CURABLE EPOXY COMPOSITION AND FILM, LAMINATED FILM, PREPREG, LAMINATE, CURED ARTICLE, AND COMPOSITE ARTICLE OBTAINED USING SAME

Abstract

A curable epoxy composition comprising a polyvalent epoxy compound (A) having a biphenyl structure and/or condensed polycyclic structure, a trivalent or higher polyvalent phenol type epoxy compound (B), and a triazine structure-containing phenol resin (C) and a film, laminated film, prepreg, laminate, cured article, and composite article obtained using the same are provided.

Claims

1. A curable epoxy composition comprising a polyvalent epoxy compound (A) having a biphenyl structure and/or condensed poly cyclic structure, a trivalent or higher polyvalent phenol type epoxy compound (B), and a triazine structure-containing phenol resin (C).

2. The curable epoxy composition according to claim 1, wherein the trivalent or higher polyvalent phenol type epoxy compound (B) includes an epoxy compound having a structure represented by the following general formula (1): ##STR00011## where, in formula (1), each of R.sup.1 respectively independently indicates a hydrogen atom or hydrocarbon group having 1 to 3 carbon atoms.

3. The curable epoxy composition according to claim 1, wherein the trivalent or higher polyvalent phenol type epoxy compound (B) includes an epoxy compound having any one of structures represented by the following general formulas (2) to (5): ##STR00012## where, in formula (2), each of R.sup.2 respectively independently indicates a hydrogen atom or hydrocarbon group having 1 to 3 carbon atoms, and “m” is an integer of 2 or more, and ##STR00013## where, in formula (4), “n” indicates a positive integer. ##STR00014##

4. The curable epoxy composition according to claim 1, wherein a ratio of content of the polyvalent epoxy compound (A) and the trivalent or higher polyvalent phenol type epoxy compound (B) is, by a weight ratio of “polyvalent epoxy compound (A):trivalent or higher polyvalent phenol type epoxy compound (B)”, 20:80 to 95:5.

5. The curable epoxy composition according to claim 1, wherein a ratio of content of the triazine structure-containing phenol resin (C) is 1 to 60 parts by weight with respect to 100 parts by weight of total of epoxy compound contained in the curable epoxy composition.

6. The curable epoxy composition according to claim 1, further comprising an active ester compound (D).

7. A film comprising a curable epoxy composition according to claim 1.

8. A laminated film comprising a binder layer which comprises the curable epoxy composition according to claim 1 and a platable layer which comprises a platable layer-use resin composition.

9. A prepreg comprising the film according to claim 7 and a fiber base material.

10. A laminate obtained by laminating a substrate with the film according to claim 7.

11. A cured article obtained by curing the curable epoxy composition according to claim 1.

12. A composite article obtained by forming a conductor layer on a surface of the cured article according to claim 11.

13. A board for an electronic material comprising the cured article according to claim 11.

14. A cured article obtained by curing the film according to claim 7.

15. A cured article obtained by curing the laminated film according to claim 8.

16. A cured article obtained by curing the prepreg according to claim 9.

17. A cured article obtained by curing the laminate according to claim 10.

18. A composite article obtained by forming a conductor layer on a surface of the cured article according to claim 14.

19. A composite article obtained by forming a conductor layer on a surface of the cured article according to claim 15.

20. A composite article obtained by forming a conductor layer on a surface of the cured article according to claim 16.

21. A composite article obtained by forming a conductor layer on a surface of the cured article according to claim 17.

Description

EXAMPLES

[0159] Below, examples end comparative examples will be given to more specifically explain the present invention. Note that, in the examples, the “parts” and “%”, unless particularly indicated otherwise, are based on weight. The various types of properties were evaluated by the following methods.

[0160] (1) Number Average Molecular Weight (Mn) and Weight Average Molecular insight (Mw) of Alicyclic Olefin Polymer

[0161] These were measured using tetrahydrofuran as a developing solvent and using gel permeation chromatography (GPC) and were found as values converted for polystyrene.

[0162] (2) Hydrogenation Ratio of Alicyclic Olefin Polymer

[0163] The ratio of the number of moles of the unsaturated bonds which were hydrogenated with respect to the number of moles of the unsaturated bonds in the polymer before the hydrogenation was found by measurement of the 400 MHz .sup.1H-NMR spectrum. This was used as the hydrogenation ratio.

[0164] (3) Glass Transition Temperature (Heat Resistance)

[0165] From the film-shaped cured article, a small piece of a width 6 mm, length 15.4 mm, and thickness 40 μm was cut. Under conditions of a distance between support points of 10 mm and a temperature elevation rate of 10° C./min, a thermomechanical analyzer (TMA/SDTA840: made by Metler Toledo) was used for measurement to obtain a stress-temperature curve. A tangent was drawn to the inflection point. From the intersecting point of this tangent, the glass transition temperature (Tg) of the film-shaped cured article was found. The heat resistance was evaluated based on the following evaluation criteria. The higher the glass transition, temperature, the better the heat resistance.

[0166] (Evaluation Criteria)

[0167] A: glass transition temperature of 150° C. or more

[0168] B: glass transition temperature of 145° C. to less than 150° C.

[0169] C: glass transition temperature of less than 145° C.

[0170] (4) Dielectric Tangent (Electrical Characteristics)

[0171] A width 2.0 mm, length 80 mm, thickness 40 μm piece was cut out from a film shaped cured article, measured for dielectric tangent (tan δ) at 10 GHz using a resonant cavity perturbation method permittivity measurement apparatus. The electrical characteristics were evaluated in accordance with the following evaluation criteria.

[0172] (Evaluation Criteria)

[0173] A: dielectric tangent of less than 0.0065

[0174] B: dielectric tangent of 0.0065 to less than 0.070

[0175] C: dielectric tangent of 0.0070 or more

[0176] (5) Initial Adhesion

[0177] A thickness 35 μm electrolytic copper foil was etched on its surface by an etchant (product name “CZ-8100”, made by MEC Co., Ltd.) by about 0.5 μm. On the etched surface of the electrolytic copper foil, the film-shaped article was superposed so that its resin layer side contacted it, then a vacuum laminator was used to hot press-bond them under the conditions of a vacuum degree of 1 kPa or less, 90° C., 30 seconds, and pressure 0.7 MPa. Next, the support was peeled off from the surface of the film-shaped article at the opposite side to the resin layer, a glass epoxy copper-clad board (FR-4) which was etched by the etchant by about 2 μm was laid over the surface of the exposed resin layer, then a vacuum laminator was used to hot press-bond them under the same conditions as above. The thus obtained composite shaped article was heated in an oven at 180° C. for 90 minutes to obtain a laminate cured article. The peel strength of the copper foil from the obtained laminate cured article was measured in accordance with JIS C6481 and the following evaluation criteria were used for evaluation.

[0178] (Evaluation Criteria)

[0179] A: peel strength of 0.55 kN/m or more

[0180] B: peel Strength Of 0.30 kN/m to less than 0.55 kN/m

[0181] C: peel strength, of less than 0.50 kN/m

[0182] (6) Adhesion After High Temperature and High Humidity Test

[0183] The same procedure was followed as the above (5) to obtain a laminate cured article. The copper foil at the surface thereof was peeled off leaving a width of 10 mm, but removing the rest. The obtained sample was allowed to stand in a constant temperature and constant humidity tank of a temperature of 130° C. and humidity of 98 % RH for 100 hours, then the peel strength of the copper foil from this laminate cured article was measured in accordance with JIS C6481 and was evaluated based on the following evaluation criteria.

[0184] (Evaluation Criteria)

[0185] A: peel strength of 0.30 kN/m or more

[0186] B: peel strength of 0.25 kN/m to less than 0.30 kN/m

[0187] C: peel strength of less than 0.25 kN/m

Example 1

[0188] (Preparation of Curable Epoxy Composition)

[0189] 50 parts of a polyvalent epoxy compound (A) having a biphenyl structure comprised of a biphenyl dimethylene-based novolac type epoxy resin (product name “NC-3000L”, made by Nippon Kayaku, epoxy equivalent 269), 50 parts of a univalent or higher polyvalent phenol type epoxy compound (B) comprised of a tetrakishydroxyphenylethane-type epoxy expound (product name “jER 1031S”, made by Mitsubishi Chemical, epoxy equivalent 200, softening point 90° C.), 30 parts of the triazine structure-containing phenol resin (C) comprised of a triazine structure-containing cresol novolac resin (product name “Phenolite LA-3018-50P” (nonvolatile content 50% propylene glycol monomethylether solution, made by DIC, active hydroxyl group equivalent 154) (15 parts converted to triazine structure-containing cresol novolac resin), 115.3 parts of, as an active ester compound (D), active ester compound (product name “Epiclon HPC-8000-65T”, nonvolatile content 65% toluene solution, made by DIC, active ester group equivalent 223) (75 parts converted to active ester compound), 350 parts of a filler comprised of silica (product name “SC2500-SXJ”, made by Admatechs), 1 part of an antiaging agent comprised of a hindered phenol-based antioxidant (product name “Irganox (registered trademark; 3114”, made by BASF), and 110 parts of anisole were mixed and stirred by a planetary mixer for 3 minutes. Furthermore, to this, 8.3 parts of a curing accelerator comprised of a solution of 30% of 1-benzyl-2-phenylimidazole dissolved in anisole (2.5 parts converted to 1-benzyl-2-phenylimidazole) was mixed and stirred by a planetary mixer for 5 minutes to obtain a varnish of a curable epoxy composition. Note that, in the varnish, the content of the filler was 64% converted to solid content.

[0190] (Preparation of Film-Shaped Article)

[0191] Next, the above obtained varnish of the curable epoxy composition was applied by a die coater on a vertical 300 mm×horizontal 300 mm size, thickness 38 μm, surface average roughness Ra 0.08 μm polyethylene terephthalate film (support: Lumirror (registered trademark) T60, made by Toray Industries Inc.), then dried in a nitrogen atmosphere at 80° C. for 10 minutes to obtain a film shaped article of thickness 43 μm resin composition on a support. The obtained film-shaped article was used in accordance with the above method to evaluate the desmearing ability and adhesion. The obtained film-shaped article was used in accordance with the above methods to evaluate the initial adhesion and adhesion after a high temperature and high humidity test. The results are shown in Table 1.

[0192] (Preparation of Film-Shaped Cured Article)

[0193] Next, a piece which was cut out from the thus obtained film shaped article of the curable epoxy composition was placed on a thickness 10 μm copper foil. This was set, in the state, with the support attached, so that the curable epoxy composition became the inside. A vacuum laminator which was provided with heat resistant rubber press plates at the top and bottom was used to reduce the pressure to 200 Pa and hot press bond the laminate at a temperature of 110° C. and a pressure of 0.1 MPa for 60 seconds, the support was peeled off, then the laminate was heated and cured at 180° C. for 120 minutes in the air. After curing, the copper foil is cut from cured resin with the copper foil, then the cut copper foil was dissolved in a 1 mol/liter ammonium persulfate aqueous solution to obtain a film shaped cured article. The obtained film shaped cured article was used in accordance with the above methods to measure the glass transition temperature and dielectric tangent. The results are shown in Table 1.

Examples 2 to 5 and Comparative Examples 1 to 5

[0194] Except for changing the formulations in accordance with the compositions of the curable epoxy compositions in Examples 2 to 5 and comparative Examples 1 to 5 of Table 1, the same procedure was followed as in Example 1 to obtain a varnish of a curable epoxy composition, a film-shaped article, and a film-sloped cured article and the same procedure was followed to measure and evaluate them. The results are shown in Table 1.

[0195] Note that, in Table 1, the “trishydroxyphenylmethane-type epoxy compound” is trivalent or higher polyvalent phenol type epoxy compound (B) comprised of the trishydroxyphenylmethane-type epoxy compound (product name “jER 1032H”, made by Mitsubishi Chemical, epoxy equivalent 170, softening point 60° C.) , the “phenol-based novolac type epoxy compound having a phosphaphenanthrene structure” is phenol-based novolac type epoxy compound having a phosphaphenanthrene structure (product name “FX-289BEK75”, made by Nippon Steel & Sumikin Chemical, solid content 75% methylethylketone solution, phosphorus content 2%, epoxy equivalent 305), and the “bisphenol A type epoxy compound” is bisphenol A type epoxy compound (product name “jER 828EL”, made by Mitsubishi Chemical, epoxy equivalent 186, liquid state).

Table 1

[0196]

TABLE-US-00001 TABLE 1 Examples Comparative Examples 1 2 3 4 5 1 2 3 4 5 Composition of curable epoxy composition (parts) Epoxy Polyvalent epoxy compound having 50 80 50 80 60 100 50 15 compound biphenyl structure Tetrakishydroxyphenylethane-type epoxy 50 20 15 100 50 compound Trishydroxyphenylmethane-type epoxy 50 20 100 compound Epoxy compound having 25 phosphaphenanthrene structure Bisphenol A type epoxy compound 85 Triazine structure-containing phenol resin (C) 15 15 15 15 15 15 15 15 15 Active ester compound (D) 75 67 85 70 65 60 90 110 100 90 Silica 350 340 370 350 340 330 380 420 370 380 Antiaging agent 1 1 1 1 1 1 1 1 1 1 Curing accelerator 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Equivalent ratio of epoxy compound/ 1.00 0.99 1.00 1.00 0.98 1.01 0.99 0.99 0.97 1.01 (triazine structure-containing phenol resin (C) + active ester compound (D)) Results of evaluation Heat resistance (glass transition temperature) A A A A A C A A A C Electrical characteristics (dielectric tangent) A A B A A A C C A A Initial adhesion A A A A A A B B C B Adhesion after high temperature and high humidity test A A A A A A B B C C
As shown in Table 1, according to the curable epoxy composition of the present invention, a film-shaped cured article excellent in heat resistance, electrical characteristics, and initial adhesion and adhesion after a high temperature and high humidity test was obtained (Examples 1 to 5). Therefore, it is confirmed that according to the curable epoxy composition of the present invention, it is possible to form an electrical insulating layer having such excellent properties.

[0197] On the other hand, when not containing a trivalent or higher polyvalent phenol type epoxy compound (B), the obtained film-shaped cured article becomes inferior in heat resistance as a result (Comparative Example 1). Further, when not containing a polyvalent epoxy compound (A) having a biphenyl structure and/or condensed polycyclic structure, the obtained film-shaped cured article becomes inferior in electrical characteristics as a result (Comparative Examples 2 and 3).

[0198] Furthermore, when not containing a triazine structure-containing phenol resin (C), the obtained film-shaped cured article becomes inferior in initial adhesion and adhesion after a high temperature and high humidity test as a result (Comparative Example 4), while when using instead of the trivalent or higher polyvalent phenol type epoxy compound (B), a bisphenol A type epoxy compound, the obtained film shaped cured article becomes inferior in heat resistance and adhesion after a high temperature and high humidity test (Comparative Example 5).

Synthesis Example 1

[0199] As a first stage of polymerization, 5-ethylidene-bicyclo[2.2.1]hept-2-ene was charged in 35 molar parts, 1-hexene in 0.9 molar part, anisole in 340 molar parts, and C1063 in 0.005 molar part to a pressure resistant glass reactor with the inside substituted with nitrogen. Under stirring, a polymerization reaction was performed at 80° C. for 30 minutes to obtain a solution of a norbornene-based ring opened polymer.

[0200] Next, as a second stage of polymerization, in the solution obtained at the first stage of polymerization, 45 molar parts of tetracyclo[6.5.0.1.sup.2,5.0.sup.8,13]trideca-3,8,10,12-tetraene, 20 molar parts of bicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic acid anhydride, 250 molar parts of anisole, and 0.01 molar part of a ruthenium-based polymerization catalyst comprised of 4-acetoxybenzylidene(dichloro) (4,5-dibromo-1,3-dimesityl-4-imidazolin-2-ylidene) (tricyclohexylphosphene)ruthenium (C1063, made by Wako Pure Chemical) were added. Under stirring, a polymerization reaction was caused at 80° C. for 1.5 hours to obtain a norbornene-based ring opened polymer. When measuring this solution by gas chromatography, it was confirmed that substantially no monomers remained. The polymerization conversion rate was 99% or more.

[0201] Next, an autoclave with a stirrer with the inside substituted with nitrogen was charged with a solution of the obtained ring-opened polymer, 0.03 molar part of C1063 was added, and a hydrogenation reaction was performed at 150° C. at a hydrogen pressure of 7 MPa for 5 hours to obtain a solution of a hydrogenated article of a norbornene-based ring-opened polymer comprised of the alicyclic type olefin polymer (1). The weight average molecular weight of the alicyclic type olefin polymer (1) was 60,000, the number average molecular weight of 30,000, and the molecular weight distribution was 2. Further, the hydrogenation rate was 95%, while the content of the repeating units having a carboxylic acid anhydride group was 20 mol %. The solid content concentration of the solution of the alicyclic type olefin polymer (1) was 22%.

Example 6

[0202] (Platable Layer-Use Resin Composition)

[0203] 454 parts of the solution of the alicyclic olefin polymer (1) which was obtained in Synthesis Example 1 (converted to alicyclic olefin polymer (1), 100 parts, 36 parts of a polyvalent epoxy compound which has a dicyclopentadiene structure (“Epiclon HP7200L”, made by DIC, “Epiclon” is a registered trademark) as a curing agent, 24.5 parts of an inorganic filler constituted by silica (“Admafine SO-C1”, made by Admatechs, average particle size 0.25 μm, “Admafine” is a registered trademark), 1 part of tris(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate (“Irganox (registered trademark) 3114”, made by BASF) as an antiaging agent, 0.5 part of 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole benzotriazole as an ultraviolet absorber, and 0.5 part of 1-benzyl-2-phenylimidazole as a curing accelerator were mixed in anisole and mixed to give a concentration of the compounding agents of 16% so as to obtain a varnish of the platable layer-use resin composition.

[0204] (Preparation of Laminated Film)

[0205] The varnish of the platable layer-use resin composition, which was obtained above was applied on a thickness 38 μm polyethylene terephthalate film (support) by using a wire bar, then was dried in a nitrogen atmosphere at 80° C. for 10 minutes to obtain a film with a support on which a thickness 3 μm platable layer comprised of an uncured platable layer-use resin composition was formed.

[0206] Next, the surface of the film with the support on which the platable layer comprised of the platable layer-use resin composition was formed was coated with the varnish of the curable epoxy composition which was obtained in Example 1 by using a doctor blade (made by Tester Sangyo Co., Ltd) and an auto film applicator (made by Tester Sangyo Co., Ltd), then was dried in a nitrogen, atmosphere at 80° C. for 10 minutes to obtain a laminated film with the support on which a total thickness 43 μm platable layer and adhesive layer were formed. The laminated film with the support was formed by the support, the platable layer comprised of the platable layer-use resin composition, and the adhesive layer comprised of the curable epoxy composition in that order.

[0207] (Preparation of Laminate Cured Article)

[0208] Next, separate from the above, a varnish which contains glass filler and a halogen-free epoxy resin was impregnated in glass fibers to obtain a core material. On the surfaces of this, thickness 18 μm copper was bonded to obtain a thickness 0.8 mm, 150 mm square (vertical 150 mm and horizontal 150 mm) two-sided copper-clad substrate. On the surfaces of this, conductor layers with interconnect widths and interconnect pitches of 50 μm and thicknesses of 30 μm and with surfaces microetched by contacting an organic acid were formed to obtain an inside layer substrate.

[0209] At the two surfaces of the inside layer substrate, the above obtained laminated film with the support cut into 150 mm square pieces were bonded with the surfaces at the curable epoxy composition sides becoming the insides, then the laminate was pressed by primary pressing. The primary pressing was hot press bonding by a vacuum laminator which is provided with press plates made of heat resistant rubber at the top and bottom under a reduced pressure of 200 Pa at a temperature 110° C. with a pressure of 0.1 MPa for 90 seconds. Furthermore, a hydraulic press apparatus which is provided with metal press plates at the top and bottom was used for hot press bonding at a press bonding temperature of 110° C. and 1 MPa for 90 seconds. Next, the supports were peeled off to obtain a laminate of a resin layer which was comprised of the curable epoxy composition and the platable layer-use resin composition and the inside layer substrate. Furthermore, the laminate was allowed to stand in an air atmosphere at 180° C. for 60 minutes to make the resin layer cure and form an electrical insulating layer on the inside layer substrate.

[0210] (Swelling Treatment Step)

[0211] The obtained laminate cured article was dipped while shaking in a 60° C. aqueous solution which was prepared to contain a swelling solution (°Swelling Dip Securiganth P°, made by Atotech, “Securiganth” is a registered trademark) 500 ml/liter and sodium hydroxide 3 g/liter for 15 minutes, then was rinsed.

[0212] (Oxidizing Treatment Step)

[0213] Next, the laminate cured article was dipped while shaking in an 80° C. aqueous solution which was prepared to contain an aqueous solution of permanganate (“Concentrate Compact CP”, made by Atotech) 640 ml/liter and a concentration of sodium hydroxide of 40 g/liter for 20 minutes, then was rinsed.

[0214] (Neutralizing/Reduction Treatment Step)

[0215] Next, the laminate cured article was dipped in a 40° C. aqueous solution which was prepared to contain an aqueous solution of 100 ml/liter of hydroxylamine sulfate (“Reduction Securiganth P 500”, made by Atotech, “Securiganth” is a registered trademark) and 35 ml/liter of sulfuric acid for 5 minutes to neutralize and reduce it, then was rinsed.

[0216] (Cleaner/Conditioner Step)

[0217] Next, the laminate cured article was dipped in a 50° C. aqueous solution which was prepared to contain a cleaner/conditioner aqueous solution (“Alcup MCC-6-A”, made by Uyemura & Co., Ltd. “Alcup” is a registered trademark) of a concentration of 50 ml/liter for 5 minutes to treat it with the cleaner and conditioner. Next, the laminate was dipped in 40° C. rinsing water for 1 minute, then was rinsed.

[0218] (Soft Etching Step)

[0219] Next, the laminate cured article was dipped in an aqueous solution which was prepared to contain a sulfuric acid concentration of 100 g/liter and sodium persulfate of 100 g/liter for 2 minutes to be soft etched, then was rinsed.

[0220] (Pickling Step)

[0221] Next, the laminate cured article was dipped in an aqueous solution which was prepared to contain a sulfuric acid concentration of 100 g/liter for 1 minute to be pickled, then was rinsed.

[0222] (Catalyst Imparting Step)

[0223] Next, the laminate cured article was dipped in a 60° C. Pd salt-containing plating catalyst aqueous solution which was prepared to contain 200 ml/liter of Alcup Activator MAT-1-A (product name, made by Uyemura & Co., Ltd. “Alcup” is a registered trademark), 30 ml/liter of Alcup Activator MAT-1-B (product name, made by Uyemura & Co., Ltd. “Alcup” is a registered trademark), and 0.35 g/liter of sodium hydroxide for 5 minutes, then was rinsed.

[0224] (Activation Step)

[0225] Next, the laminate cured article was dipped in an aqueous solution which was prepared to contain 50 ml/liter of Alcup Reducer MAB-4-A (product name, made by Uyemura & Co., “Alcup” is a registered trademark) and 200 ml/liter of Alcup-Reducer MAB-4-B (product name, made by Uyemura & Co., Ltd. “Alcup” is a registered trademark) at 35° C. for 3 minutes to reduce the plating catalyst, then was rinsed.

[0226] (Accelerator Treatment Step)

[0227] Next, the laminate cured article was dipped in an aqueous solution which was prepared to contain 50 ml/liter of Alcup Accelerator MEL-3-A (product name, made by Uyemura & Co., Ltd. “Alcup” is a registered trademark) at 25° C. for 1 minute.

[0228] (Electroless Plating Step)

[0229] The thus obtained laminate eared article was dipped in an electroless copper plating solution which was prepared to contain 100 ml/liter of Thru-Cup PEA-6-A (product name, made by Uyemura & Co., Ltd. “Thru-Cup” is a registered trademark), 50 ml/liter of Thru-Cop PEA-6-B-2X (product name, made by Uyemura & Co. Ltd.), 14 ml/liter of Thru-Cup PEA-6-C (product name, made by Uyemura & Co. Ltd.), 15 ml/liter of Thru-Cup PEA-6-D (product name, made by Uyemura & Co. Ltd.) 50 ml/liter of Thru-Cup PEA-6-E (product name, made by Uyemura & Co. Ltd.), and 5 ml/liter of 37 wt % formalin aqueous solution, while blowing in air, at a temperature of 36° C. for 20 minutes for electroless copper plating so as to form an electroless plating film on the laminate cured article surface (surface of platable layer comprised of platable layer-use resin composition).

[0230] Next, the laminate cured article which was formed with the electroless plating film was annealed in an air atmosphere at 150° C. for 30 minutes.

[0231] The annealed laminate cured article was electroplated with copper to form a thickness 30 μm electroplated copper layer. Next, the laminate cured article was heat treated at 180° C. for 60 minutes to thereby obtain a two-sided two-layer multilayer printed circuit board comprised of a laminate-cured article on which a conductor layer comprised of a thin metal layer and electroplated copper film.