JP2009242531A - Composite resin molded product, laminate, and multilayer circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a multilayer wiring board capable of forming a high-density wiring pattern and having a good laser processed shape, excellent in low linear expansion, flame retardancy and flatness of an insulating layer, and harmful when incinerated. Provided is a composite resin molded body for an electrical insulating layer that hardly generates substances.
A polymer (A) having a weight average molecular weight of 10,000 to 250,000, having a carboxyl group or an acid anhydride group, and having an acid value of 5 to 200 mgKOH / g, and a curing agent (B). A composite resin molded article obtained by impregnating a fibrous base material having a fiber diameter of 0.05 to 2 μm with a curable resin composition comprising
The polymer (A) is preferably an alicyclic olefin polymer.
[Selection figure] None

Description

  The present invention relates to a composite resin molded article, and a cured product, a laminate and a multilayer circuit board obtained using the same. More specifically, it is suitable for obtaining a multilayer wiring board capable of forming a high-density wiring pattern and having a good laser processing shape, excellent in low linear expansion, flame retardancy and flatness of the insulating layer, and at the time of incineration. The present invention relates to a composite resin molded body for an electrical insulating layer that hardly generates harmful substances.

  With downsizing, multi-functionalization, high-speed communication, and the like of electronic devices, circuit boards used in electronic devices are required to have higher density, and therefore circuit boards are being made multilayer. A multilayer circuit board is usually formed by laminating and forming an electrical insulating layer on an inner layer substrate composed of an electrical insulating layer and a conductor layer formed on the surface, and laser processing is applied to the electrical insulating layer for interlayer connection. It is obtained by forming a via hole and then forming a conductor layer thereon. The electrical insulating layer and the conductor layer can be laminated in several stages as required. When the conductor layer of such a multilayer circuit board has a high-density pattern, the conductor layer or the board often generates heat, causing a fire in the electronic device or a linear expansion between the conductor layer and the electrical insulating layer. There arises a problem that the circuit breaks due to the difference. Therefore, improvement in flame retardancy and low linear expansion of the electrical insulating layer and connection reliability between the layers are required.

  In addition, used multilayer circuit boards are often incinerated. Conventionally, since halogen-based flame retardants are blended in the electrical insulation layer (Patent Document 1), it is said that halogen-based harmful substances are generated during incineration. There was a problem.

  Furthermore, an electrical insulating layer containing a flame retardant has insufficient strength and may experience impact and thermal history, resulting in occurrence of cracks, increased linear expansion, and decreased electrical characteristics. In order to increase the strength of the electrical insulating layer and to reduce the linear expansion, it is reinforced with glass cloth, but this method further reduces the electrical characteristics, and the flame retardant is applied to the entire electrical insulating layer. In some cases, the flame retardancy may be insufficient without uniform distribution.

  On the other hand, as an adhesive sheet for multilayer wiring boards used in electrical insulation layers, instead of reinforcing with glass cloth, a semi-cured composite resin molding is proposed by impregnating a thermosetting resin composition into a nonwoven fabric made of polyester and drying it. (Patent Document 2).

JP-A-2-255848 International Publication No. WO2007-023944

In recent years, it has been studied to suppress the thickness of the layers constituting the multilayer circuit board and measure the density.
When a non-woven fabric having the same fiber diameter as that specifically used in Patent Document 2 and thinner than that specifically used in Patent Document 2 is used, the via hole for interlayer connection is not processed with a uniform size. I understood that.
An object of the present invention is to provide a multilayer circuit board that can form a fine wiring pattern and has a good laser processing shape, and is suitable for obtaining this, and has low linear expansion, flame retardancy, and flatness of an insulating layer. An object of the present invention is to provide a composite resin molded article that is excellent and hardly generates harmful substances during incineration.

  As a result of intensive studies to solve the above problems, the present inventor has found that the use of a non-woven fabric made of fibers having a fiber diameter within a predetermined range finds that the laser processing shape is stable, and based on this finding, the present invention has been completed. It was.

Thus, according to the present invention, the following (1) to (7) are provided.
(1) A polymer (A) having a weight average molecular weight of 10,000 to 250,000, a carboxyl group or an acid anhydride group, and an acid value of 5 to 200 mgKOH / g, and a curing agent (B). A composite resin molded article obtained by impregnating a fibrous base material having a fiber diameter of 0.05 to 2 μm with a curable resin composition contained therein.
(2) The composite resin molded article according to (1), wherein the polymer (A) is an alicyclic olefin polymer.
(3) a polymer (A) having a weight average molecular weight of 10,000 to 250,000, having a carboxyl group or an acid anhydride group, and having an acid value of 5 to 200 mgKOH / g, a curing agent (B), and A method for producing a composite resin molded article, comprising impregnating a fibrous base material having a fiber diameter of 0.05 to 2 μm with a curable resin composition containing an organic solvent and drying.
(4) Hardened | cured material formed by hardening | curing the composite resin molding as described in said (1) or (2).
(5) A laminate formed by laminating a substrate having a conductor layer on the surface and an electrical insulating layer made of the cured product described in (4) above.
(6) The above-mentioned (4), wherein the composite resin molded body according to (1) or (2) is thermocompression-bonded on a substrate having a conductor layer on the surface and cured to form an electrical insulating layer. The manufacturing method of the laminated body of description.
(7) A multilayer circuit board obtained by further forming a conductor layer on the electrically insulating layer of the laminate according to (4).

1) Composite resin molded body The composite resin molded body of the present invention has a weight average molecular weight of 10,000 to 250,000, and is referred to as a carboxyl group or an acid anhydride group (hereinafter, both are collectively referred to as “carboxyl group etc.”). A curable resin composition containing a polymer (A) having an acid value of 5 to 200 mg KOH / g, and a curing agent (B), having a fiber diameter of 0.05 to 2 μm. A certain fibrous base material is impregnated.

  The weight average molecular weight (Mw) of the polymer (A) used in the present invention is usually 10,000 to 250,000, preferably 15,000 to 150,000, more preferably 20,000 to 100,000. is there. If the Mw of the polymer (A) is too small, the strength of the obtained electrical insulation layer becomes insufficient, and the electrical insulation properties may be lowered. On the other hand, if Mw is too large, the compatibility between the polymer (A) and the curing agent (B) decreases, the surface roughness of the electrical insulating layer increases, and the accuracy of the wiring pattern may decrease.

  The content of the carboxyl group and the like of the polymer (A) is preferably in a range where the acid value is 30 to 100 mgKOH / g, and more preferably in a range where it is 40 to 80 mgKOH / g. If the acid value is too small (that is, there are too few carboxyl groups, etc.), the plating adhesion and heat resistance may be lowered, and if the acid value is too large, the electrical insulation property may be lowered.

A polymer (A) will not be restrict | limited if it has said Mw, a carboxyl group, etc., and is an electrical insulation thing. Regarding the electrical insulation of the polymer (A), the volume resistivity according to ASTM D257 is preferably 1 × 10 ¹² Ω · cm or more, more preferably 1 × 10 ¹³ Ω · cm or more. It is particularly preferable that it is × 10 ¹⁴ Ω · cm or more.

The polymer constituting the skeleton of the polymer (A) (that is, a polymer having a structure in which a carboxyl group or the like is substituted with hydrogen, or a polymer having a structure in which a carboxyl group or the like is removed) is not particularly limited, but specific examples thereof As epoxy resin, maleimide resin, (meth) acrylic resin, diallyl phthalate resin, triazine resin, alicyclic olefin polymer, aromatic polyether polymer, benzocyclobutene polymer, cyanate ester polymer, and polyimide resin These may be used alone or in combination of two or more. Among these, alicyclic olefin polymer, aromatic polyether polymer, benzocyclobutene polymer, cyanate ester polymer and polyimide resin are preferable because of excellent electrical properties such as dielectric constant and dielectric loss tangent. An olefin polymer and an aromatic polyether polymer are more preferable, and an alicyclic olefin polymer is particularly preferable.

In the present invention, the alicyclic olefin polymer is a general term for alicyclic olefin homopolymers and copolymers, and derivatives thereof (hydrogenated products, etc.), as well as polymers having structures equivalent to these. . The polymerization mode may be addition polymerization or ring-opening polymerization.
Specific examples of alicyclic olefin polymers include ring-opening polymers of norbornene monomers and hydrogenated products thereof, addition polymers of norbornene monomers, addition weights of norbornene monomers and vinyl compounds. Examples thereof include a polymer, a monocyclic cycloalkene addition polymer, an alicyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer, and a hydrogenated product thereof. An example is a polymer in which an alicyclic structure is formed by hydrogenation after polymerization, such as an aromatic olefin hydrogenated product of an aromatic olefin polymer, and has a structure equivalent to an alicyclic olefin polymer. It is. 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 hydrogenated product is preferable, and a hydrogenated product of a ring-opening polymer of a norbornene monomer is particularly preferable.

  When the polymer (A) is an alicyclic olefin polymer, a carboxyl group or the like may be directly bonded to a carbon atom forming an alicyclic structure, but a methylene group, an oxy group, an oxycarbonyloxyalkylene group, a phenylene group And may be bonded through other divalent groups.

The method which makes the acid value of the polymer (A) used by this invention the said range is not restrict | limited. For example, (i) a monomer (ethylene, 1-hexene, 1,4-hexadiene, etc.) that is homopolymerized or copolymerizable with an alicyclic olefin monomer containing a carboxyl group or the like A method of copolymerizing; (ii) by graft-bonding a carbon-carbon unsaturated bond-containing compound having a carboxyl group or the like to an alicyclic olefin polymer not containing a carboxyl group or the like, for example, in the presence of a radical initiator. A method of introducing a carboxyl group, etc .; (iii) after polymerizing a norbornene-based monomer having a carboxyl group precursor, such as a carboxylic acid ester group, the precursor group is converted into a carboxyl group by hydrolysis or the like. There is a method of conversion;

As the carboxyl group-containing alicyclic olefin monomer used in the method (i), 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 (i) include bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic acid 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.

Specific examples of the monomer for obtaining an alicyclic olefin polymer having no carboxyl group and the like used in the method (ii) include bicyclo [2.2.1] hept-2-ene (conventional 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 and the like.

  Examples of the carbon-carbon unsaturated bond-containing compound having a carboxyl group or the like used in the method (ii) include acrylic acid, methacrylic acid, α-ethylacrylic acid, 2-hydroxyethyl (meth) acrylic acid, maleic acid. 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-2 Unsaturated carboxylic acid compounds such as 1,3-dicarboxylic acid; unsaturated carboxylic acid anhydrides such as maleic anhydride, chloromaleic anhydride, butenyl succinic anhydride, tetrahydrophthalic anhydride, citraconic anhydride; and the like.

As a norbornene-type monomer containing the group used as the precursor of a carboxyl group used for the method of (iii), 8-methyl-8-methoxycarbonyl tetracyclo [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 polymer (A) may have a functional group other than a carboxyl group or the like (hereinafter also referred to as “other functional group”). Examples of other functional groups include an alkoxycarbonyl group, a cyano group, a hydroxyl group, an epoxy group, an alkoxyl group, an amino group, an amide group, and an imide group. The amount of these other functional groups is 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 method for adjusting the Mw of the polymer (A) to the above range may be in accordance with a conventional method. For example, when ring-opening polymerization of an alicyclic olefin using a titanium-based or tungsten-based catalyst, a vinyl compound or a diene compound. The method of adding about 0.1-10 mol% of molecular weight modifiers, such as such with respect to the monomer whole quantity, is mentioned. Specific examples of such molecular weight regulators include, as vinyl compounds, α-olefin compounds such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrene compounds such as styrene and vinyltoluene; ethyl vinyl ether and isobutyl vinyl ether. And ether compounds such as allyl glycidyl ether; halogen-containing vinyl compounds such as allyl chloride; and other vinyl compounds such as allyl acetate, allyl alcohol, glycidyl methacrylate, and acrylamide. Examples of the diene compound include non-conjugated compounds such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, and 2,5-dimethyl-1,5-hexadiene. Diene 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; Can be mentioned.

  It is preferable that the glass transition temperature (Tg) of a polymer (A) is 120-300 degreeC. If the Tg is too low, the resulting electrical insulation layer cannot maintain sufficient electrical insulation at high temperatures, and if the Tg is too high, the multilayer wiring board is cracked and the conductor layer is damaged when subjected to a strong impact. there is a possibility.

  The curing agent (B) used in the present invention is not limited as long as it can crosslink the polymer (A) by heating. Especially, the compound which can react with the carboxyl group etc. of a polymer (A) and can form a crosslinked structure is preferable. Examples of such crosslinking agents include polyvalent epoxy compounds, polyvalent isocyanate compounds, polyvalent amine compounds, polyvalent hydrazide compounds, aziridine compounds, basic metal oxides, and organometallic halides. Further, a peroxide may be used.

  Examples of the polyvalent epoxy compound include 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, a brominated bisphenol A type epoxy compound, and a brominated bisphenol F. Type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, phosphorus-containing bisphenol F type epoxy compounds and other glycidyl ether type epoxy compounds; alicyclic epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, isocyanurate type epoxy compounds Compounds having two or more epoxy groups in the molecule, such as polyvalent epoxy compounds such as, and the like, and these may be used alone or in combination of two or more. Can.

  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. Two or more types can be used in combination.

  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 can be used together.

  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 and the like. 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 etc. are mentioned, These can be used 1 type or in combination of 2 or more types.

  Among these curing agents, the reactivity with the polymer (A) is moderate, and the resulting composite resin molded body is easy to melt, process and laminate, so a polyvalent epoxy compound is preferred, and bisphenol A bis (propylene glycol) Bisphenol A type epoxy compounds such as glycidyl ether) ether are preferred. The usage-amount of a hardening | curing agent (B) is 1-100 weight part normally with respect to 100 weight part of polymers (A), Preferably it is 5-80 weight part, More preferably, it is the range of 10-50 weight part.

  The curable resin composition used in the present invention preferably further contains a curing accelerator. When the curable resin composition contains a curing accelerator, 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), a curing accelerator such as a tertiary amine compound or a boron trifluoride complex compound is preferably used. Among these, the use of a tertiary amine compound is preferable because the lamination property to fine wiring, insulation resistance, heat resistance, chemical resistance, and the like are improved.

  Specific examples of tertiary amine compounds include chain tertiary amine compounds such as benzylmethylamine, triethanolamine, triethylamine, tributylamine, tribenzylamine, dimethylformamide; pyrazoles, pyridines, pyrazines, pyrimidines And nitrogen-containing heterocyclic compounds such as indazoles, quinolines, isoquinolines, imidazoles, and triazoles. Among these, imidazoles, particularly substituted imidazole compounds having a substituent are preferable.

  Specific examples of the substituted imidazole compound include 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, 1-methyl-2-ethylimidazole, 2-isopropylimidazole, 2, Alkyl-substituted imidazole compounds such as 4-dimethylimidazole and 2-heptadecylimidazole; 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, benzimidazole, 2-ethyl-4-methyl -1- (2′-cyanoethyl) imidazole, 2-ethyl-4-methyl-1- [2 ′-(3 ″, 5 ″ -diaminotriazinyl) ethyl] imidazole, 1-benzyl-2-phenylimidazole, and the like Having a ring structure such as an aryl group or an aralkyl group Imidazole compounds substituted with a hydrocarbon group; and the like. Among these, an imidazole compound substituted with a hydrocarbon group having a ring structure is preferable, and 1-benzyl-2-phenylimidazole is particularly preferable.

  These curing accelerators are used alone or in combination of two or more. Although the compounding quantity of a hardening accelerator is suitably set according to a use purpose, 0.001-30 weight part normally with respect to 100 weight part of polymers (A), Preferably it is 0.01-10 weight part, or more. Preferably it is 0.03-5 weight part.

The fibrous base material is obtained by molding fibers, and examples thereof include woven fabrics and nonwoven fabrics, and nonwoven fabrics are particularly preferable.
The fiber constituting the fibrous base material is a thermoplastic resin and preferably has a melting point of 160 ° C. or higher. Suitable thermoplastic resins include polyesters, polyester amides, polyimides, polyaramids, polyphenylene sulfides, and the like, and polyesters, polyimides, and polyaramids are particularly preferable.
The weight average molecular weight of the thermoplastic resin constituting the fiber is usually 1,000 to 1,000,000, preferably 5,000 to 500,000.

Among polyesters, liquid crystalline ones such as liquid crystalline polyester and liquid crystalline polyester amide are preferable.
The liquid crystalline polyester is a polymer having an ester bond and showing a liquid crystal state. Examples of such a liquid crystal polymer include known liquid crystal polyesters and liquid crystal polyester amides obtained by appropriately combining the following compounds (1) to (4) and their derivatives.
(1) Aromatic or aliphatic dihydroxy compounds (2) Aromatic or aliphatic dicarboxylic acids (3) Aromatic hydroxycarboxylic acids (4) Aromatic diamines, aromatic hydroxylamines or aromatic aminocarboxylic acids A wholly aromatic polyester having substantially no aliphatic hydrocarbon in the main chain is preferred. Specific examples of the wholly aromatic polyester include a copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, and a copolymer of p-hydroxybenzoic acid, terephthalic acid, and 4,4′-dihydroxybiphenyl. Examples of the polymer include a copolymer obtained by reacting an aromatic diol with an aromatic dicarboxylic acid and / or an aromatic hydroxycarboxylic acid.

Polyimide is synthesized from both carboxylic dianhydride and diamine having an aromatic ring, and in this case, it is excellent in mechanical strength and heat resistance.
Specific polyimide resin is exemplified by a combination of carboxylic dianhydride and diamine. For example, a polycondensate of pyromellitic dianhydride (PMDA) and oxydianiline (ODA); biphenyltetracarboxylic dianhydride ( Polycondensates of BTDA) and paraphenylenediamine (PPD); polycondensates of benzophenonetetracarboxylic dianhydride (BTDA) and benzophenonediamine (BDA), etc., from the viewpoint of heat resistance, mechanical strength, etc. A polycondensate of BTDA and PPD is preferred.

  Polyaramid is a wholly aromatic polyamide resin, and is not particularly limited, but specific examples of wholly aromatic polyamide resin include, for example, para-aramid resin co-polymerized paraphenylene diamide and terephthalic acid chloride, metaphenylene diamide and Examples thereof include meta-aramid resins obtained by co-condensation polymerization of isophthalic acid chloride. Para-aramid resins are preferred from the viewpoint of heat resistance and mechanical strength.

The fiber diameter of a fibrous base material is the thickness of the fiber of a fibrous base material, and is 0.05-2 micrometers normally, Preferably it is 0.1-1.5 micrometers, More preferably, it is 0.2-1 micrometer. When the fiber diameter is within this range, a fibrous base material having a thin and high flatness can be formed. If the fiber diameter is less than 0.05 μm, the strength of the fiber base material itself is impaired, and if it exceeds 2 μm, the flatness of the fiber base material itself is deteriorated.
The fiber diameter in this invention is the value calculated | required by 50 point average value of the fiber cross section observed with an electron microscope or microscope.

Among the non-woven fabrics that are fibrous base materials suitably used in the present invention, non-woven fabrics prepared by electrospinning the above-described polymers are preferable.
In the electrospinning method, a spinning solution having a spinnability is supplied into a positive electric field formed between electrodes, the solution is made to fiber toward the electrodes, and the fibrous material to be formed is collected on a collection substrate (collector). It is a method of obtaining fibers by laminating to each other, and as usual spinning conditions, the spinning solution can be placed in a positive electric field, and an appropriate voltage, spinning distance, etc. can be selected for each spinning solution, but it is particularly limited Although not intended, the voltage is preferably 5.0 to 50 kV, the spinning distance is 5.0 to 50 cm, and the voltage per unit distance is preferably 0.5 to 5.0 kv / cm.

  Examples of the spinning solution supply unit include a method of extruding from a nozzle or a base, and a method of supplying by spinning a spinning solution so that it becomes a required amount on a disk or drum immersed in the spinning solution and continuously rotating. When supplying from a nozzle or a nozzle | cap | die, since the internal diameter of a discharge part has no correlation with the fiber diameter of a nonwoven fabric, there is no limitation.

  The solution used for the spinning solution is not particularly limited as long as it can dissolve resins made of polyester, polyesteramide, polyimide, and polyaramid. The density | concentration of resin which consists of polyester, polyesteramide, a polyimide, and polyaramid in a spinning solution is 0.5 to 50 weight% normally, Preferably it is 1.0 to 40 weight%, More preferably, it is 5.0 to 30 weight%. When the amount is less than 0.5% by weight, fiberization becomes difficult. When the amount exceeds 50% by weight, the fiber diameter becomes too large, and the density of the nonwoven fabric increases.

The thickness of the fibrous base material used in the present invention is usually 0.5 to 50 μm, preferably 2 to 35 μm, more preferably 5 to 20 μm. Moreover, as a fabric weight, it is 0.1-50 g / m < ² > normally, Preferably it is 0.5-35 g / m < ² >, More preferably, it is 1-25 g / m < ² >. The basis weight is the weight per unit area of the fibrous base material.

  The composite resin molded body of the present invention is formed by impregnating a fibrous base material with the above curable resin composition, but the composite resin molded body may be uncured or semi-cured. Here, “uncured” refers to a state in which substantially all of the polymer (A) is dissolved in a solvent capable of dissolving the polymer (A). Semi-cured is a state in which the polymer (A) is partially cured to a degree that can be further cured by heating, and preferably a part of the polymer (A) (specifically, in a solvent capable of dissolving the polymer (A)) 7% by weight or more) is dissolved, or the swelling rate when the composite resin molded body is immersed in a solvent for 24 hours is 200% or more of the volume before immersion.

  The amount of the fibrous base material in the composite resin molded body of the present invention is usually 10 to 95% by weight, preferably 20 to 85% by weight. For example, when the polymer (A) is uncured, the amount of the fibrous base material is obtained by dissolving the composite resin molded body in a solvent that can dissolve the polymer (A) but not the fibrous base material. It can be measured from the insoluble matter. If the amount of the fibrous base material is too small, the flame retardancy may decrease, and if it is too large, it may be difficult to control the thickness at the time of lamination.

  The method for impregnating the fibrous base material with the curable resin composition is not particularly limited, but a varnish obtained by dissolving or dispersing the curable resin composition in an organic solvent is impregnated into the fibrous base material and dried. Is preferred. When the curable resin composition is used as a varnish, the polymer (A) is preferably soluble in the organic solvent at room temperature.

  The organic solvent to be used has a boiling point of preferably 30 to 250 ° C, more preferably 50 to 200 ° C. When the boiling point is within this range, it is suitable for heating and volatilizing and drying later. 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 a polymer (A), a hardening | curing agent (B), an organic solvent, and the arbitrary component mix | blended as needed according to a conventional method. Examples of the mixer used for mixing include a magnetic stirrer, a high-speed homogenizer, a disper, a planetary stirrer, a twin-screw stirrer, a ball mill, and a three roll. The mixing temperature is preferably within the range where no curing reaction is caused by the curing agent (B) and not more than the boiling point of the organic solvent. The amount of the organic solvent used is appropriately selected according to the desired thickness and surface flatness of the composite resin molded article, but the solid content concentration of the varnish is usually 5 to 70% by weight, preferably 10 to 65% by weight, More preferably, it is the range which becomes 20 to 60 weight%.

  The method of impregnating the varnish into the fibrous base material is not particularly limited, and examples thereof include a method of applying by dip coating, roll coating, curtain coating, die coating, slit coating and the like.

At the time of application, a fibrous base material may be previously set on a support and the varnish may be applied thereto. Examples of the support 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 and a polyethylene naphthalate film are preferable from the viewpoints 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. Among these, a copper foil, particularly an electrolytic copper foil or a rolled copper foil is preferable from the viewpoint of good conductivity.

  Although there is no restriction | limiting in the thickness of a support body, from viewpoints of workability | operativity etc., it is 1-150 micrometers normally, Preferably it is 2-100 micrometers, More preferably, it is 5-80 micrometers. 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. If the surface average roughness Ra of the support is too large, the surface average roughness Ra of the electrically insulating layer formed by curing the resulting composite molded body increases, making it difficult to form a fine wiring pattern as a conductor layer. Become.

  Drying conditions for drying the fibrous base material coated with the varnish to obtain the composite resin molded body of the present invention are appropriately selected depending on the type of the organic solvent. Specifically, the drying temperature is usually 20 to 300 ° C, preferably 30 to 200 ° C. If the drying temperature is too high, the curing reaction proceeds and the resulting composite resin 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.

  Although the composite resin molding of the present invention has high flame retardancy, it may further contain a flame retardant for the purpose of improving flame retardancy. As the flame retardant, a halogen-free flame retardant that generates little harmful substances during incineration is preferable. Specific examples of the halogen-free flame retardant include antimony compounds such as antimony trioxide, antimony pentoxide, and sodium antimonate; aluminum hydroxide, magnesium hydroxide, zinc borate, guanidine sulfamate, zirconium compound, molybdenum compound, aluminum borate Inorganic flame retardants such as tin compounds; organometallic compounds such as ferrocene; phosphate esters, aromatic condensed phosphate esters, phosphazene compounds, phosphorus-containing epoxy compounds, reactive phosphorus compounds, ammonium polyphosphate, melamine phosphate, Examples thereof include melamine polyphosphate, melam salt polyphosphate, melem salt polyphosphate, melamine polymelamine / melam / melem double salt, red flame retardants such as red phosphorus and organometallic phosphorus compounds. Of these, preferred are magnesium hydroxide, aluminum hydroxide, phosphazene compounds, melamine phosphate, melamine polyphosphate, melam salt polyphosphate, and melem salt polyphosphate, particularly heat resistance, moisture resistance and flame retardancy. From the viewpoint of excellent improvement of magnesium, magnesium hydroxide, polyphosphate melamine / melam / melem double salt, and phosphazene compound are preferable.

  The composite resin molded article of the present invention may further contain an amount of fillers and additives in a range that does not impair the original properties for the purpose of imparting desired performance depending on the application. Examples of the filler include carbon black, fullerene, carbon nanotube, porous silica, hollow silica, silica, alumina, barium titanate, talc, mica, organic bentonite, glass beads, and glass hollow spheres. Additives include soft polymer, heat stabilizer, weather stabilizer, anti-aging agent, leveling agent, antistatic agent, slip agent, anti-blocking agent, anti-fogging agent, lubricant, dye, pigment, natural oil, synthetic oil , Wax, emulsion, magnetic material, dielectric property adjusting agent, toughening agent, and the like.

  The method of blending optional components such as the above-mentioned flame retardant, filler and additive is not particularly limited, but is usually used by being contained in the curable resin composition, and preferably in the preparation of the varnish, the polymer (A ), A curing agent (B) and an organic solvent.

  Although the shape of the composite resin molding of this invention is not specifically limited, It is preferable that it is a film or a sheet | seat. The thickness of the film or sheet is usually 1 to 100 μm, preferably 3 to 80 μm, more preferably 5 to 50 μm.

2) Cured product The cured product of the present invention is obtained by curing the composite resin molded body of the present invention. The composite resin molded body is usually cured by heating the composite resin molded body. Curing conditions are appropriately selected according to the type of curing agent. The curing temperature is usually 30 to 400 ° C, preferably 70 to 300 ° C, more preferably 100 to 200 ° C. The curing time is 0.1 to 5 hours, preferably 0.5 to 3 hours. The heating method is not particularly limited, and may be performed using, for example, an electric oven.

  In addition, it is preferable to have the process of making the compound which has metal coordination ability contact a composite resin molding before hardening, and then wash | cleaning with good solvents of these compounds, such as water. Examples of such compounds having metal coordination ability include imidazoles such as 1- (2-aminoethyl) -2-methylimidazole; pyrazoles; triazoles; triazines; By this step, the surface of the composite resin molded body can be smoothed, and the adhesiveness with the metal thin film coated thereon in the subsequent step can be improved.

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

  The substrate having a conductor layer on the surface used in the present invention is preferably pretreated on the surface of the conductor layer in order to improve adhesion to the electrical insulating layer. As a pretreatment method, a known technique 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 strong alkali oxidizing solution is brought into contact with the surface of the conductor layer to form a copper oxide layer on the conductor surface and roughened, After oxidation with this method, reduce with sodium borohydride, formalin, etc., deposit and roughen the plating on the conductor layer, contact the organic acid with the conductor layer to elute the copper grain boundaries and roughen And a method of forming a primer layer with a thiol compound or a silane compound on the conductor layer. Among these, from the viewpoint of easy maintenance of the shape of a fine wiring pattern, a method in which an organic acid is brought into contact with a conductor layer to elute and roughen the grain boundaries of copper, and a primer using a thiol compound or a silane compound A method of forming a layer is preferred.

  The laminate of the present invention can be produced by forming the electrical insulating layer by heat-pressing and curing the composite resin molded body of the present invention on a substrate having a conductor layer on the surface. As a specific example of the thermocompression bonding method, a composite resin molded body with a support is superposed so as to be in contact with the conductor layer of the substrate, and a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator or the like is used. And a method of forming a composite resin molded body layer on the conductor layer by thermocompression bonding (lamination). By heating and pressurizing, bonding can be performed so that there is substantially no void at the interface between the conductor layer on the substrate surface and the composite resin molded body layer. Further, when a metal foil is used as the support, the adhesion between the composite resin molded body layer and the metal foil is also improved, so that the metal foil can be used as it is as a conductor layer of a multilayer circuit board described later.

  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 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 of the atmosphere in which thermocompression bonding is performed is usually 100 kPa to 1 Pa, preferably 40 kPa to 10 Pa.

  The composite resin molded body to be heat-pressed is cured to form an electrical insulating layer, whereby the laminate of the present invention is manufactured. Curing is usually performed by heating the entire substrate on which the composite resin molded body is formed on the conductor layer. Curing can be performed simultaneously with the thermocompression bonding operation. Alternatively, the thermocompression may be performed after the thermocompression operation is performed under conditions that do not cause curing, that is, at a relatively low temperature for a short time.

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

4) Multilayer circuit board The multilayer circuit board of the present invention is formed by forming a conductor layer on the electrical insulating layer of the laminate of the present invention. In the production of the laminate, when a resin film is used as a support for the composite resin molded body, after peeling it off, a conductor layer is formed on the electrical insulating layer by plating or the like to form the multilayer circuit board of the present invention. Can be manufactured. When a metal foil is used as the support for the composite resin molded body, the conductor layer can be formed by etching the metal foil into a pattern by a known etching method.

  Hereinafter, a method for producing a multilayer circuit board of the present invention by forming a conductor layer on the electrical insulating layer by plating or the like will be specifically described. In manufacturing a multilayer circuit board, a via hole penetrating the multilayer body is usually provided to connect the conductor layers in the multilayer circuit board before forming the conductor layers. The via hole can be formed by a chemical process such as a photolithography method, or a physical process such as a drill, laser, or plasma etching. Among these methods, a method using a laser (a carbon dioxide laser, an excimer laser, a UV-YAG laser, or the like) can form a finer via hole without deteriorating the characteristics of the electrical insulating layer. In the laser method, a carbon dioxide laser or a UV-YAG laser is preferable.

  Next, the surface of the electric insulating layer is roughened by oxidizing the surface in order to enhance the adhesion to the conductor layer, and adjusted to a desired surface average roughness. In the present invention, the surface average roughness Ra of the electrical insulating layer is usually 0.05 μm or more and less than 0.3 μm, preferably 0.06 μm or more and 0.2 μm or less, and the surface 10-point average roughness Rzjis is usually 0.3 μm or more. It is less than 4 μm, 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.

  In order to oxidize the surface of the electrical insulating layer, the surface of the electrical insulating layer and the oxidizing compound may be brought into contact with each other. Examples of the oxidizing compound include known compounds having an oxidizing ability such as inorganic peroxides and organic peroxides; gas. In particular, it is preferable to use an inorganic peroxide or an organic peroxide from the viewpoint of easy control of the surface average roughness of the electrical insulating layer. Inorganic peroxides include permanganate, chromic anhydride, dichromate, chromate, persulfate, activated manganese dioxide, osmium tetroxide, hydrogen peroxide, periodate, ozone, etc. Examples of the organic peroxide include dicumyl peroxide, octanoyl peroxide, m-chloroperbenzoic acid, and peracetic acid.

  There is no particular limitation on the method for oxidizing the surface of the electrical insulating layer using an inorganic peroxide or an organic peroxide. For example, an oxidizing compound solution prepared by dissolving the above oxidizing compound in a solvent capable of being dissolved can be electrically charged. The method of making it contact with the surface of an insulating layer is mentioned. There is no particular limitation on the method of bringing the inorganic peroxide or organic peroxide or these solutions into contact with the surface of the electrical insulating layer. For example, a dipping method in which the electrical insulating layer is immersed in an oxidizing compound solution, an oxidizing compound solution Any method may be used, such as a liquid filling method in which the surface tension is applied to the electrical insulating layer, or a spraying method in which a solution of an oxidizing compound is sprayed onto the substrate.

  The temperature and time for bringing these inorganic peroxides and organic peroxides into contact with the surface of the electrical insulating layer may be set arbitrarily in consideration of the concentration and type of peroxide, the contact method, etc. It is 10 to 250 ° C, preferably 20 to 180 ° C, and the time is usually 0.5 to 60 minutes, preferably 1 to 30 minutes.

  As a method for oxidizing using gas, plasma treatment for radicalizing or ionizing gas such as reverse sputtering or corona discharge can be given. Examples of the gas include air, oxygen, nitrogen, argon, water, carbon disulfide, and carbon tetrachloride. When the gas for oxidation treatment is liquid at the treatment temperature but becomes gas under reduced pressure, the oxidation treatment is performed under reduced pressure. When the gas for oxidation treatment is a gas at the treatment temperature and pressure, the oxidation treatment is performed after pressurizing to a pressure capable of radicalization or ionization. The temperature and time for bringing the plasma into contact with the surface of the second electrical insulating layer may be set in consideration of the type and flow rate of the gas, and the temperature is usually 10 to 250 ° C., preferably 20 to 180 ° C., and the time is Usually 0.5 to 60 minutes, preferably 1 to 30 minutes.

  When oxidizing the surface of the electrical insulating layer with an oxidizing compound solution, the curable resin composition constituting the second electrical insulating layer should contain a polymer or inorganic filler soluble in the oxidizing compound solution. In this case, the polymer (A) and a fine sea-island structure are formed and then selectively dissolved, so that it is easy to control the above-described surface average roughness range, which is preferable.

  Examples of the polymer soluble in the solution of the oxidizing compound include liquid epoxy resin, polyester resin, bismaleimide-triazine resin, silicone resin, polymethylmethacrylate resin, natural rubber, styrene rubber, isoprene rubber, butadiene Examples thereof include rubber, nitrile rubber, ethylene rubber, propylene rubber, urethane rubber, butyl rubber, silicone rubber, fluorine rubber, norbornene rubber, and ether rubber. There is no particular limitation on the blending ratio of the polymer soluble in the solution of the oxidizing compound, and usually 1 to 30 parts by weight, preferably 3 to 25 parts by weight, more preferably 100 parts by weight of the polymer (A). Is 5 to 20 parts by weight.

  Examples of inorganic fillers that are soluble in a solution of oxidizing compounds include calcium carbonate, magnesium carbonate, barium zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, hydrated alumina, Examples thereof include magnesium hydroxide, aluminum hydroxide, barium sulfate, silica, talc, and clay. Among these, calcium carbonate and silica are easy to obtain fine particles and are easily eluted with a filler-soluble aqueous solution, and are suitable for obtaining a fine rough surface shape. Further, these inorganic fillers may be those subjected to a silane coupling agent treatment or an organic acid treatment such as stearic acid.

  Moreover, it is preferable that the inorganic filler added is a non-conductive thing which does not reduce the dielectric property of an electric insulation layer. Moreover, the shape of the inorganic filler is not particularly limited, and may be spherical, fibrous, plate-like, or the like, but in order to obtain a fine rough surface shape, a fine powder is preferable. The average particle size of the inorganic filler is usually 0.008 μm or more and less than 2 μm, preferably 0.01 μm or more and less than 1.5 μm, particularly preferably 0.02 μm or more and less than 1 μm. If the average particle size is too small, uniform adhesion may not be obtained on a large substrate. Conversely, if the average particle size is too large, a large rough surface may be generated on the electrical insulating layer, and a high-density wiring pattern may not be obtained. There is sex. The amount of the inorganic filler soluble in the solution of the oxidizing compound is appropriately selected according to the required degree of adhesion, but is usually 1 to 80 with respect to 100 parts by weight of the polymer (A). Parts by weight, preferably 3 to 60 parts by weight, more preferably 5 to 40 parts by weight.

  Polymers and inorganic fillers soluble in the oxidizing compound solution as described above are optionally added to the curable resin composition used in the present invention as a flame retardant aid, heat stabilizer, and dielectric property adjustment. It can be used as a part of an agent or toughening agent.

  After the oxidation treatment of the electrical insulating layer, the surface of the electrical insulating layer is usually washed with water in order to remove the oxidizing compound. If a substance that cannot be washed with water alone is attached, wash the substance with a soluble cleaning solution or contact with other compounds to make it soluble in water, and then wash with water. You can also. For example, when an alkaline aqueous solution such as an aqueous potassium permanganate solution or an aqueous sodium permanganate solution is brought into contact with the electrical insulating layer, a mixed solution of hydroxyamine sulfate and sulfuric acid is used to remove the generated manganese dioxide film. The solution is neutralized and reduced with an acidic aqueous solution.

  After the electrical insulating layer is oxidized to adjust the average surface roughness, a conductor layer is formed on the surface of the electrical insulating layer and the inner wall surface of the via hole by plating or the like. The method for forming the conductor layer is not particularly limited. For example, a method of forming a metal thin film by plating or the like on the electrical insulating layer and then growing the metal layer by thick plating is employed.

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

  As the electroless plating solution used in the electroless plating method, a known autocatalytic electroless plating solution may be used, and the metal species, reducing agent species, complexing agent species, hydrogen ion concentration, The dissolved oxygen concentration and the like are not particularly limited. For example, electroless copper plating solution using ammonium hypophosphite, hypophosphorous acid, ammonium borohydride, hydrazine, formalin, etc. as a reducing agent; electroless nickel-phosphorous plating solution using sodium hypophosphite as a reducing agent Electroless nickel-boron plating solution using dimethylamine borane as a reducing agent; electroless palladium plating solution; electroless palladium-phosphorous plating solution using sodium hypophosphite as a reducing agent; electroless gold plating solution; electroless silver Plating solution: An electroless plating solution such as an electroless nickel-cobalt-phosphorous plating solution using sodium hypophosphite as a reducing agent can be used. After the metal thin film is formed, the substrate surface can be brought into contact with a rust preventive agent for rust prevention treatment.

  Moreover, after forming a metal thin film, a metal thin film can be heated for the adhesive improvement etc. The heating temperature is usually 50 to 350 ° C, preferably 80 to 250 ° C. Heating may be carried out under pressurized conditions, and examples of the pressing method at this time include physical pressing methods such as a hot press machine and a pressurized heating roll machine. The applied pressure is usually 0.1 to 20 MPa, preferably 0.5 to 10 MPa. If it is this range, the high adhesiveness of a metal thin film and an electrically insulating layer is securable.

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

  By using the multilayer circuit board thus obtained as a new laminate, the above-described steps of forming the electrical insulating layer and forming the conductor layer can be repeated to further increase the number of layers. A multilayer circuit board can be obtained.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. In the examples and comparative examples, “part” and “%” are based on weight unless otherwise specified.

In addition, the definition and evaluation method of each characteristic are as follows.
(1) Fiber diameter of fibrous base material The diameter of 50 fiber cross sections was measured with a scanning electron microscope, and the average value was obtained.
(2) Thickness of fibrous base material Using a micrometer ("Lightmatic VL-50" manufactured by Mitutoyo Co., Ltd., measuring load 0.01N, measuring terminal 3mmφ), 50 points were measured with a sense of 1cm, and the average value was obtained. It was.

(3) Number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer
It was measured as a standard polystyrene conversion value by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent.
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.

The sample was prepared by dissolving the measurement sample in tetrahydrofuran so that the sample concentration was 1 mg / ml, and then filtering with a cartridge filter (made of polytetrafluoroethylene, pore size 0.5 μm).
The measurement was performed under the conditions of using TSKgel G4000HXL, G2000HXL, and G1000HXL (manufactured by Tosoh Corporation) in series in a column, using a flow rate of 1.0 ml / min, a sample injection amount of 20 μl, and a column temperature of 40 ° C.

(4) Hydrogenation rate of polymer The hydrogenation rate refers to the ratio of the number of moles of unsaturated bonds hydrogenated to the number of moles of unsaturated bonds in the polymer before hydrogenation. ¹ H-NMR spectrum measurement Determined by

(5) Maleic anhydride group content of polymer The ratio of the number of moles of acid anhydride groups to the total number of monomer units in the polymer was determined by ¹ H-NMR spectrum measurement.
(6) Acid value of polymer The acid value of the polymer (A) having a carboxyl group or an acid anhydride residue was measured according to JIS K0070.
(7) Glass transition temperature (Tg) of polymer
The temperature was measured at 10 ° C./min by a differential scanning calorimetry (DSC method).
(8) Volume resistivity of polymer Measured based on ASTM D257.

(9) Linear expansion coefficient of composite resin molded body A part of the composite resin molded body was cut out, laminated on one side of a rolled copper foil having a thickness of 75 μm, and after peeling the polyethylene terephthalate film as a support, under a nitrogen atmosphere, The composite resin molded body was cured by heating at 60 ° C. for 30 minutes and then at 170 ° C. for 60 minutes. Subsequently, all of the rolled copper foil was removed by etching with a cupric chloride / hydrochloric acid mixed solution to obtain a sheet-like molded body. A test piece having a width of 5.95 mm and a length of 15.4 mm was cut out from the obtained sheet-like molded body, and a thermogravimetric / differential thermal simultaneous measurement apparatus (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) and determined according to the following criteria.
○: The value of the linear expansion coefficient is less than 25 ppm / ° C. Δ: The value of the linear expansion coefficient is 25 ppm / ° C. or more and less than 40 ppm / ° C. ×: The value of the linear expansion coefficient is 40 ppm / ° C. or more.

(10) Flatness of composite resin-formed body A 10 cm square test piece was cut out from the molded body obtained in the same manner as in (9) above, and a contact-type film thickness meter ("Lightmatic VL-50" manufactured by Mitutoyo Corporation) was measured. 100 points were measured using a load of 0.01 N and a measurement terminal of 3 mmφ, and the determination was made according to the following criteria.
○: Maximum film thickness—minimum film thickness of less than 1.0 μm Δ: Maximum film thickness—minimum film thickness of 1.0 μm or more and less than 5.0 μm ×: Maximum film thickness—minimum film thickness of 5.0 μm (11) Patterning property A multilayer circuit board having 200 wiring patterns with a wiring width of 10 μm, an inter-wiring distance of 10 μm, and a wiring length of 5 cm is formed. The case where there was a defect and the shape was disordered but there was no broken portion was judged as Δ, and the case where there was a broken portion was judged as x.

(12) Flame Retardant As the inner layer substrate, the core material used in Example 1 (having no copper attached to the surface) is used, and composite resin molding with a support obtained in this and the Examples and Comparative Examples is used. Using this body, an inner layer substrate having a composite resin molded body layer was prepared in the same manner as in Example 1. The inner layer substrate having this composite resin molded body layer was cut into strips having a width of 13 mm and a length of 100 mm to prepare test pieces. Using this test piece, a Bunsen burner flame was contacted according to the UL94V vertical flammability test method. The flame was removed immediately after ignition of the test piece, and the time during which the test piece was burning was measured. As soon as the test piece was extinguished, the flame was contacted until the test piece ignited again. After the second ignition, the flame was immediately removed, the time during which the test piece was burning was measured, and the determination was made according to the following criteria based on the result.
○: The total of the first burning time and the second burning time is within 20 seconds, and the burning area does not reach the upper part of the test piece.
Δ: The sum of the first burning time and the second burning time is more than 20 seconds and not more than 30 seconds, and the combustion area does not reach the upper part of the test piece.
X: The sum of the first burning time and the second burning time exceeds 30 seconds, or the burning area reaches the upper part of the test piece.

(13) Laser workability As the inner layer substrate, the double-sided copper-clad substrate used in Example 1 was used, and this and the composite resin molded body with a support obtained in Examples and Comparative Examples were used. Similarly, an inner layer substrate having a composite resin molded body layer was produced. This composite resin molded body layer was formed with 100 via-holes having a diameter of 30 μm using a UV-YAG laser third harmonic. The machining shape was judged according to the following criteria.
○: The diameter of all via holes is 30 ± 2 μm and holds a proper circular shape.
(Triangle | delta): The via hole diameter of less than 20 holes in 100 holes is 30 +/- 5micrometer, and does not hold | maintain the perfect circle.
X: The via hole diameter of 20 holes or more in 30 holes is 30 ± 5 μm, and does not hold a proper circle.

Fibrous substrate production example 1
10 parts of a liquid crystalline polyester resin (product name “Vectra”, manufactured by Polyplastics) was dissolved in 90 parts of tetrafluorophenol. A fibrous base material a was obtained by an electrospinning method in which this solution was sprayed at a voltage of 10 kV and a liquid feed speed of 10 μL using Esplayer ES2000 (manufactured by Huence). The fibrous substrate had a fiber diameter of 0.2 μm and a thickness of 10 μm.

Fibrous substrate production example 2
20 parts of a liquid crystalline polyester resin (product name “Vectra”, manufactured by Polyplastics) was dissolved in 80 parts of tetrafluorophenol. A fibrous base material b was obtained by an electrospinning method in which this solution was sprayed using Esplayer ES2000 (manufactured by Huence Co., Ltd.) at a voltage of 10 kV and a liquid feeding speed of 20 μL. The fibrous base material had a fiber diameter of 1.0 μm and a thickness of 10 μm.

Fibrous substrate production example 3
10 parts of a polycondensate (polyimide resin) of biphenyltetracarboxylic dianhydride (BTDA) and paraphenylenediamine (PPD) was dissolved in 90 parts of N-methylpyrrolidone. A fibrous base material c was obtained by an electrospinning method in which this solution was sprayed using Esplayer ES2000 (manufactured by Huence Co., Ltd.) at a voltage of 10 kV and a liquid feeding speed of 10 μL. The fibrous substrate had a fiber diameter of 0.2 μm and a thickness of 10 μm.

Fibrous substrate production example 4
10 parts of a para-aramid resin obtained by co-condensation of paraphenylenediamide and terephthalic acid chloride was dissolved in 90 parts of tetrafluorophenol. A fibrous base material d was obtained by an electrospinning method in which this solution was sprayed using Esplayer ES2000 (manufactured by Huence Co., Ltd.) at a voltage of 10 kV and a liquid feeding speed of 10 μL. The fibrous substrate had a fiber diameter of 0.2 μm and a thickness of 10 μm.

Fibrous substrate production example 5
A fibrous base material e composed of fibers obtained by highly orienting a liquid crystalline polyester resin (product name “Vectra”, manufactured by Polyplastics Co., Ltd.) at the time of spinning was obtained. The fibrous substrate had a fiber diameter of 5 μm and a thickness of 10 μm.

Fibrous substrate production example 6
A fibrous base material f composed of highly oriented fibers of a para-aramid resin obtained by co-condensation of paraphenylene diamide and terephthalic acid chloride by spinning was obtained. The fibrous substrate had a fiber diameter of 5 μm and a thickness of 10 μm.

Example 1
8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] dodec-3-ene (hereinafter abbreviated as ETD) 70 parts and bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride 30 parts Butene was added as a molecular weight modifier for ring-opening copolymerization, and then hydrogenation reaction was performed to obtain a hydrogenated ring-opening copolymer. Mn of the obtained hydrogenated ring-opening copolymer was 23,000, Mw was 50,000, and Tg was 142 ° C. The hydrogenation rate was 99% or more. The acid value was 76 mgKOH / g, and the volume resistivity was 1 × 10 ¹⁴ Ω · cm or more.
100 parts of ring-opening copolymer hydrogenated product as polymer (A) component, 40 parts of bisphenol A bis (propylene glycol glycidyl ether) ether as curing agent (B) component, 2- [2-hydroxy as laser processability improver −3,5-bis (α, α-dimethylbenzyl) phenyl] benzotriazole, 0.1 part of 1-benzyl-2-phenylimidazole as a curing accelerator, and liquid polybutadiene as a polymer soluble in the oxidation treatment liquid 10 parts (Nisseki Polybutadiene B-1000: manufactured by Nippon Petrochemical Co., Ltd.) was dissolved in a mixed solvent consisting of 215 parts of xylene and 54 parts of cyclopentanone to obtain a varnish of a curable resin composition.

  A fiber having a size of 250 mm long × 250 mm wide and 10 μm thick on a polyethylene naphthalate film (support) having a size of 300 mm long × 300 mm wide, a thickness of 40 μm, and an average surface roughness Ra of 0.08 μm. The fibrous base material a was installed, and then the varnish obtained above was applied to the fibrous base material a using a die coater and impregnated. Subsequently, it dried for 10 minutes at 80 degreeC in nitrogen atmosphere, and obtained the composite resin molding with a support whose thickness is 30 micrometers and fibrous base material content is 30%.

10 μm thick copper is pasted on the surface of the core material obtained by impregnating glass fiber with varnish containing glass filler and halogen-free epoxy resin. An inner layer that is a substrate having a conductor layer formed on the surface by forming a conductor layer having a wiring width and a distance between the wirings of 15 μm and a thickness of 10 μm on the surface of the copper-clad substrate and microetching the surface by contact with an organic acid. A substrate was obtained. The composite resin 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 composite resin 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 110 ° C. and a pressure of 1.0 MPa for 300 seconds (primary press). Furthermore, using a vacuum laminator equipped with a heat-resistant rubber press plate covered with a metal press plate, the pressure was reduced to 200 Pa and thermocompression bonded at a temperature of 140 ° C. and 1.0 MPa for 300 seconds (secondary press ). Next, the support was peeled off to obtain an inner layer substrate having a composite resin 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 under a nitrogen atmosphere at 170 ° C. for 60 minutes to cure the resin layer and form an electrical insulating layer on the inner layer substrate. An interlayer connection via hole having a diameter of 30 μm was formed in this electrical insulating layer using a third harmonic of a UV-YAG laser, to obtain a multilayer circuit board with a via hole.

  The obtained multilayer circuit board with via holes was rock-immersed in an aqueous solution at 70 ° C. adjusted to have 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 pre-plating treatment, Alcup activator MAT-1-A (manufactured by Uemura Kogyo Co., Ltd.) is 200 ml / liter, and Alcup activator MAT-1-B (manufactured by Uemura Kogyo Co., Ltd.) is 30 ml. / 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.

Subsequently, the multilayer circuit board after the pre-plating treatment 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.

  A dry film of a commercially available photosensitive resist is attached to the surface of the multilayer circuit board that has been subjected to the antirust treatment by thermocompression bonding, and a mask having a pattern corresponding to the adhesion evaluation pattern is adhered to the dry film. After exposure, development was performed to obtain a resist pattern. Next, it was immersed in an aqueous solution of 100 g / liter sulfuric acid at 25 ° C. for 1 minute to remove the rust preventive, and electrolytic copper plating was applied to the resist non-formed portion to form an electrolytic copper plating film having a thickness of 10 μm. Next, the resist pattern is stripped and removed with a stripping solution, and an etching process is performed with a mixed aqueous solution of cupric chloride and hydrochloric acid to form a wiring pattern composed of the metal thin film and the electrolytic copper plating film. A patterned multilayer circuit board a was obtained. Finally, annealing was performed at 170 ° C. for 30 minutes to obtain a multilayer printed wiring board. Circuit patternability was evaluated for the obtained multilayer circuit board a.

Example 2
A multilayer circuit board b was obtained in the same manner as in Example 1 except that the fibrous base material b was used instead of the fibrous base material a in Example 1. The same items as in Example 1 were tested and evaluated.
Example 3
A multilayer circuit board c was obtained in the same manner as in Example 1 except that the fibrous base material c was used instead of the fibrous base material a in Example 1. The same items as in Example 1 were tested and evaluated.
Example 4
A multilayer circuit board d was obtained in the same manner as in Example 1 except that the fibrous base material d was used instead of the fibrous base material a in Example 1. The same items as in Example 1 were tested and evaluated.

Comparative Example 1
A multilayer circuit board e was obtained in the same manner as in Example 1 except that the fibrous base material e was used instead of the fibrous base material a in Example 1. The same items as in Example 1 were tested and evaluated.
Comparative Example 2
A multilayer circuit board f was obtained in the same manner as in Example 1 except that the fibrous base material f was used instead of the fibrous base material a in Example 1. The same items as in Example 1 were tested and evaluated.

  The results of Examples and Comparative Examples are shown in the table below.

  From this result, it can be seen that when a fibrous base material having a large fiber diameter is used, flatness, patterning property, and laser processability are inferior.

Claims (7)

Curing containing a polymer (A) having a weight average molecular weight of 10,000 to 250,000, having a carboxyl group or an acid anhydride group and an acid value of 5 to 200 mgKOH / g, and a curing agent (B) A composite resin molded article obtained by impregnating a fibrous base material having a fiber diameter of 0.05 to 2 μm with a functional resin composition. The composite resin molded article according to claim 1, wherein the polymer (A) is an alicyclic olefin polymer. A polymer (A), a curing agent (B), and an organic solvent having a weight average molecular weight of 10,000 to 250,000, a carboxyl group or an acid anhydride group, and an acid value of 5 to 200 mgKOH / g. The method for producing a composite resin molded article according to claim 1, wherein the curable resin composition is impregnated into a fibrous base material having a fiber diameter of 0.05 to 2 μm and dried. Hardened | cured material formed by hardening | curing the composite resin molding of Claim 1 or 2. The laminated body formed by laminating | stacking the board | substrate which has a conductor layer on the surface, and the electrically insulating layer which consists of hardened | cured material of Claim 4. The method for producing a laminate according to claim 4, wherein the composite resin molded body according to claim 1 or 2 is thermocompression-bonded on a substrate having a conductor layer on a surface and cured to form an electrical insulating layer. . A multilayer circuit board obtained by further forming a conductor layer on the electrically insulating layer of the laminate according to claim 4.