formed from the curable resin composition of the present invention, the insulating film formed from the curable resin composition of the present invention is a plating blister or plating layer. Therefore, it is preferable to form the conductor layer by plating. Examples of the plating for providing the conductor layer include electroless plating and / or electrolytic plating that are usually used. A method of growing the plating layer by electroplating after forming the plating layer by electroless plating is preferably used. .

  Since the circuit board obtained in this way has the insulating film made of the curable resin composition of the present invention, it is excellent in flame retardancy, and it is easy to provide a conductor layer having a fine circuit pattern by plating. In addition, since the adhesion of the conductor layer is excellent, it can be suitably used as a semiconductor element such as a CPU or a memory or a substrate for other mounting parts in an electronic device such as a computer or a mobile phone.

  Hereinafter, although this invention is demonstrated based on a more detailed Example, this invention is not limited to these Examples. In the following, “part” is based on weight unless otherwise specified. The test and evaluation were as follows.

(1) Molecular weight of polymer Measured by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent, and a number average molecular weight (Mn) and a weight average molecular weight (Mw) were determined as polystyrene conversion values. As a measuring device, GPC-8220 series (manufactured by Tosoh Corporation) was used. As the standard polystyrene, standard polystyrene (Mw of 500, 2630, 10200, 37900, 96400, 427000, 909000, 5480000, a total of 8 points, manufactured by Tosoh Corporation) was used.
(2) Hydrogenation rate of polymer The ratio of the number of moles of unsaturated bonds hydrogenated to the number of moles of unsaturated bonds in the polymer before hydrogenation was determined by ¹ H-NMR spectrum measurement.
(3) Acid anhydride group content of polymer This refers to the ratio of the number of moles of acid anhydride groups to the total number of monomer units in the polymer, and was determined by ¹ H-NMR spectrum measurement.
(4) Glass transition temperature (Tg) of polymer
The temperature was measured at 10 ° C./min by a differential scanning calorimetry (DSC method).
(5) Flame retardancy The curable resin composition was coated on a polyethylene terephthalate film having a size of 250 mm in length and 300 mm in width with a thickness of 100 μm and a surface roughness Ra of 0.08 μm using a die coater. . Subsequently, it dried for 10 minutes at 80 degreeC, and obtained the 30-micrometer-thick film molded object on the support body. The obtained film molded body was laminated on both sides of a halogen-free substrate having a thickness of 0.6 mm × length of 11 cm × width of 16 cm obtained by etching copper on both sides, only the film support was peeled off, and a nitrogen atmosphere at 60 ° C. for 30 minutes. Then, the film molded body was cured by heating at 160 ° C. for 30 minutes and further at 170 ° C. for 60 minutes to form an insulating film. The board | substrate with which this insulating film was formed was cut | disconnected in the strip shape of width 13mm and length 100mm, and the flame-retardant evaluation board | substrate was created. The small piece was measured according to the UL94V vertical flame retardant test method.
○: UL94 V-1 or more ×: UL94 V-1 or less (6) Plating blister A glass fiber and a varnish containing a halogen-free epoxy resin are impregnated into glass fiber, and the thickness of the core material is 18 μm. A film molded body obtained in the same manner as in (5) was laminated on the surface of a double-sided copper-clad substrate with a thickness of 0.8 mm, length 150 mm × width 150 mm, to which copper was applied, and only the film support was peeled off. The film molded body was cured by heating at 60 ° C. for 30 minutes and then at 160 ° C. for 30 minutes to form an insulating film. The substrate on which this insulating film was formed was subjected to electroless copper plating and electrolytic copper plating to form a conductor layer having a thickness of 35 μm. The substrate on which the electroless plating film was formed was annealed at 170 ° C. for 60 minutes, and the surface shape was observed.
○: No change in surface shape before and after annealing at 170 ° C. ×: Swelling after plating at 170 ° C. (7) Adhesion with conductor layer Peeling strength between conductor layer and electrical insulating layer conforms to JIS C6481-1996 And based on the results, the following criteria were used.
○: Average peel strength is 8 N / cm or more
Δ: Average peel strength is 5 N / cm or more and less than 8 N / cm ×: Average peel strength is less than 5 N / cm (8) Phenolic content of phosphazene compound A mixed solvent of acetonitrile and water as a developing solution, Using ultra high performance liquid chromatography (UFLC), the number of μg of phenols contained in 1 g of the phosphazene compound containing the impurity to be measured was measured.

[Example 1]
8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-4-ene 70 parts, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride 30 parts, 1-hexene 1.1 parts, xylene 300 parts and A ruthenium-based polymerization catalyst (C1063, manufactured by Wako Pure Chemical Industries, Ltd.) (0.009 parts) was charged into a nitrogen-substituted pressure-resistant glass reactor and subjected to a polymerization reaction at 80 ° C. for 2 hours with stirring to obtain a solution of a ring-opening metathesis polymer. Got. When this solution was measured by gas chromatography, it was confirmed that substantially no monomer remained, and the polymerization conversion rate was 99.9% or more. Next, 100 parts of the obtained ring-opening metathesis polymer solution was charged into an autoclave equipped with a stirrer substituted with nitrogen and stirred at 150 ° C. and a hydrogen pressure of 7 MPa for 5 hours to conduct a hydrogenation reaction. A solution of a hydrogenated product (alicyclic olefin polymer) was obtained. The obtained ring-opening copolymer hydrogenated product had a weight average molecular weight of 63,000, a number average molecular weight of 28,000, a molecular weight distribution of 2.3, and a glass transition temperature of 142 ° C. The hydrogenation rate was 99.9%, and the carboxylic acid anhydride group content was 30 mol%. The polymer concentration of the solution of the ring-opening copolymer hydrogenated product was 25% by weight.

  Meanwhile, 30 parts of a phosphazene compound represented by the following chemical formula (9) (trade name SPH100, manufactured by Otsuka Chemical Co., Ltd.) was dissolved in a mixed solvent consisting of 35 parts of cyclohexanone and 35 parts of cyclopentanone to obtain a solution of a phosphazene compound. . To this solution was added 10 parts of activated clay (made by Wako Pure Chemical Industries, Ltd.) as an adsorbent, heat-treated with stirring with a magnetic stirrer at 60 ° C. for 1 hour, followed by filtration, and a phosphazene compound adsorption treatment solution Got. About the obtained adsorption treatment solution, the phenol content of the phosphazene compound was measured. The measurement results are shown in Table 1.

  Next, 400 parts of the solution of the ring-opening copolymer hydrogenated product obtained as described above as the alicyclic olefin polymer (A) component (100 parts as the amount of the ring-opened copolymer hydrogenated product), 36 parts of hydrogenated bisphenol A diglycidyl ether (trade name YX8000, manufactured by Japan Epoxy Resin Co., Ltd.) as a curing agent (B) component, 2- (2H-benzotriazol-2-yl) -4,6 as a laser processability improver 1 part of bis (1-methyl-1-phenylethyl) phenol, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5- as anti-aging agent 1 part of triazine-2,4,6-trione, 0.5 part of 1-benzyl-2-phenylimidazole as a curing accelerator, and liquid polybutadiene (trade name) as an elastomer 10 parts (icon, manufactured by Sartomer Japan) and 100 parts of the phosphazene compound adsorption treatment solution obtained as described above (30 parts as the amount of the phosphazene compound) were mixed using a planetary stirrer to obtain a curable resin composition. A varnish was obtained. Next, this varnish was coated using a die coater on a polyethylene naphthalate film (support) having a size of 300 mm in length × 300 mm in width and a thickness of 100 μm and a surface average roughness Ra of 0.08 μm, In a nitrogen atmosphere, the film was dried at 80 ° C. for 10 minutes to obtain a film molded body having a thickness of 30 μm.

  Both surfaces of 0.8 mm in thickness, 150 mm in length and 150 mm in width, in which copper having a thickness of 18 μm is pasted on the surface of a core material obtained by impregnating glass fiber with a varnish containing a glass filler and a halogen-free epoxy resin An inner layer which is a substrate having a conductor layer formed on a surface of a copper-clad substrate by forming a conductor layer having a wiring width and distance between wirings of 25 μm, a thickness of 10 μm, and a surface subjected to microetching by contact with an organic acid A substrate was obtained. The film molded body obtained above was cut into a size of 150 mm in length and 150 mm in width, and superimposed on both surfaces of the inner substrate so that the surface of the film molded body was on the inside and the support was on the outside. This was depressurized to 200 Pa using a vacuum laminator provided with heat-resistant rubber press plates at the top and bottom, and thermocompression bonded at a temperature of 105 ° C. and a pressure of 1.0 MPa for 60 seconds. Subsequently, the support was peeled off to obtain an inner layer substrate having a film molded body layer.

  This inner layer substrate was immersed in a 1.0% aqueous solution of 1- (2-aminoethyl) -2-methylimidazole at 30 ° C. for 10 minutes, and then immersed in water at 25 ° C. for 1 minute, and then with an air knife. Excess solution was removed. This was left to stand at 160 ° C. for 30 minutes in a nitrogen atmosphere, the film molded body layer was cured to form an insulating film on the inner layer substrate, and a multilayer circuit board was obtained. The obtained multilayer circuit board was rock-immersed in a 70 ° C. aqueous solution adjusted to a permanganate concentration of 60 g / liter and a sodium hydroxide concentration of 28 g / liter for 10 minutes. Next, this multilayer circuit board was immersed in a water tank for 1 minute and further washed in water by immersion in another water tank for 1 minute. Subsequently, the multilayer circuit board was immersed for 5 minutes in a 25 ° C. aqueous solution adjusted to a hydroxylamine sulfate concentration of 170 g / liter and sulfuric acid 80 g / liter, neutralized and reduced, and then washed with water.

  Next, as a pretreatment for plating, the above-mentioned washed multilayer circuit board is 200 ml / liter of Alcup activator MAT-1-A (manufactured by Uemura Kogyo Co., Ltd.) and 30 ml of Alcup activator MAT-1-B (manufactured by Uemura Kogyo Co., Ltd.). / L, and immersed in a 60 ° C. Pd salt-containing plating catalyst aqueous solution adjusted to 0.35 g / L of sodium hydroxide for 5 minutes. Next, the multilayer circuit board was immersed in a water tank for 1 minute and further washed in a water tank for 1 minute, and then washed with water. After that, Alcapredeuser MAB-4-A (manufactured by Uemura Kogyo Co., Ltd.) was 20 ml. The plating catalyst was reduced by immersion for 3 minutes at 35 ° C. in a solution adjusted to 200 ml / liter of Alcapredeuser MAB-4-B (manufactured by Uemura Kogyo Co., Ltd.). In this way, a plating catalyst was adsorbed to obtain a multilayer circuit board subjected to plating pretreatment.

  Next, the multilayer circuit board after the plating pretreatment is 100 ml / liter of Sulcup PSY-1A (manufactured by Uemura Kogyo Co., Ltd.), 40 ml / liter of Sulcup PSY-1B (manufactured by Uemura Kogyo Co., Ltd.), and 0.2 mol / liter of formalin. Electroless copper plating treatment was performed by dipping for 5 minutes at a temperature of 36 ° C. while blowing air into the aqueous solution prepared. The multilayer circuit board on which the metal thin film layer is formed by electroless plating is further immersed in a water tank for 1 minute, and further washed in a water tank for 1 minute, and then washed and dried to prevent rust. To obtain a multilayer circuit board on which an electroless plating film was formed.

  The multilayer circuit board on which the electroless plating film is formed is immersed in an aqueous solution of 100 g / liter sulfuric acid at 25 ° C. for 1 minute to remove the rust preventive agent, and electrolytic copper plating is performed to form an electrolytic copper plating film having a thickness of 30 μm. It was. Finally, annealing was performed at 170 ° C. for 60 minutes to complete the multilayer circuit board. The resulting multilayer circuit board was evaluated for adhesion to the conductor layer. The evaluation results are shown in Table 1.

[Example 2]
A curable resin composition in the same manner as in Example 1 except that 10 parts of activated carbon (trade name special white birch, manufactured by Nihon Enviro Chemicals) was used as an adsorbent for treating the phosphazene compound, instead of activated clay. A multilayer circuit board was manufactured, and the same items were tested and evaluated. The results are shown in Table 1.

[Comparative Example 1]
A curable resin composition and a multilayer circuit board were produced in the same manner as in Example 1 except that the treatment with the adsorbent (active clay) of the phosphazene compound was not performed, and the same items were tested and evaluated. The results are shown in Table 1.

  As can be seen from Table 1, when an insulating film is obtained using a curable resin composition containing a phosphazene compound which is treated with an adsorbent and has a phenol content of 20 μg / g or less, the insulating film On the other hand, when the conductor layer was formed by plating, no plating swelling occurred, and the adhesion between the insulating film and the conductor layer was excellent (Examples 1 and 2). On the other hand, when an insulating film is obtained using a curable resin composition containing a phosphazene compound having a phenol content exceeding 20 μg / g without treatment with an adsorbent, the insulating film is plated. When the conductor layer was formed by plating, plating swelling occurred, and the adhesion between the insulating film and the conductor layer was inferior (Comparative Example 1). Therefore, according to the present invention, it is easy to provide a conductor layer having a fine circuit pattern by plating, and it can be seen that a curable resin composition that provides an insulating film having excellent adhesion of the conductor layer can be obtained.

Claims (4)

Content of phenols contained as curing agent (B) and impurities in alicyclic olefin polymer (A) having a carboxyl group or acid anhydride group having a weight average molecular weight of 10,000 to 250,000 Is a curable resin composition obtained by blending at least one phosphazene compound (C) selected from the following general formula (1) and the following general formula (2).

(In General Formula (1), X ¹ is an arbitrary monovalent group, Y represents —N═P (R ² ) ₃ or —N═P (═O) R ² , and Y represents —P ( ═O) represents R ³ or —P (R ³ ) _3. R ^{1 to} R ³ independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenylaryl group, A haloalkyl group, an alkoxy group, a haloalkoxy group, an aryloxy group, an aralkyloxy group, an acyloxyalkoxy group, an arylmercapto group, an alkylamino group, an arylamino group, an arylglycidyloxy group, or an amino group or a halogen atom. Is an integer from 1 to 1500.)

(In the general formula (2), X ² is an arbitrary monovalent group, and R ⁴ is an alkyl group having 1 to 8 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenylaryl group, a haloalkyl group. A group, an alkoxy group, a haloalkoxy group, an aryloxy group, an aralkyloxy group, an acyloxyalkoxy group, an arylmercapto group, an alkylamino group, an arylamino group, an arylglycidyloxy group, or an amino group or a halogen atom. (It is an integer of 1-1500.)   The curable resin composition according to claim 1, which is used for an insulating film of a circuit board.   The insulating film for circuit boards formed by hardening | curing the curable resin composition of Claim 2.   The circuit board which has the insulating film for circuit boards of Claim 3 by which the conductor layer was formed in the surface by plating.