JP2002232138A - Manufacturing method of multilayer circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the manufacturing method of a multilayer circuit board that has high adhesion property between an electrical insulating layer and a conductor layer, and improved patterning properties. SOLUTION: In the manufacturing method of the multilayer circuit board, the surface of the electrical insulating layer, where a curing resin composition containing an alicyclic olefin polymer or aromatic series polyether polymer is cured is heated to 50-250 deg. for retaining the temperature and brought into contact with plasma, then is subjected to dry plating, and then wet plating or dry plating, thus forming the conductor layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a multilayer circuit board, and more particularly, to a method for manufacturing a multilayer circuit board having high adhesion between an electrical insulating layer and a conductor layer and excellent patterning properties. .

[0002]

2. Description of the Related Art As electronic devices have become smaller and more multifunctional,
Circuit boards used in electronic devices have also been required to have higher densities. As a general method of increasing the density of a circuit board, it is well known that the circuit board is multilayered. The multilayer circuit board usually has an electric insulating layer (1).
An electric insulating layer (2) is laminated on an inner layer substrate comprising a conductive circuit (1) formed on the surface thereof, and a conductive circuit (2) is formed on the electric insulating layer (2). By doing so, it can be obtained by further laminating an electric insulating layer and a conductor circuit in a plurality of stages as necessary. The conductor circuit in the multilayer circuit board is coated with a conductor such as copper on the entire surface of the electrical insulating layer by wet plating, dry plating, etc., and if necessary, the desired circuit pattern using a resist etc. Are formed by etching so as to form.

It is well known that the surface roughness of an electric insulating layer is increased in order to increase the adhesion between the electric insulating layer and a conductor layer formed by plating. However, a conductor layer provided on an electric insulating layer having a large surface roughness has poor patterning properties. For this reason, desired impedance and conductance cannot be obtained, and noise can be easily picked up. On the other hand, when the surface roughness is reduced, the adhesion between the electric insulating layer and the conductor layer is reduced. In order to increase the adhesion between the electric insulating layer and the conductor layer, it is known that the electric insulating layer made of a polymer material is subjected to a surface etching treatment with plasma (Japanese Patent Application Laid-Open No. Hei 6 (1994) -176).
-69644). Plasma surface treatment of plastic is performed at a low temperature ("Plastic Processing Technology Handbook", edited by The Society of Polymer Science, P1167-). However, since the conductor layers have become finer with the increase in the density of circuit boards, the adhesion may be insufficient even at low-temperature plasma treatment.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a multilayer circuit board having high adhesion between an electric insulating layer and a conductive layer and excellent in patternability. The present inventor has conducted intensive studies to achieve the above object,
An electric insulating layer made of a polymer material is coated at a surface temperature of 50 to 250.
It has been found that the above object can be achieved by performing a plasma treatment at a temperature of ° C. and then forming a conductor layer on the surface, and the present invention has been completed based on this finding.

[0005]

According to the present invention, (1) the electric insulating layer made of a polymer material has a surface temperature of 5.
There is provided a method for producing a multilayer circuit board, comprising contacting with a plasma at 0 to 250 ° C., and then forming a conductor layer on the surface. In a preferred embodiment, (2) the polymer material is an alicyclic olefin A production method comprising curing a curable resin composition containing a polymer or an aromatic polyether polymer, (3) a production method comprising forming a conductor layer by a method including dry plating, (4) A manufacturing method including forming a conductor layer by dry plating and then wet plating or dry plating, and (5) forming a conductor layer by repeating dry plating a plurality of times and then wet plating. There is provided a manufacturing method comprising:

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The method for manufacturing a multilayer circuit board according to the present invention comprises contacting an electrical insulating layer made of a polymer material with plasma at a specific surface temperature, and then forming a conductor layer on the surface. . In the manufacturing method of the present invention, the electric insulating layer is brought into contact with plasma. Plasma refers to a state in which atoms forming molecules are ionized and separated into positively charged ions and electrons.For example, arc discharge in a gas,
It is obtained by performing glow discharge, corona discharge, and the like.

[0007] The plasma is the gas between the electrodes of the arc discharge;
Light emitting portion in discharge tube; highly ionized gas such as corona. As a gas for generating plasma, neon, argon, krypton, xenon, hydrogen, oxygen, nitrogen, carbon tetrafluoride, trifluoromethane, carbon tetrachloride,
Ammonia and the like. In the production method of the present invention,
The lower limit of the electric insulating layer surface temperature during the plasma treatment is 50 ° C.
Preferably at 100 ° C. with an upper limit of 250 ° C., preferably 1
Bring to 80 ° C. By setting the temperature in this range, the adhesion between the electric insulating layer and the conductor layer is significantly increased. The method for setting the surface temperature of the electric insulating layer to the above range is not particularly limited,
For example, heating is performed using an external heater or the like. The plasma processing time is not particularly limited, but is usually 1 second to 30 minutes, preferably 10 seconds to 15 minutes. The conditions for generating the plasma are not particularly limited, but the output of the high-frequency power supply is usually 50 to 200 W, preferably 100 to 150 W, and the partial pressure of the gas for generating the plasma is usually 0.
The pressure is preferably set to 01 to 2000 Pa, more preferably 0.1 to 500 Pa, particularly preferably 0.3 to 100 Pa. The frequency of the high frequency power supply for generating plasma is not particularly limited, but 13.56 MHz is often used, and this frequency is also awarded in the present invention.

In the manufacturing method of the present invention, the surface of the electric insulating layer can be brought into contact with a permanganate before the surface treatment with high-temperature plasma in order to further improve the adhesion. Examples of the permanganate include alkali metal salts such as potassium permanganate and sodium permanganate. The permanganate is usually brought into contact with the surface of the electrical insulating layer in an aqueous solution. The concentration of the aqueous solution of permanganate is usually 0.001 to 5 mol /
1, 0.005 to 3 mol / l. The temperature of the aqueous solution when the permanganate is brought into contact with the electrical insulating layer is usually 1
It is 0-100 degreeC, Preferably it is 40-90 degreeC. The contact time is usually 0.1 to 120 minutes, preferably 1 to 60 minutes. The method of contacting with the permanganate is not particularly limited, and examples thereof include a brush coating method, a dipping method, and a spray method.

In the manufacturing method of the present invention, after the surface of the electric insulating layer is brought into contact with plasma, a conductor layer is formed on the surface of the electric insulating layer. The conductor layer can be formed by dry plating or wet plating. In a preferred manufacturing method of the present invention, the conductor layer is formed by a method including dry plating. Dry plating includes physical vapor deposition (PVD) such as vacuum deposition, ion plating, sputtering, molecular beam epitaxy, ion implantation, and ion beam mixing; and chemical vapor deposition such as thermal CVD, plasma CVD, and optical CVD. Of these, physical vapor deposition, particularly sputtering, is preferred. The basic structure of sputtering is that a base material (a substance that forms the conductor layer) called a target is connected to a high-frequency power source by direct current or capacitive coupling in a vacuum chamber such as a discharge tube to form a cathode, which is then connected to a conductor. An electric insulating layer on which the layer is deposited is placed opposite to the base material, and the base material is deposited on the electric insulating layer in a thin film form. Examples of the sputtering method include direct current bipolar sputtering, high frequency sputtering, magnetron sputtering, facing target sputtering, ECR sputtering, bias sputtering, plasma controlled sputtering, and multi-target sputtering. Of these, DC bipolar sputtering or high-frequency sputtering is preferred.

Examples of the conductive layer formed by dry plating include those formed of a conductive metal such as nickel, copper, aluminum, gold, silver, chromium, a nickel-chromium alloy, and a nickel-chromium-copper alloy. Can be Dry plating is performed once or a plurality of times. When dry plating is performed a plurality of times in order to obtain a conductor layer having the same film thickness, the adhesion between the conductor layer and the electrical insulating layer is lower than when dry plating is performed once. Get higher. When dry plating is performed a plurality of times, the same conductor may be used each time, but it is preferable to dry-plate different conductors in order to prevent migration of the conductor and improve adhesion. When different conductors are dry-plated in a plurality of times, in the first dry-plating, any one of nickel, chromium, nickel-chromium alloy or nickel-chromium-copper alloy is used, and the subsequent dry plating is performed. It is preferable to use copper for plating. The total thickness of the conductor layer formed by dry plating is usually 0.01 to 50 μm, preferably 0.05 to 20 μm, more preferably 0.2 to 10 μm.
It is.

Although the conductor layer may be obtained only by dry plating, in the preferred manufacturing method of the present invention, dry plating and then wet plating are performed to improve the adhesion between the conductor layer and the electric insulating layer. Preferred to increase. Examples of wet plating include electroplating, electroless plating, and hot-dip plating. By wet plating, an additional conductor layer is deposited on the conductor layer obtained by dry plating. Examples of the conductor layer formed by wet plating include those formed of a metal such as nickel, copper, aluminum, gold, silver, and chromium. The thickness of the conductor layer formed by wet plating is usually 5 to 50 μm, preferably 10 to 40 μm. The thickness of the conductor layer formed by dry plating with respect to the thickness of the conductor layer formed by wet plating is usually 0.01 to 50%, preferably 0.05 to 50%.
10%. If the thickness of the conductor layer formed by dry plating is thin, the dry plating layer will be damaged by the plating solution during wet plating after dry plating, and the pattern width etc. tends to be uneven, so it is formed by dry plating If the thickness of the conductor layer to be formed is large, cracks tend to be easily generated in the pattern. The total thickness of the conductor layer formed by performing dry plating and then performing wet plating is usually about 5 to 5.
It is about 52 μm, preferably about 10 to about 41 μm.

The preferred manufacturing method of the present invention includes, after plating as described above, annealing. Annealing is performed to reconstruct the structure of the conductor layer formed by plating. The temperature at the time of annealing is appropriately selected depending on the type of the conductor forming the conductor layer, but is usually 20 to 250 ° C, preferably 100 to 200 ° C. Annealing time is usually 1 to 60 minutes.

The electric insulating layer used in the present invention is made of a polymer material. The polymer material may be one conventionally used as an insulating layer of a multilayer circuit board, for example,
Epoxy resin; ethylene / fluoroethylene copolymer; alicyclic olefin polymer; polyimide such as maleimide resin; (meth) acrylic resin; diallyl phthalate resin;
Triazine resin; one obtained by curing a curable composition containing any polymer such as polyphenylene ether. Further, the polymer material constituting the electric insulating layer may contain glass fiber, aramid fiber, or the like for improving strength.

As the polymer material constituting the electric insulating layer,
It is preferable to use an alicyclic olefin polymer or an aromatic polyether polymer, preferably a cured product of a curable resin composition containing the alicyclic olefin polymer. Hereinafter, a curable resin composition containing an alicyclic olefin polymer or an aromatic polyether polymer will be described. The alicyclic olefin polymer is an olefin polymer having an alicyclic structure. Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure, and a cycloalkane structure is preferable from the viewpoint of mechanical strength, heat resistance, and the like. The alicyclic structure may be any of a monocyclic ring and a polycyclic ring (such as a condensed polycyclic ring, a bridged ring, or a polycyclic ring obtained by combining these rings). The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 2.
0, more preferably in the range of 5 to 15,
Various properties such as mechanical strength, heat resistance and moldability are highly balanced and suitable. The alicyclic olefin polymer used in the present invention is usually a thermoplastic one.

The alicyclic olefin polymer usually contains a repeating unit derived from an olefin having an alicyclic structure (hereinafter sometimes referred to as an alicyclic olefin). The proportion of the repeating unit derived from the alicyclic olefin in the alicyclic olefin polymer is appropriately selected depending on the purpose of use,
It is usually from 30 to 100% by weight, preferably from 50 to 100% by weight, more preferably from 70 to 100% by weight. If the proportion of the repeating unit derived from an alicyclic olefin is too small, the heat resistance may be poor and may not be preferable.

The alicyclic olefin polymer used in the present invention preferably has a polar group. As a polar group, a hydroxyl group, a carboxyl group, an alkoxyl group, an epoxy group, a glycidyl group, an oxycarbonyl group,
Examples thereof include a carbonyl group, an amino group, an ester group, and a carboxylic anhydride group, and a carboxyl group or a carboxylic anhydride group is particularly preferable.

The alicyclic olefin polymer is usually obtained by addition polymerization or ring-opening polymerization of an alicyclic olefin and, if necessary, hydrogenation of an unsaturated bond portion or addition polymerization of an aromatic olefin. And hydrogenation of the aromatic ring portion of the polymer. Further, the alicyclic olefin polymer having a polar group includes, for example, 1) a monomer having a polar group by introducing a compound having a polar group into the alicyclic olefin polymer by a modification reaction. Or 3) by copolymerizing a monomer containing a polar group such as an ester group as a copolymerization component, and then hydrolyzing the ester group.

The alicyclic olefin used to obtain the alicyclic olefin polymer includes bicyclo [2.2.
1] -hept-2-ene (common name: norbornene), 5
-Methyl-bicyclo [2.2.1] -hept-2-ene, 5,5-dimethyl-bicyclo [2.2.1] -hept-2-ene, 5-ethyl-bicyclo [2.2.1] ]-
Hept-2-ene, 5-butyl-bicyclo [2.2.
1] -Hept-2-ene, 5-hexyl-bicyclo [2.2.1] -hept-2-ene, 5-octyl-bicyclo [2.2.1] -hept-2-ene, 5-octadecyl -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, 5-propenyl-bicyclo [2.
2.1] -hept-2-ene, 5-methoxycarbonyl-bicyclo [2.2.1] -hept-2-ene, 5-cyano-bicyclo [2.2.1] -hept-2-ene, 5
-Methyl-5-methoxycarbonyl-bicyclo [2.
2.1] -Hept-2-ene, 5-ethoxycarbonyl-bicyclo [2.2.1] -hept-2-ene, bicyclo [2.2.1] -hept-5-enyl-2-methylpro Pionate, bicyclo [2.2.1] -hept-5-
Enyl-2-methyloctaneate,

Bicyclo [2.2.1] -hept-2-ene-5,6-dicarboxylic anhydride, 5-hydroxymethylbicyclo [2.2.1] -hept-2-ene, 5,6
-Di (hydroxymethyl) -bicyclo [2.2.1]-
Hept-2-ene, 5-hydroxy-i-propylbicyclo [2.2.1] -hept-2-ene, 5,6-dicarboxy-bicyclo [2.2.1] -hept-2-ene, Bicyclo [2.2.1] -hept-2-ene-5,
6-dicarboxylic imide, 5-cyclopentyl-bicyclo [2.2.1] -hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] -hept-2-ene, 5
-Cyclohexenyl-bicyclo [2.2.1] -hept-2-ene, 5-phenyl-bicyclo [2.2.1]-
Hept-2-ene, tricyclo [4.3.0.1 ^2,5
Deca-3,7-diene (common name: dicyclopentadiene), tricyclo [4.3.0.1 ^2,5 ] deca-
3-ene, tricyclo [4.4.0.1 ^2,5 ] undeca-3,7-diene, tricyclo [4.4.0.1
^2,5 ] undeca-3,8-diene, tricyclo [4.
4.0.1 ^2,5] undec-3-ene, tetracyclo [7.4.0.1 ^{10, 13.} 0 ^2,7 ] -trideca-2,4,6,11-tetraene (alias: 1,4-methano-1,4,4a, 9a-tetrahydrofluorene),
Tetracyclo ^{[8.4.0.1 11,14.} 0 ^3,8 ]
-Tetradeca-3,5,7,12-tetraene (alias:
1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene),

Tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -dodec-3-ene (common name: tetracyclododecene), 8-methyl-tetracyclo [4.4.0.
1 ^2, 5. 17, ¹⁰ ] -dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 .
17, ¹⁰ ] -dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . ^{17, 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] - dodeca-3-ene, 8-methoxycarbonyloxy - tetracyclo [4.4.0.1 ^2, 5. 1 ^7,10 ] -dodeca-3-
Ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ]-dodeca-
3-ene, 8-hydroxymethyl-tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene,
8-carboxy-tetracyclo [4.4.0.
^12,5 . ^{17 , 10} ] -Dodeca-3-ene, 8-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -dodec-3-ene, 8-cyclohexyl-
Tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ]-
Dodeca-3-ene, 8-cyclohexenyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -dodeca-3
-Ene, 8-phenyl-tetracyclo [4.4.0.1
^2,5 . ^{17, 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 ^{1 0,13.} 0 ^2,7 ] -pentadeca-4,11-diene, tetracyclo [6.5.0.1
^2,5 . 0 ^8,13] Torideka 3,8,10,12-
Tetraene, tetracyclo [6.6.0.1 ^2,5 . 1
^8,13] Tetoradeka 3,8,10,12- tetraene such as norbornene monomer;

Cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7- Monocyclic cycloalkenes such as methano-1H-indene and cycloheptene; vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane; alicyclic conjugated diene monomers such as cyclopentadiene and cyclohexadiene; Is mentioned. As aromatic olefins, styrene, α
-Methylstyrene, divinylbenzene and the like. The alicyclic olefin and / or the aromatic olefin are
Each can be used alone or in combination of two or more.

The alicyclic olefin polymer may be obtained by copolymerizing the alicyclic olefin and / or aromatic olefin with a monomer copolymerizable therewith. Examples of monomers copolymerizable with an alicyclic olefin or an aromatic olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 3-methyl-1-.
Butene, 3-methyl-1-pentene, 3-ethyl-1-
Pentene, 4-methyl-1-pentene, 4-methyl-1
-Hexene, 4,4-dimethyl-1-hexene, 4,4
-Dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene Ethylene or α-olefin having 2 to 20 carbon atoms, such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-
Diene such as methyl-1,4-hexadiene, 1,7-octadiene, 1,3-butadiene, and isoprene; and the like. These monomers can be used alone or in combination of two or more.
In the ring-opening polymerization, the copolymerizable monomer may function as a molecular weight regulator. The method of polymerizing the alicyclic olefin or / and the aromatic olefin and the method of hydrogenation performed as required are not particularly limited,
It can be performed according to a known method.

Specific examples of the alicyclic olefin polymer include a ring-opened polymer of a norbornene-based monomer and a hydrogenated product thereof, an addition polymer of a norbornene-based monomer, a norbornene-based monomer and a vinyl compound. Addition polymers, monocyclic cycloalkene polymers, alicyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers and hydrogenated products thereof, and aromatic ring hydrogenated aromatic olefin polymers. . Among these, a ring-opening polymer of a norbornene-based monomer and a hydrogenated product thereof, an addition polymer of a norbornene-based monomer, an addition polymer of a norbornene-based monomer and a vinyl compound, and an aromatic olefin polymer. Aromatic hydrogenated products are preferred,
Particularly, a hydrogenated product of a ring-opening polymer of a norbornene-based monomer is preferable. The alicyclic olefin polymers described above can be used alone or in combination of two or more.

The alicyclic olefin polymer is not particularly limited by its molecular weight. The molecular weight of the alicyclic olefin polymer is determined by gel permeation chromatography (GPC) using cyclohexane or toluene as a solvent. The weight average molecular weight (Mw) in terms of polystyrene is measured.
And usually 1,000 to 1,000,000, preferably 5,000 to 500,000, more preferably 10,000.
The range is from 00 to 250,000. When the weight average molecular weight (Mw) of the alicyclic olefin polymer is within this range, heat resistance, smoothness of the surface of the molded product, and the like are balanced, which is preferable.

The molecular weight distribution of the alicyclic olefin polymer is
Weight average molecular weight (Mw) and number average molecular weight (Mw) measured by GPC using cyclohexane or toluene as a solvent
The ratio (Mw / Mn) to n) is usually 5 or less, preferably 4 or less, more preferably 3 or less. The above ranges of the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) and the measuring method are suitably adapted to the norbornene-based polymer, but are not limited thereto. In the case of an alicyclic olefin polymer whose weight-average molecular weight or molecular weight distribution cannot be measured by the above method, a polymer having a melt viscosity and a degree of polymerization sufficient to form a resin layer by a normal melt processing method is used. be able to. The glass transition temperature of the alicyclic olefin polymer may be appropriately selected depending on the purpose of use, but is usually 50 ° C. or higher, preferably 70 ° C. or higher, more preferably 100 ° C. or higher, and most preferably 125 ° C. or higher. is there.

The aromatic polyether polymer constituting the curable resin composition is a polyether having an aromatic ring, and is usually a 2,6-dimethylphenol or 2,6-diphenylphenol such as 2,6-dimethylphenol. It can be obtained by reacting a disubstituted phenol with oxygen in the presence of a basic copper (II) salt such as a copper (II) amine complex. As the aromatic polyether polymer, polyphenylene ether,
Modified polyphenylene ether and the like can be mentioned. Among these, modified polyphenylene ether having a small dielectric constant and a small dielectric tangent is preferable.

The curable resin composition used in the present invention may contain a curing agent. As the curing agent, there is no particular limitation, for example, an ionic curing agent, a radical curing agent or a curing agent having both ionic and radical properties, and the like, insulation resistance, heat resistance, chemical resistance, An ionic curing agent is preferable from the viewpoint of compatibility with the alicyclic olefin polymer.

Examples of the ionic curing agent include aliphatic polyamine compounds; alicyclic polyamine compounds; aromatic polyamine compounds; bisazide compounds; carboxylic acid anhydrides; dicarboxylic acids; diol compounds; triols; Amide compounds; diisocyanate compounds; polyepoxy compounds and the like. Examples of the radical curing agent include organic peroxides. Among these, a diol compound, a polyhydric phenol compound, and a normal-temperature solid polyvalent epoxy compound are preferable, and a normal-temperature solid polyvalent epoxy compound is particularly preferable. Each of these curing agents can be used alone or in combination of two or more. The compounding ratio of the curing agents is set to alicyclic olefin polymer or aromatic polyether polymer (hereinafter, referred to as “polyaliphatic olefin polymer”).
It is called an alicyclic olefin polymer or the like. 5) 150 parts by weight, preferably 15 to 110 parts by weight, per 100 parts by weight
Parts by weight, more preferably 30 to 100 parts by weight.

In order to accelerate the curing reaction between the alicyclic olefin polymer or the like and the curing agent, a curing accelerator or a curing assistant may be used. The curing accelerator is not particularly limited. When the curing agent is, for example, a polyvalent epoxy compound,
Tertiary amine compounds and boron trifluoride complex compounds are preferred. Above all, when a tertiary amine compound is used, lamination properties, insulation resistance, heat resistance, and chemical resistance to fine wiring are improved. These curing accelerators are used alone or in combination of two or more. The compounding amount of the curing accelerator is appropriately selected according to the purpose of use, but based on 100 parts by weight of the alicyclic olefin polymer or the like,
Usually 0.001 to 30 parts by weight, preferably 0.01 to 1 part
0 parts by weight, more preferably 0.03 to 5 parts by weight.

The curing assistant is not particularly limited. For example, oxime / nitroso-based curing aids; maleimide-based curing aids; allyl-based curing aids; methacrylate-based curing aids; vinyl-based curing aids; These curing aids can be used alone or in combination of two or more, respectively.
It is usually in the range of 1 to 1000 parts by weight, preferably 10 to 500 parts by weight with respect to 0 parts by weight.

The curable resin composition used in the present invention preferably contains a liquid epoxy resin. Liquid epoxy resin is an epoxy compound (or resin) that is liquid at room temperature in the absence of a solvent. Specifically, as a phenol type liquid epoxy resin, CAS 58421-55
-9, CAS 9003-85-4, CAS 306
21-65-9, CAS 89118-70-7, dibromocresyl glycidyl ether; as amine type liquid epoxy resin, CAS 28768-32-3, existing chemical substance 3-2792, CAS 2095-06-9,
CAS 40027-50-7; as alcohol type liquid epoxy resins, CAS 34629-78-2, CA
S 29611-97-0, CAS 7-343, CA
S 9072-62-2, CAS 30499-70-
8, CAS 30583-72-3, CAS 1112
1-15-6; As the ester type liquid epoxy resin,
CAS 27103-66-8, CAS 7195-4
5-1, CAS 36343-81-4, CAS 36
221-25-7, CAS 68475-94-5, C
AS68991-71-9; CAS25085-98-7, CAS29 as other liquid epoxy resins.
797-71-5, CAS 26616-47-7, C
AS 28825-96-9; epoxy-modified liquid rubber (specifically, epoxy-modified liquid polybutadiene), rubber-dispersed liquid epoxy resin, bisphenol A type liquid epoxy resin, bisphenol F type liquid epoxy resin, phenol novolak type liquid epoxy resin, etc. No.

Each of these liquid epoxy resins can be used alone or in combination of two or more, and the compounding ratio thereof is 100 or less.
1 to 100 parts by weight, preferably 5 to 100 parts by weight,
-80 parts by weight, more preferably 7-60 parts by weight.

The curable resin composition used in the present invention may further contain, if desired, a polymer other than the alicyclic olefin polymer and other compounding agents.
Examples of the polymer other than the alicyclic olefin polymer and the like include a rubbery polymer and a resin. The rubbery polymer is a polymer having a Tg of usually 30 ° C. or less, and specific examples include natural rubber, polyisobutylene rubber, butyl rubber, polybutadiene rubber, polyisoprene rubber, acrylonitrile / butadiene copolymer rubber, and styrene. Diene rubbers such as butadiene copolymer rubber, styrene / isoprene copolymer rubber, styrene / butadiene / isoprene terpolymer rubber, and hydrogenated products of these diene rubbers; ethylene such as ethylene / propylene copolymer; Saturated polyolefin rubbers such as α-olefin copolymers, propylene / other α-olefin copolymers; ethylene / propylene / diene copolymers, α-
Α- such as olefin / diene copolymer, isobutylene / isoprene copolymer, isobutylene / diene copolymer
Olefin / diene polymer rubber; special rubbers such as urethane rubber, polyether rubber, acrylic rubber, propylene oxide rubber, and ethylene acrylic rubber; styrene
Styrene-based thermoplastic elastomers such as butadiene / styrene block copolymer rubber and styrene / isoprene / styrene block copolymer rubber and hydrogenated products thereof; urethane-based thermoplastic elastomer; polyamide-based thermoplastic elastomer; 1,2-polybutadiene -Based thermoplastic elastomer; silicone rubber and the like.

As the resin, for example, low density polyethylene, high density polyethylene, linear low density polyethylene,
Polyolefins such as ultra low density polyethylene, polypropylene, syndiotactic polypropylene, polybutene and polypentene; polyamides such as nylon 66; ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer; polyester; polycarbonate; Silicone resin and the like can be mentioned.

These polymers can be used alone or in combination of two or more. The mixing ratio of the other polymers is 1 such as an alicyclic olefin polymer.
The amount is usually 100 parts by weight or less, preferably 70 parts by weight or less, more preferably 50 parts by weight or less with respect to 00 parts by weight, and the lower limit is 0 parts by weight.

Other compounding agents include fillers, flame retardants, flame retardant aids, heat stabilizers, weather stabilizers, leveling agents, antistatic agents, slip agents, antiblocking agents,
Examples include anti-fogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, emulsions, and the like.

In order to improve insulation resistance and peeling resistance as a compounding agent, a thiol compound, particularly a polyvalent thiol compound having at least two thiol groups in a molecule, is preferable. Those having a structure are more preferred. As the structure of the hetero ring, a triazine ring structure is preferable. In consideration of the wiring embedding property, a triazine thiol compound is particularly preferable. The compounding amount of the thiol compound is 1
The amount is usually 0.001 to 30 parts by weight, preferably 0.01 to 10 parts by weight, based on 00 parts by weight. If the amount is too small, the effect of improving insulation resistance and peeling resistance is difficult to be exhibited, and if the amount is too large, heat resistance and chemical resistance tend to decrease.

The electric insulating layers of the multilayer circuit board include those forming an inner layer substrate (electric insulating layer (1)) and those forming an interlayer insulating film (electric insulating layer (2)). The electrical insulating layer to which the manufacturing method of the present invention can be applied may be any of those forming an inner layer substrate and those forming an interlayer insulating film, but preferably forms an interlayer insulating film. Specific examples of the inner layer substrate include a printed wiring board and a silicon wafer substrate. The thickness of the inner layer substrate is usually 50 μm to 2 mm, preferably 60 μm to 1.6 mm,
More preferably, it is 100 μm to 1 mm. The inner layer substrate is formed from a material containing the above-mentioned polymer material, preferably glass fiber, aramid fiber or the like for improving the strength, and is usually obtained by a method such as a hot press method.

The interlayer insulating film is formed by laminating an electric insulating layer (2) on the inner layer substrate. As a forming method, after applying a solution or dispersion of the curable resin composition or the like on the inner layer substrate, the solvent is removed and dried to form a coating layer of the curable composition. Curing method: a method in which the curable resin composition is formed into a film or a sheet, and the sheet or the film is laminated on an inner layer substrate by heat compression and the like, and then cured. In the present invention, an electric insulating layer (2) formed by a method of heat-pressing a sheet or a film is preferable. The thickness of the electrically insulating layer (2) is usually 0.1 to 150 μm.
m, preferably 0.5 to 100 μm, more preferably 1.0 to 80 μm.

In order to laminate a film or sheet made of the curable resin composition on the inner layer substrate, the film or sheet is overlaid so as to be in contact with the surface of the inner layer substrate, and a pressure laminator, a press, a vacuum laminator, a vacuum press, Thermocompression bonding is performed using a press machine such as a roll laminator. The thermocompression bonding is preferably performed under vacuum in order to improve the embedding property in the wiring and suppress generation of bubbles and the like. The temperature during thermocompression bonding is usually 30 to 250 ° C, preferably 70 to 200 ° C.
° C, pressure bonding force is usually 0.1 to 200 kgf / cm ² , preferably 1 to 100 kgf / cm ² , and pressure bonding time is usually 30 seconds to 5 hours, preferably 1 minute to 3 hours, and preferably 300 mmHg ~. Reduce the pressure to 0.1 mmHg. Then, usually 30 to 400 ° C, preferably 70 to 300
Curing the film or sheet at a temperature of 100C, more preferably 100-200C.

In the manufacturing method of the present invention, vias can be formed for connecting the conductor circuits separated by the electric insulating layer (2). The via can be formed by a physical treatment such as a drill or a laser, or can be formed by so-called photolithography, in which the curable resin composition is masked and cured with light to remove an uncured portion. Among these via forming methods, a method using a laser such as a carbon dioxide gas laser, an excimer laser, and a UV-YAG laser is preferable from the viewpoint that finer vias can be formed without deteriorating the characteristics of the insulating layer.

[0042]

The present invention will be specifically described below with reference to examples and comparative examples. In the examples, “parts” means “parts by weight” unless otherwise specified.

(Evaluation and Measurement Methods) (1) Unless otherwise specified, the molecular weight was measured in terms of polystyrene by gel permeation chromatography (GPC) using toluene as a solvent. (2) The hydrogenation rate and carboxyl group content are ¹ H-N
Measured by MR. (3) The glass transition temperature (Tg) is determined by the differential scanning calorimetry (D
SC method). (4) Adhesion test The peel strength of the inner insulating layer and the upper insulating layer of the wiring board was measured according to JIS.
It was determined by a 90 degree peel test in accordance with C6481. (5) Patterning test 100 wiring patterns were formed with a wiring width of 30 μm and a distance between wirings of 30 μm, and “A” was given if none of the 100 wirings was disturbed in shape, and “A” was disturbed in shape but was defective. Those with no defect were evaluated as "B" and those with defects were evaluated as "D".

Example 1 8-ethylidene-tetracyclo [4.4.0.
^12,5 . [ ^7,10 ] -dodec-3-ene is subjected to ring-opening polymerization, followed by a hydrogenation reaction to obtain a number average molecular weight (Mn).
= 31,200, weight average molecular weight (Mw) = 55,80
A hydrogenated polymer having a Tg of about 155 ° C. was obtained. The hydrogenation rate of the obtained polymer was 99% or more. 28 parts of the obtained polymer, 10 parts of maleic anhydride, and 3 parts of dicumyl peroxide were dissolved in 130 parts of t-butylbenzene.
The reaction was performed at 40 ° C. for 6 hours. The obtained reaction product solution was poured into 300 parts of methanol, and the reaction product was solidified to obtain a maleic acid-modified hydrogenated polymer. The modified hydrogenated polymer was vacuum dried at 100 ° C. for 20 hours. The molecular weight of this modified hydrogenated polymer is Mn = 33,200, Mw = 6.
At 8,300, the Tg was 170 ° C. The maleic acid group content was 25 mol%.

100 parts of the above modified hydrogenated polymer, 1,3
-Diallyl-5-glycidyl isocyanurate 50 parts,
A varnish was obtained by dissolving in a mixed solvent consisting of 5 parts of dicumyl peroxide, 40 parts of a melamine polyphosphate having an average particle diameter of 3 μm, 175 parts of toluene and 117 parts of methyl isobutyl ketone. The varnish was filtered through a precision filter made of Teflon (registered trademark) having a pore diameter of 10 μm, and then applied to a polyethylene naphthalate film (carrier film) having a thickness of 75 μm using a die coater. After drying at 210 ° C. for 210 seconds, a dry film with a carrier film having a resin thickness of 35 μm was obtained.

When the wiring width and the distance between the wirings are 75 microns,
A conductor wiring layer having a wiring layer thickness of 18 microns and a diameter of 0.2
0.8mm thick with plated through hole of mm
The above-mentioned dry film with a carrier film is placed on both sides of the core substrate such that the resin surface is on the inner side of the core substrate with a thickness of 1 mmHg using a vacuum laminator.
At a temperature of 150 ° C. and a pressure of 5 kgf / cm ² .
The laminate was obtained by heating and pressing for minutes. The obtained laminate was taken out of the laminator, and only the polyethylene naphthalate film was peeled off.
The resin was cured by heating at 60 ° C. for 60 minutes and then at 180 ° C. for 60 minutes to form an electric insulating layer.

In the obtained laminated plate, UV-
Via holes of 30 μm in diameter for interlayer connection were formed using a YAG laser. Next, the laminate is washed with water and dried, and then heated to 170 ° C. in advance to obtain a frequency of 13.
It was exposed to argon plasma of 56 MHz, output of 100 W and gas pressure of 0.8 Pa for 10 minutes. During processing, the laminate
It was kept at 0 ° C. Next, the laminate is subjected to nickel sputtering at an output of 500 W and a gas pressure of 0.8 Pa to form a nickel film having a thickness of 0.03 μm.
Copper sputtering was performed at a gas pressure of 0.8 Pa to form a 0.3 μm thick copper thin film. A commercially available photosensitive dry film was bonded to the surface of the laminated plate by thermocompression bonding, and a mask having a predetermined pattern was brought into close contact with the dry film, exposed, and then developed to obtain a resist pattern. Next, electrolytic copper plating was applied to the non-resist forming portion to form an electrolytic copper plating film having a thickness of 18 μm. Next, the resist pattern was stripped and removed with a stripping solution, and the sputtered film hidden under the resist-formed portion was removed with a mixed solution of cupric chloride and hydrochloric acid to form a wiring pattern. Finally, annealing was performed at 170 ° C. for 30 minutes to obtain a circuit board.

0.1 part of 2-dibutylamino-4,6-dimercapto-S-triazine was dissolved in 100 parts of isopropyl alcohol to obtain a conductor layer pretreatment solution. The circuit board obtained above was immersed in a conductor layer pretreatment solution at room temperature for 1 minute, and then dried at 90 ° C. for 15 minutes. Using this processed circuit board as the core board,
An insulating layer and a conductor layer were repeatedly formed in the same manner as above to obtain a multilayer circuit board having a total of six layers on both sides. Table 1 shows the evaluation results.

Comparative Example A multilayer circuit board was obtained in the same manner as in Example 1, except that the temperature of the laminate during the argon plasma treatment was kept at 20 ° C. Table 1 shows the evaluation results.

Example 2 A multilayer circuit board was obtained in the same manner as in Example 1, except that the temperature of the laminate during the argon plasma treatment was kept at 130 ° C. Table 1 shows the evaluation results. Example 3 In Example 1, the electrolytic copper plating thickness was changed from 18 μm to 40 μm.
A multilayer circuit board was obtained in the same manner as in Example 1 except that m was used. Table 1 shows the evaluation results. Example 4 A multilayer circuit board was obtained in the same manner as in Example 1 except that the temperature of the laminated plate during the argon plasma treatment was kept at 150 ° C. and a chromium film was formed instead of the nickel film. Table 1 shows the evaluation results.

[0051]

[Table 1]

From Table 1, it can be seen that, as compared with those contacted with plasma at room temperature, those contacted with plasma at high temperature are:
It can be seen that the adhesion strength of a sputtered film of a conductor such as nickel, chromium, or copper is increased.

[0053]

According to the manufacturing method of the present invention, a multilayer circuit board having high adhesion between an electric insulating layer and a conductor layer and excellent in patternability can be easily obtained. The multilayer circuit board obtained by the method of the present invention is used in electronic devices such as computers and mobile phones, semiconductor elements such as CPUs and memories,
It can be used as a printed wiring board for mounting other mounting components. In particular, those having fine wiring are suitable as high-density printed wiring boards, and as wiring boards for high-speed computers and portable terminals used in high-frequency regions.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C25D 5/56 C25D 5/56 B 7/00 7/00 J H05K 3/14 H05K 3/14 A 3 / 38 3/38 A // C08L 101: 00 C08L 101: 00 F term (reference) 4F073 AA04 BA06 BA22 BA27 BA48 BB01 BB07 CA01 HA04 HA09 HA11 4K024 AA09 AB03 AB08 AB15 BA14 BB11 FA05 GA01 GA16 5E343 AA02 AA12 AA16 BB15 BB16 BB16 BB25 BB28 BB44 BB71 DD22 DD23 DD25 DD43 EE36 EE39 ER33 FF16 FF23 GG04 GG06 5E346 AA06 AA12 AA15 AA32 AA43 AA51 CC08 CC32 DD02 DD15 DD22 DD24 DD32 DD44 EE06 EE18 EE31 EE33 GG18 GG18 GG18 GG18 GG38

Claims (3)

[Claims] 1. A method for manufacturing a multilayer circuit board, comprising: contacting an electrically insulating layer made of a polymer material with plasma at a surface temperature of 50 to 250 ° C., and then forming a conductor layer on the surface. 2. The production of a multilayer circuit board according to claim 1, wherein the polymer material is obtained by curing a curable resin composition containing an alicyclic olefin polymer or an aromatic polyether polymer. Method. 3. The method according to claim 1, further comprising forming the conductive layer by a method including dry plating.