JP2007030326A - Copper foil with resin, laminate for producing printed wiring boad, and multilayer printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide copper foil with a resin which improves low transmission loss properties during high frequency transmission by copper foil constituting the conductor layer of a printed wiring board and problematic adhesive properties between a copper foil layer and a resin layer during heating in a re-flow solder process etc., and a multilayer printed wiring board using the copper foil. <P>SOLUTION: The copper foil with the resin comprises laminating the resin layer containing a polyphenylene oxide resin composition in which the dielectric constant of a cured substance having unsaturated double bonds is 3.5 or below and the copper foil, wherein the surface roughness of the side on which the resin layer of the copper foil formed is 1-2 μm, a metal treatment layer is formed on the surface, and a silane coupling agent is applied on the metal treatment layer. The amount of zinc, the amount of nickel, and the amount of silicon in the surface are each within a specified range. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a resin-coated copper foil, a laminate for producing a printed wiring board, and a multilayer printed wiring board, and more particularly, a resin-coated copper foil capable of reducing electrical signal transmission loss in high frequency applications, and a laminate for producing a printed wiring board. And a multilayer printed wiring board.

  In recent years, printed wiring boards used in various electronic devices have been developed with higher integration of semiconductor devices to be mounted and higher density of packages, etc., and accordingly, low transmission loss characteristics especially at high frequency transmission. Improvement is demanded.

  In order to improve the low transmission loss, it is preferable that the copper foil forming the circuit portion has a low surface roughness. However, if the surface roughness is too low, the adhesion between the copper foil and the resin layer that is an insulating layer is low, and in the reflow soldering process when mounting various electronic components on the printed wiring board, There was a problem of causing peeling and swelling.

  In order to solve the above-mentioned problem, for example, the following Patent Document 1 includes a component having an unsaturated double bond and a thermosetting resin composition having a cured product having a dielectric constant of 3.5 or less. In the laminated material for producing a printed wiring board constituted by laminating a resin layer and a copper foil, the surface of the copper foil on which the resin layer is formed is treated with zinc or a zinc alloy, and then vinyl. A technique using a material treated with a coupling agent by a group-containing silane coupling agent is disclosed.

  When the technique is used, even if a copper foil having a small surface roughness is used, the unsaturated double bond in the thermosetting resin composition is bonded to the vinyl group-containing silane coupling agent, and in this bond, zinc or Since the zinc alloy works catalytically to improve the adhesive force between the copper foil and the thermosetting resin composition, the printed wiring board or multilayer having low high-frequency transmission loss and high adhesion between the conductor layer and the insulating layer It is described that a printed wiring board can be easily obtained.

However, when the above technique is used, the low transmission loss at the time of high-frequency transmission is insufficient, and the problem of peeling or swelling of the copper foil has not been solved even in the reflow soldering process.
JP 2003-283098 A

  The present invention has been made in view of the above points, and improves the low transmission loss at the time of high-frequency transmission in the copper foil constituting the conductor layer of the printed wiring board, and becomes a problem in the reflow soldering process and the like. It aims at providing the copper foil with resin which improved the adhesiveness of the copper foil layer and resin layer at the time of a heat | fever, and a multilayer printed wiring board using the same.

The resin-coated copper foil of the present invention contains a resin layer containing a polyphenylene oxide resin composition containing a component having an unsaturated double bond and a dielectric constant of the cured product of 3.5 or less, and a copper foil. In the resin-coated copper foil, the surface roughness on the side of the copper foil on which the resin layer is formed is 0.5 to 2 μm, and the surface of the copper foil after the metal treatment layer is formed is a silane coupling agent There are applied, the amount of zinc in the surface 1-2 mg / dm ^2, the amount of nickel 0.10~0.3mg / dm ² and a silicon amount is 0.005-0.05 / dm ² It is a characteristic (claim 1).

Moreover, the chromium amount in the said surface of the said copper foil with resin is 0.05-0.15 mg / dm < ² > (Claim 2).

  Furthermore, in the amount of silicon on the surface of the copper foil with resin, the ratio of the number of atoms where the amount of adhesion is small and where the amount of adhesion is large is 1 to 6 times (Claim 3).

  Moreover, it is a copper foil with a resin which contains 20-80 mass% of polyphenylene oxide resin and 20-70 mass% of triallyl isocyanurate resin in the resin component whole quantity of the said polyphenylene oxide resin composition (Claim 4).

  Furthermore, it is a resin-attached copper foil containing 20 to 80% by mass of ethenylbenzylated polyphenylene oxide resin in the total amount of the resin component of the polyphenylene oxide resin (Claim 5).

  The silane coupling agent is vinyl silane.

  Further, in the copper foil with resin, a prepreg obtained by impregnating the base material with the polyphenylene oxide resin composition as the resin layer and semi-curing by heat drying is used, and the copper foil is laminated on both sides or one side of the prepreg. A laminate for manufacturing a printed wiring board obtained by heating and pressing.

  And it is a multilayer printed wiring board obtained using the said laminated copper foil with resin and / or printed wiring board manufacture (Claim 8).

  The copper foil with a resin according to claim 1 of the present invention is one in which an unsaturated double bond in a polyphenylene oxide resin composition is combined with a silane coupling agent to obtain a high adhesive strength and adheres to the surface of the copper foil. The zinc acted catalytically in the bonding reaction between the silane coupling agent and the copper foil, and the bonding reaction between the silane coupling agent and the double bond in the polyphenylene oxide resin composition, and the copper foil and the polyphenylene oxide resin composition. In addition, the nickel adhered to the surface maintains the adhesive strength with the resin layer even when the reflow soldering process or the like is at a high temperature. For this reason, by using this resin-coated copper foil, high-frequency transmission loss is low, and high adhesion can be maintained even when exposed to high temperatures such as the reflow soldering process, particularly the adhesion between the copper foil and the resin layer. It can be done.

  Moreover, the invention of claim 2 can obtain the antirust / anti-discoloration effect of the copper foil in claim 1 because chromium is adhered to the surface at a specific ratio.

  Furthermore, the invention of claim 3 is the portion according to claim 1 or 2, wherein the ratio of the number of atoms is high, that is, where the adhesion strength between the copper foil and the resin layer is low if there is a difference in the amount of Si adhesion from a microscopic viewpoint, high A location exists and it becomes low as copper foil adhesive strength of resin-coated copper foil. Moreover, since it is easy to be eroded by an acid in the location where the adhesion between the copper foil and the resin layer is low and the acid deterioration rate becomes high, the Si atom number ratio is preferably 1 to 6 times.

  The invention according to claim 4 is the copper foil with resin according to any one of claims 1 to 3, wherein the cured product has a polyphenylene oxide resin composition having a dielectric constant of 3.5 or less, further moldability and heat resistance. It is an excellent one.

  Furthermore, the invention of claim 5 is the copper foil with resin according to any one of claims 1 to 4, wherein the loss tangent is reduced by including an ethenylbenzylated polyphenylene oxide resin, further reducing transmission loss. Can be lowered.

  Moreover, the laminated board which concerns on Claim 6 is preferable in the copper foil with a resin in any one of Claims 1-5 since the adhesive strength of copper foil and a resin layer becomes high especially.

  Furthermore, the laminate for producing a printed wiring board according to claim 7 can easily obtain a multilayer printed wiring board having low transmission loss of high frequency and high adhesion between the conductor layer and the insulating layer.

  The multilayer printed wiring board according to claim 8 has a surface having a low transmission loss in a high frequency application, in which an adhesive strength between an insulating layer formed of a resin layer and a conductor layer formed of a copper foil is increased. Even when a copper foil having a small roughness is used, sufficient adhesive strength can be obtained.

The resin-coated copper foil of the present invention contains a component having an unsaturated double bond, and is formed by laminating a polyphenylene oxide resin composition and a copper foil whose cured product has a dielectric constant of 3.5 or less. In the attached copper foil, the surface roughness of the copper foil on which the resin layer is formed is 0.5 to 2 μm, and the surface is coated with a silane coupling agent after the metal treatment layer is formed. , in which the amount of zinc in the surface 1-2 mg / dm ^2, the amount of nickel 0.10~0.3mg / dm ² and the amount of silicon is characterized in that it is a 0.005-0.05 / dm ² is there.

  In the present invention, the polyphenylene oxide resin composition containing a component having an unsaturated double bond includes a crosslinkable resin such as a polyphenylene oxide resin composition containing ethenylbenzylated polyphenylene oxide or a triallyl isocyanurate resin. The polyphenylene oxide resin composition containing can be mentioned.

の構造で表されるポリ（２，６−ジメチル−１，４−フェニレンオキサイド）等の高分子量ポリフェニレンオキサイドを後述する分子量低減方法により数平均分子量が２０００〜１００００程度にまで分子量を低減させることにより得られる。 The polyphenylene oxide used in the present invention is, for example, the following general formula (1) having a number average molecular weight (Mn) of about 13,000 to 25000 synthesized by the method disclosed in US Pat. No. 4,059,568.

By reducing the molecular weight of the high molecular weight polyphenylene oxide such as poly (2,6-dimethyl-1,4-phenylene oxide) represented by the following structure to a number average molecular weight of about 2000 to 10,000 by a molecular weight reduction method described later. can get.

  As a method for obtaining a polyphenylene oxide having a reduced molecular weight, a known method for reducing the molecular weight, specifically, for example, by reducing the molecular weight by reacting a high molecular weight polyphenylene oxide with a phenol species, “The Journal of Organic Chemistry , 34,297-303 (1969) ", an improved known method thereof, and the like can be used.

  Examples of the method include, in a solvent, a high molecular weight polyphenylene oxide having a number average molecular weight of about 13,000 to 25,000 together with a phenol species, a decomposition peroxide, and a fatty acid metal salt such as cobalt naphthenate that accelerates a decomposition reaction as necessary. Examples of the method include a method in which the number average molecular weight is decomposed to about 2000 to 10,000 by reaction.

  Examples of the phenol species include phenol, cresol, xylenol, hydroquinone, bisphenol A, 2,6-dimethylphenol, 4,4′-dihydroxydiphenyl ether, and the like.

  Examples of the decomposed peroxide include di (t-butylperoxyisopropyl) benzene, benzoyl peroxide, 3,3 ′, 5,5′-tetramethyl-1,4-diphenoquinone chloranil, 2 , 4,6-tri-t-butylphenoxyl, t-butylperoxyisopropyl monocarbonate, azobisisobutyronitrile and the like.

  Further, when the polyphenylene oxide resin composition containing the ethenylbenzylated polyphenylene oxide is used as the component having an unsaturated double bond in the present invention, the terminal phenol group of the polyphenylene oxide having a reduced molecular weight is used. It can be obtained by including an ethenylbenzylated polyphenylene oxide obtained by substituting a hydrogen atom with an ethenylbenzyl group represented by the following general formula (2).

  As a method for producing ethenylbenzylated polyphenylene oxide, for example, the polyphenylene oxide having a reduced molecular weight can be reacted with halogenated methylstyrene in the presence of an alkali metal hydroxide.

  More specifically, ethenyl benzylation is performed by dissolving polyphenylene oxide having a phenol group at the terminal and halogenated methylstyrene in an organic solvent such as toluene and dropping an aqueous solution of an alkali metal hydroxide into this solution. be able to. At this time, the alkali metal hydroxide functions as a dehydrohalogenating agent (for example, a dehydrochlorinating agent), and the alkali metal hydroxide desorbs the hydrogen halide from the phenol group and halogenated methylstyrene, The structure represented by the general formula (2) is bonded to O instead of H of the phenol group (—OH) at the terminal of the polyphenylene oxide. In addition, it is preferable that reaction temperature is 30-100 degreeC and reaction time is 0.5 to 20 hours.

  Examples of the halogenated methylstyrene include p-chloromethylstyrene, m-chloromethylstyrene, a mixture of p-chloromethylstyrene and m-chloromethylstyrene, p-bromomethylstyrene, m-bromomethylstyrene, A mixture of p-bromomethylstyrene and m-bromomethylstyrene or the like can be used. In particular, the halogenated methylstyrene is preferably at least one selected from the group consisting of p-chloromethylstyrene and m-chloromethylstyrene. When such a halogenated methylstyrene is used, the structure represented by the general formula (2) becomes at least one selected from the group consisting of a p-ethenylbenzyl group and an m-ethenylbenzyl group, and polyphenylene oxide The melting point and softening point of can be arbitrarily changed. For example, when p-chloromethylstyrene is used, the symmetry becomes good and a polyphenylene oxide having a high melting point and a high softening point can be obtained. Also, a mixture of p-chloromethylstyrene and m-chloromethylstyrene is used. When used, a polyphenylene oxide having a low melting point and a low softening point can be obtained, and workability during molding is improved.

  The alkali metal hydroxide is not particularly limited, and for example, potassium hydroxide, sodium hydroxide, a mixture thereof, and the like can be used. In addition, it is preferable that the mixture ratio of an alkali metal hydroxide is about 1.1-2.0 times mole with respect to 1 mol of phenol groups.

  In carrying out ethenyl benzylation, a phase transfer catalyst may be used. The phase transfer catalyst has a function of incorporating an alkali metal hydroxide and is soluble in both a phase composed of a polar solvent such as water and a phase composed of a nonpolar solvent such as an organic solvent. It is a catalyst that can move. In the case of not using a phase transfer catalyst, it is difficult to solubilize only alkali metal hydroxide in a nonpolar solvent. Therefore, hydrogen halide from polyphenylene oxide and halogenated methylstyrene dissolved in the nonpolar solvent. It may take a long time to desorb. However, in the presence of the phase transfer catalyst, the alkali metal hydroxide dissolved in the polar solvent is taken into the phase transfer catalyst and then transferred into the nonpolar solvent by the phase transfer catalyst. Hydroxides can be easily solubilized in nonpolar solvents, and ethenylbenzylation can be promoted. The phase transfer catalyst is not particularly limited, and for example, a quaternary ammonium salt such as tetra-n-butylammonium bromide can be used. In the presence of a phase transfer catalyst, the ethenyl benzylation reaction is preferably performed at a temperature of 100 ° C. or lower.

  By the method described above, a polyphenylene oxide having at least one structure (substantially upper limit of 4) represented by the general formula (2) at the molecular end can be produced.

  When the component having an unsaturated double bond of the present invention is the ethenylbenzylated polyphenylene oxide resin, the content of the ethenylbenzylated polyphenylene oxide resin in the total amount of the resin component is 20 to 80% by mass, 30 to 70% by mass is preferable. When the ratio is more than 80% by mass, the resin composition has a high viscosity and may cause voids or blurring at the time of molding. When the ratio is less than 20% by mass, a cured product is obtained. Tend to be brittle.

  On the other hand, a polyphenylene oxide resin composition containing a crosslinkable resin such as the triallyl isocyanurate resin can also be used as a polyphenylene oxide resin composition containing a component having an unsaturated double bond.

  Examples of the crosslinkable resin include triallyl isocyanurate (TAIC), triallyl cyanurate, diallyl phthalate, diallyl isophthalate, diallyl maleate, diallyl fumarate, diethylene glycol diallyl carbonate, triallyl phosphate, ethylene glycol diallyl ether, triaryl ether Resins such as allyl ether of methylolpropane, partially allyl ether of pentaerythritol, diallyl sebacate, allylated novolak, allylated resole resin are used. Among these, TAIC is preferable because the dielectric loss tangent that affects the variation in transmission time can be lowered.

  As a content rate of TAIC in the resin component whole quantity in case the component which has an unsaturated double bond of this invention is TAIC, it is preferable that it is 20-70 mass%, Furthermore, it is preferable that it is 20-55 mass%. When the ratio exceeds 70% by mass, the viscosity of the resin composition is high, and there is a risk of forming voids or blurring during molding. When the ratio is less than 20% by mass, the cured product tends to be brittle. There is.

  In addition, as a component which has an unsaturated double bond of this invention, you may use together and use ethenyl benzylation polyphenylene oxide resin and TAIC.

  In addition, the polyphenylene oxide resin composition in the present invention may contain other resin components such as an epoxy resin other than the resin component, and additives such as inorganic fillers, compatibilizers, and flame retardants. However, when a component having a high dielectric constant is introduced, the dielectric constant of the cured product of the polyphenylene oxide resin composition also increases. Therefore, it is desirable to select and blend a component having a low dielectric constant.

  Specific examples of the inorganic filler include various metal oxides such as silica, boron nitride, wollastonite, talc, kaolin, clay, mica, alumina, zirconia, and titania, nitrides, silicides, borides, and the like. These may be used alone or in combination of two or more.

  Among these, in order to adjust the dielectric constant of the polyphenylene oxide resin composition to 3.5 or less, it is preferable to use a low dielectric constant filler such as silica or boron nitride.

The blending ratio of the inorganic filler is preferably 5 to 50% by mass in the cured product of the polyphenylene oxide resin composition from the balance of various properties such as moldability and dielectric properties.

  The compatibilizing agent is blended to improve heat resistance, adhesion, and dimensional stability. For example, styrene / butadiene block copolymer, styrene / isoprene block copolymer, 1,2-polybutadiene, 1,4- At least one compatibilizing agent selected from the group consisting of polybutadiene, maleic modified polybutadiene, acrylic modified polybutadiene, and epoxy modified polybutadiene can be blended. The content of the compatibilizer is preferably 10% by mass or less in the resin component.

  Moreover, it is preferable to use a halogen compound as the flame retardant. As this halogen compound, for example, halogenated polyphenylene oxide, halogenated triallyl isocyanurate, fluorinated aliphatic resin, etc. can be blended. In this case, the flame retardancy is improved and the dielectric constant is sufficiently reduced. can do. The halogenated polyphenylene oxide is blended as a part or all of the polyphenylene oxide resin of the cured product of the polyphenylene oxide resin composition. In particular, when a brominated polyphenylene oxide is added, flame retardancy can be obtained even with a small amount of added halogen, and the dielectric constant can be sufficiently reduced.

  Furthermore, the halogenated triallyl isocyanurate is blended as part or all of the triallyl isocyanurate of the polyphenylene oxide resin composition. When brominated triallyl isocyanurate is blended as the halogenated triallyl isocyanurate, flame retardancy can be obtained even with a small amount of added halogen, and the dielectric constant can be sufficiently reduced.

  When a fluorinated aliphatic resin is blended, particularly preferred are tetrafluoroethylene resin, tetrafluoroethylene hexafluoropropylene copolymer resin, tetrafluoroethylene-perfluoroalkyl vinyl ether, tetrafluoroethylene-ethylene. It is preferable to use at least one of copolymer resins, and these have a particularly low dielectric constant even in organic compounds, and greatly contribute to the reduction of the dielectric constant of the polyphenylene oxide resin composition.

  These flame retardants are preferably blended so that the halogen content in the solid content of the polyphenylene oxide resin composition is 8 to 40% by mass in the cured product.

  In addition, the polyphenylene oxide resin composition in the present invention is mixed with an organic solvent as necessary to prepare a varnish for use. The organic solvent is not particularly limited as long as it does not dissolve the resin component and adversely affects the reaction. For example, ketones such as methyl ethyl ketone, ethers such as dibutyl ether, esters such as ethyl acetate, Examples thereof include amides such as dimethylformamide, aromatic hydrocarbons such as benzene, toluene, and xylene, and organic solvents such as chlorinated hydrocarbons such as trichloroethylene. These may be used alone or in combination of two or more.

  The concentration of the resin solid content of the varnish may be appropriately adjusted according to the workability when the resin-coated copper foil of the present invention is produced. For example, 40 to 90% by mass is appropriate.

  And the dielectric constant of the hardened | cured material of the polyphenylene oxide resin composition in this invention is 3.5 or less.

  When the dielectric constant exceeds 3.5, the transmission loss of an electric signal increases in a high frequency region, which is not preferable for the use of the present invention. The lower the dielectric constant, the lower limit is not particularly limited.

  Next, the copper foil used in the present invention will be described.

  The surface roughness on the side where the resin layer of the copper foil used in the present invention is formed is 0.5 to 2 μm. In high frequency applications, there is a case where the phenomenon called skin effect concentrates on the surface layer of the conductor, but when the surface shape of the copper foil exceeds 2 μm, the current flows along the surface layer, causing signal delay and transmission. Loss may increase, and if it is less than 0.5 μm, adhesion to the resin layer formed may be reduced.

  Moreover, the copper foil in the present invention includes a metal treatment layer, specifically, a zinc layer, a zinc alloy layer, a nickel layer, and a nickel alloy layer on at least the side of the copper foil on which the resin layer is formed. It is preferably one or more layers selected from the group consisting of a metal-treated layer having the above-mentioned metal content and, if necessary, the surface of the metal-treated layer further subjected to chromate treatment.

  As the method for forming the metal treatment layer and the method for chromate treatment, for example, the method described in JP-A-60-86894 can be employed.

  Examples of the zinc alloy for forming the zinc alloy layer include Zn—W, Zn—V, Zn—Tl, Zn—Sn, Zn—Se, Zn—Sb, Zn—Pt, Zn—Pb, and Zn—. Ni, Zn-Mo, Zn-Mn, Zn-In, Zn-Fe, Zn-Ge, Zn-Ga, Zn-Cu, Zn-Cr, Zn-Co, Zn-Cd, Zn-Au, Zn-Ag, etc. Can be mentioned. Of these, Zn-Cu is preferable.

  Examples of the nickel alloy for forming the nickel alloy layer include Ni-P, Ni-W, Ni-Co, Ni-Mo, Ni-Pd, Ni-Sn, Ni-Zn, Ni-Cu, Ni-Mn, Ni-Fe, Ni-Mn-Zn, etc. can be mentioned. Of these, Ni-P is preferred.

  The thickness of the metal treatment layer thus formed is preferably 0.0005 to 0.002 μm.

  The chromate treatment refers to a treatment in which chromium oxide and its hydrate, or a mixture of zinc or its oxide and chromium oxide and its hydrate are attached to the surface of the metal treatment layer.

  The copper foil in the present invention is further coated with a silane coupling agent on the formed metal treatment layer. The application of the silane coupling agent can be performed by applying an aqueous solution of the silane coupling agent on the surface of the copper foil, attaching the solution, and drying.

  As the silane coupling agent treatment, a vinyl group-containing silane coupling agent such as vinyltrimethoxysilane is preferably used.

  Moreover, it is preferable to use 0.001-5 mass% aqueous solution as said silane coupling agent aqueous solution. When the concentration of the silane coupling agent in this aqueous solution is less than 0.001% by mass, the effect of the silane coupling agent cannot be expected, and when it exceeds 5% by mass, the silane coupling agent is dissolved. There is a tendency that the improvement of the corresponding effect is not expected.

  When the resin layer formed from the polyphenylene oxide resin composition is laminated on the surface of the copper foil subjected to the surface treatment as described above, the unsaturated double bond in the polyphenylene oxide resin composition contains a vinyl group. Bonding with a silane coupling agent provides a high adhesive strength, and zinc or a zinc alloy is used in the bonding reaction between a silane coupling agent and a copper foil, and the double bonding in the silane coupling agent and the polyphenylene oxide resin composition. It acts catalytically in the bonding reaction with the bond and contributes to improved adhesion between the copper foil and the polyphenylene oxide resin composition.

And in this invention, the amount of zinc adhering to the surface of the said copper foil by the said metal treatment and a silane coupling agent process is 1-2 mg / dm < ² >, nickel amount 0.1-0.3 mg / dm < ² >, and silicon the amount is adjusted to 0.005-0.05 / dm ^2.

Zinc content of the surface is 1-2 mg / dm ^2, when the zinc content is less than 1 mg / dm ^2, the adhesive strength is lowered at the time of heating, such as a reflow soldering process, it becomes greater than 2 mg / dm ² In addition, since zinc is eroded by acid, deterioration of adhesive strength due to acid treatment during circuit formation becomes high.

Further, the nickel amount on the surface is 0.1 to 0.3 mg / dm ² , and if the nickel amount is smaller than 0.1 mg / dm ² , the adhesive strength decreases when the reflow soldering process or the like is at a high temperature, and 0 When it exceeds 3 mg / dm ² , the low transmission loss is reduced.

Furthermore, the chromium amount of the surface by the chromate treatment is preferably in the range of 0.05-0.15 mg / dm ^2. Since chromium has a relatively high resistance value, low transmission loss is reduced when the amount of chromium is too large. However, the above range is preferable because of the effect of preventing rust and discoloration of the copper foil.

On the other hand, the treatment amount of the silane coupling agent by applying the silane coupling agent of the copper foil is applied so that the silicon amount is 0.005 to 0.05 mg / dm ² . If the silicon content is less than 0.005 mg / dm ² , the adhesive strength between the copper foil and the resin layer to be formed cannot be increased, and if it is greater than 0.05 mg / dm ² , There is a high possibility that the silicon component adhering at the time of loading and winding adheres and transfers to the surface on which the resin layer of the copper foil is not formed, thereby causing circuit formation failure.

  Moreover, as said silicon amount, it is preferable that the ratio of the number of atoms of a place with little adhesion amount and a place with many is 6 times or less. If the ratio exceeds 6 times, the difference in the number of atoms present is too high. If there is a large difference in the amount of Si attached from a microscopic viewpoint, the adhesive strength between the copper foil and the resin layer is low and high. A location will exist and copper foil adhesive strength will become low. Moreover, since it is easy to be eroded by an acid in the location where adhesion | attachment of copper foil and a resin layer is low, and an acid deterioration rate becomes high, it is preferable that it is 1-6 times as Si atom number ratio.

  The copper foil with resin of the present invention is prepared by applying a varnish-prepared polyphenylene oxide resin composition varnish to the surface of the copper foil that has been surface-treated, and semi-curing by heating and drying as necessary. Alternatively, a substrate obtained by impregnating a polyphenylene oxide resin composition into a base material as described below is used as a resin layer, and copper foil is laminated on both sides or one side of the prepreg to produce a printed wiring board. It is produced as a laminated body for use.

  As the substrate, organic fiber or glass fiber woven or non-woven fabric can be used. The amount of impregnation into the base material is preferably such that the mass ratio of the resin solid content in the prepreg is 35% by mass or more. In general, the dielectric constant of the substrate is larger than that of the resin. Therefore, in order to reduce the dielectric constant of the resin-coated copper foil obtained using this prepreg, the content of the resin solid content in the prepreg is set to the mass ratio. More is better.

  Next, the multilayer printed wiring board obtained using the laminated foil for resin-coated copper foil and / or printed wiring board of the present invention will be described.

  In the first example, a printed wiring board can be obtained by forming a circuit pattern on one side or both sides of the laminated body for manufacturing a printed wiring board by etching the copper foil of the laminated body for manufacturing a printed wiring board. . At this time, the hardened | cured material of the prepreg which is a resin layer forms an insulating layer, and copper foil comprises a conductor layer.

  In the second example, as in the first example, a circuit pattern is formed on one or both sides of the laminate for manufacturing a printed wiring board as an inner layer material, and the laminate is used on one side or both sides of the laminate. One or a plurality of prepregs similar to those are stacked, and if necessary, the outermost layer is laminated with a copper foil that has been subjected to the surface treatment as described above, and laminated and integrated by heat and pressure molding, A multilayer printed wiring board can be obtained. At this time, the cured product of the prepreg which is a resin layer in the laminate for manufacturing a printed wiring board and the cured product of the prepreg disposed on the outer surface of the laminate for manufacturing a printed wiring board form an insulating layer, and the copper foil constitutes a conductor layer To do.

  In the third example, an inner layer material is formed by forming a circuit pattern on one or both sides of the laminate for manufacturing a printed wiring board as in the first example, and a resin-coated copper foil is provided on one or both sides of the laminate. A multilayer printed wiring board can be obtained by stacking layers so as to face the surface of the inner layer material and stacking and integrating them by heat and pressure molding. At this time, the cured product of the prepreg which is the resin layer in the laminate and the cured product of the resin layer in the copper foil with resin form an insulating layer, and the copper foil constitutes the conductor layer.

The molding conditions of the laminate for manufacturing a printed wiring board or the multilayer printed wiring board described above are conditions according to the blending composition of the polyphenylene oxide resin composition, and are not particularly limited. It is preferable to heat and press for an appropriate time under the conditions of not more than ° C. and a pressure of 0.98 MPa (10 kg / cm ² ) or more and 5.9 MPa (60 kg / cm ² ) or less.

  Since the laminate for manufacturing a printed wiring board or the multilayer printed wiring board obtained as described above uses a surface-treated copper foil, it is composed of an insulating layer formed from a resin layer and a copper foil. Adhesive strength with the conductor layer is increased, and sufficient adhesive strength can be obtained even when a copper foil with low surface roughness and low transmission loss is used in high frequency applications.

  In particular, the adhesiveness is not lost even during heat such as a reflow soldering process.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the examples.

The raw materials used in this example are shown below.
High molecular weight polyphenylene ether: polyphenylene ether having a number average molecular weight of 14,000
(Made by Nippon GE Plastics Co., Ltd.
“Noryl PX9701”)
Phenol species: Bisphenol A
Decomposed peroxide: t-butylperoxyisopropyl monocarbonate
("Perbutyl I" manufactured by NOF Corporation)
Cobalt naphthenate solution: 8% solution initiator dissolved in toluene: Di (t-butylperoxyisopropyl) benzene
("Perbutyl P" manufactured by Nippon Oil & Fats Co., Ltd.)
Glass cloth: “WEA116E” manufactured by Nitto Boseki Co., Ltd.
Inorganic filler: Silica-based filler manufactured by Denki Kagaku Kogyo Co., Ltd., FB3SDC (trade name)
Flame retardant: Brobe flame retardant manufactured by Albemarle Asano Co., Ltd., SAYTEX 8010 (trade name)
Silane coupling agent: Vinyltrimethoxysilane ("SZ6300" manufactured by Dow Corning Toray Silicone Co., Ltd.)

First, a method for reducing the molecular weight of a polyphenylene ether resin will be described.
(Low molecular weight high molecular weight polyphenylene ether resin)
200 g of toluene was placed in a 2000 ml flask equipped with a stirrer and a stirring blade. While controlling the flask at an internal temperature of 80 ° C., 100 g of high molecular weight polyphenylene ether and 4.3 g of bisphenol A were added with 2.94 g of perbutyl I and 0.0042 g of cobalt naphthenate solution until the high molecular weight polyphenylene ether was completely dissolved. A low molecular weight polyphenylene ether (PPE-1) was prepared by stirring.

  On the other hand, a low molecular weight polyphenylene ether (PPE-2) was prepared by the same method except that the formulation shown in Table 1 was used in the preparation of PPE-1.

  The obtained low molecular weight polyphenylene ether (PPE-1, PPE-2) was reprecipitated with a large amount of methanol to remove impurities and dried under reduced pressure at 80 ° C./3 hours to completely remove toluene. The number average molecular weight of the obtained polyphenylene ether compound was about 2400 for PPE-1 and about 9000 for PPE-2. The number average molecular weight was measured by gel permeation chromatograph (GPC).

  Next, a method for ethenylbenzylation of low molecular weight PPE-1 is shown below.

(Ethenylbenzylation of PPE-1)
In a 500 liter three-necked flask equipped with a temperature controller, a stirrer, a cooling device and a dropping funnel, 100 g of low molecular weight PPE-1, 7.3 g of chloromethylstyrene, 0.41 g of tetra-n-butylammonium bromide, 200 g of toluene was charged, dissolved by stirring, the liquid temperature was adjusted to 75 ° C., an aqueous sodium hydroxide solution (5.5 g of sodium hydroxide / 5.5 g of water) was added dropwise over 20 minutes, and stirring was further continued at 75 ° C. for 4 hours. . Next, after neutralizing the contents of the flask with a 10% aqueous hydrochloric acid solution, a large amount of methanol was added to obtain ethenylbenzylated polyphenylene ether as a precipitate. The precipitate filtrate is washed three times with a mixture of methanol 80 and water 20 and then treated under reduced pressure at 80 ° C. for 3 hours to remove ethenylbenzylated polyphenylene ether from which solvent and water have been removed. I took it out. This is referred to as “modified PPE-1”.

  Next, a varnish of a polyphenylene ether resin composition was prepared using the modified PPE-1 and PPE-2.

(Preparation of varnish of polyphenylene ether resin composition)
After adding modified PPE-1 and / or PPE-2 in 100 parts by mass of toluene controlled at 80 ° C. and stirring for 30 minutes at 80 ° C. to dissolve, further TAIC and A peroxide was added to obtain a resin varnish.

  Let the obtained resin varnish be the resin varnish A, the resin varnish B, the resin varnish C, and the resin varnish D, respectively.

<Example 1>
Resin varnish A was used as a resin component, and the resin varnish, inorganic filler, and flame retardant were stirred and mixed with a homodisper at a blending ratio shown in Table 3 to obtain a varnish of a polyphenylene ether resin composition.

  A glass cloth was impregnated with the varnish of the obtained polyphenylene ether resin composition, and then heated and dried at 120 ° C. for 5 minutes to obtain a prepreg. Next, only the polyphenylene ether resin composition component adhering to the glass cloth from the prepreg was collected as a resin composition powder.

  And the powder of the said polyphenylene ether resin composition was filled into the 100 mm x 100 mm mold, and it heat-pressed on 200 degreeC, 3.0 Mpa, and the molding conditions for 180 minutes, and obtained the hardened | cured material of the polyphenylene ether resin composition.

  After the obtained cured product was cut into 86 mm × 86 mm, the dielectric constant at 1 GHz was measured based on JIS C 6481. As a result, it was 2.7.

Next, using the obtained prepreg, the laminated body for producing a printed wiring board in which a 35 μm-thick copper foil having a surface roughness and a metal adhesion amount shown in Table 3 is stretched on both sides is passed through the prepreg. By arranging a copper foil with a thickness of 35 μm which is the surface roughness and metal adhesion amount described in Table 3, by heating and pressurizing under the molding conditions of temperature 200 ° C., pressure 3.0 MPa (30 kg / cm ² ), 180 minutes, The multilayer printed wiring board which is a double-sided copper clad laminated body was obtained.

  The surface roughness of the copper foil is indicated by the Rz value measured by the measuring method specified in JIS B 0601. The metal adhesion amount is the fluorescent X-ray method, and the silicon amount is the atomic amount. The number ratio is a value measured by Auger electron spectroscopy (AES method).

And various characteristics were evaluated with the following evaluation methods using the obtained multilayer printed wiring board.
(Peel strength)
The copper foil peeling strength on the surface of the multilayer printed wiring board was measured according to JIS C 6481. At this time, a pattern having a width of 10 mm and a length of 100 mm was formed on a test piece having a width of 20 mm and a length of 100 mm, and the copper foil was peeled off at a rate of 50 mm / min with a tensile tester, and the peeling strength at that time was measured. .
(Oven heat resistance)
Each multilayer printed wiring board cut to 50 × 50 (mm) was held in an oven set at 230 to 280 ° C. for 1 hour, and the lowest temperature at which the surface was swollen at that time was specified.
(Evaluation of acid degradation resistance)
A pattern having a width of 1 mm and a length of 100 mm was formed on the surface of the multilayer printed wiring board. In this state, the peel strength of the copper foil was measured in the same manner as in the above-described peel strength evaluation. Similarly, the laminate having the pattern formed thereon was subjected to hydrochloric acid treatment in which it was immersed in a 12% hydrochloric acid aqueous solution for 30 minutes, and then the peel strength was measured. The deterioration rate of the peel strength before and after the hydrochloric acid treatment was expressed as a percentage.
(Transmission loss evaluation)
Ten linear circuits having a width of 50 μm and a length of 300 mm were formed by etching on one side of a 420 mm × 500 mm multilayer printed wiring board at intervals of 40 mm in the vertical direction.

After the circuit is formed, the same copper foil as that used for the prepreg and the double-sided board is superimposed on the circuit forming surface, and heat-press molding is performed under the same conditions as in the production of the printed wiring board, and a split line is provided. A multilayer printed wiring board was obtained. A 1.6 GHz signal was applied to the inner layer circuit of the multilayer printed wiring board, and the transmission loss was measured.
(Circuit formation characteristics)
Ten strip lines having a width of 100 μm and a length of 500 mm were formed on a 340 × 510 mm multilayer printed wiring board at intervals of 25 mm.

<Examples 2-12 and Comparative Examples 1-5>
A prepreg and a laminate were obtained in the same manner as in Example 1 except that the varnish of the polyphenylene ether resin composition was obtained at the blending ratios in Tables 3 and 4 and the copper foils with the metal adhesion amounts shown in Tables 3 and 4 were used. Were made and evaluated.

  The results are shown in Tables 3 and 4.

  Comparison between Examples 1 and 2 shows that the smaller the roughness, the better the transmission characteristics. In addition, when the amount of Si is large as in Example 3, the peel strength and acid deterioration rate are good even when compared with other examples, but even if the Si amount is increased to the amount of Comparative Example 1, it is compared with Example 3. Thus, there is no significant improvement in peel strength, and there is a difficulty in circuit formation that seems to be due to the transfer of the S surface of the coupling agent. Further, when the Si amount is 0 as in Comparative Example 2, the peel strength is considerably low, and the effect of the coupling treatment can be seen.

In conclusion, when the Si adhesion amount is less than 0.005 mg / dm ² , the adhesion between the copper foil and the resin layer cannot be sufficiently obtained, and as the Si adhesion amount increases, the adhesion strength with the resin layer increases, but 0.05 mg / dm 2 ^When the amount exceeds ² , there is no significant improvement in adhesion strength, and during the copper foil manufacturing process, when loading and winding the copper foil, the deposited Si is transferred to the side where the copper foil resin layer is not formed, Since there is a possibility of causing poor formation, 0.05 mg / dm ² is the upper limit.

  In addition, when Examples 1 and 10 are compared, Example 1 having a smaller variation in the Si atom number ratio is superior in peel strength and acid deterioration resistance. This is because the difference in the number ratio of atoms is high, that is, if there is a difference in Si adhesion amount from a microscopic viewpoint, there are places where the adhesion strength between the copper foil and the resin layer is low and high, and the copper foil adhesion strength of the laminated board As it becomes low. Moreover, since it is easy to be eroded by an acid in the location where the adhesiveness of copper foil and a resin layer is low, and an acid deterioration rate becomes high, it is preferable that it is the range of 1-6 as Si atom number ratio.

On the other hand, when Examples 1, 4, 11 and Comparative Examples 3 and 4 are compared, if the amount of Zn is large, the oven heat resistance is good, but the acid deterioration rate deteriorates, so the Zn amount is 1 to ² mg / dm ^2. is necessary.

Further, when Examples 1, 5, 12 and Comparative Example 5 are compared, if the amount of Ni is large, the oven heat resistance is slightly improved, but the transmission characteristics are deteriorated. Although it is preferable that the amount of Ni is small for transmission characteristics, it is necessary to contain 0.1 to 0.3 mg / dm ^{2 in} order to obtain a transverse stripe prevention effect in the copper foil manufacturing process.

Further, from Comparative Example 5 as well as Ni, Cr has high resistance and low transmission characteristics. Therefore, it is preferable that the amount is small. However, in order to prevent discoloration and rusting of the copper foil, 0.05 to 0. It is preferably 15 mg / dm ² .

Examples 1, 6, 7, 8, and 9 show comparisons between the resin dielectric constant and the resin composition, and it can be seen that there is a correlation between the dielectric constant and the transmission characteristics. Although the peel strength slightly changes depending on the resin blending, this blending range is an acceptable range. For example, the peel strength of Example 8 is slightly weaker than that of Examples 1 and 9, but the peel strength can be improved by slightly increasing the Si amount from 0.005 mg / dm ^{2 of the} Example.

Claims (8)

Resin-coated copper foil comprising a resin layer containing a polyphenylene oxide resin composition containing a component having an unsaturated double bond and a dielectric constant of the cured product of 3.5 or less, and a copper foil. In
The surface roughness of the copper foil on which the resin layer is formed is 0.5 to 2 μm, and the surface is coated with a silane coupling agent after the metal treatment layer is formed,
Resin coated copper, wherein the amount of zinc in the surface 1-2 mg / dm ^2, the amount of nickel 0.1 to 0.3 mg / dm ² and a silicon amount is 0.005-0.05 / dm ² Foil. ^{2. The} copper foil with resin according to claim 1, wherein an amount of chromium on the surface is 0.05 to 0.15 mg / dm ² .   3. The resin-attached copper foil according to claim 1, wherein in the amount of silicon on the surface, the ratio of the number of atoms with a small amount of adhesion and a large number of atoms is 1 to 6 times.   The polyphenylene oxide resin is contained in 20 to 80% by mass of polyphenylene oxide resin and 20 to 70% by mass of triallyl isocyanurate resin in the total amount of the resin component of the polyphenylene oxide resin composition. The copper foil with resin of description.   The copper foil with resin of any one of Claims 1-4 which contains 20-80 mass% of polyphenylene oxide resin ethenyl benzylated in the resin component whole quantity of the said polyphenylene oxide resin.   The resin-coated copper foil according to claim 1, wherein the silane coupling agent is vinyl silane. In the laminated body for printed wiring board manufacture using the copper foil with resin of any one of Claims 1-6,
Using the prepreg obtained by impregnating the polyphenylene oxide resin composition into the base material as the resin layer and semi-curing by heating and drying, the copper foil is laminated on both sides or one side of the prepreg and obtained by heating and pressing. Printed circuit board manufacturing laminate.   A multilayer printed wiring board obtained by using the resin-coated copper foil according to any one of claims 1 to 6 and / or the laminate for producing a printed wiring board according to claim 7.