JP2002307608A - Laminate manufacturing method and multilayered printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently manufacturing a laminate suitable for a build-up method under such a condition that an adhesive layer has sufficient adhesiveness, and a multilayered printed wiring board using the laminate. SOLUTION: The laminate is manufactured by laminating a metal foil 1 to one surface of a polymeric film 10 through a first adhesive layer 11 and laminating a second thermosetting adhesive layer 12 to the other surface of the polymeric film 10. Alternatively, an adhesive is applied to both surfaces of the polymeric film 10 to be dried to bring the adhesive layers on both surfaces of the polymeric film 10 to a semicured state and the metal foil 13 is laminated to the adhesive layer 11 on the single surface under a condition capable of holding the adhesive layers on both surfaces to the semicured state.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a laminate having a laminated structure of a conductor layer / polymer film / adhesive layer, and more particularly to a high heat resistance, a narrow pitch wiring pattern, and a small diameter via. The present invention relates to a method for manufacturing a laminate capable of providing a multilayer wiring board having a stable thickness of an insulating layer and a stable adhesion between a metal and a polymer film.

[0002]

2. Description of the Related Art As electronic devices have become smaller, higher in performance and higher in function, wiring boards have been required to be able to cope with high-density mounting. To meet these demands, multilayer wiring boards, thinner insulating layers, the use of interstitial via holes instead of conventional through holes, smaller via diameters, and narrower circuit pitches are being developed. .

As a technique for realizing these, there is a multilayer wiring board manufacturing technique by a build-up method. Manufacturers of the build-up wiring board employ various methods of manufacture. Among them, the method using copper foil with insulating adhesive is easy to handle the material, and since the conductor layer is already formed, the process can be greatly shortened.
Used by many wiring board manufacturers.

[0004] The copper foil with an insulating adhesive has a two-layer structure of a copper foil and an adhesive layer, and is manufactured by a method of applying a solution adhesive on the copper foil and drying. For example, a general build-up multilayer wiring board using a copper foil with an insulating adhesive is manufactured as follows.

[0005] A copper foil with an insulating adhesive is laminated on a glass cloth-containing copper-clad laminate having a circuit formed in advance and subjected to through-hole processing by a method such as press processing or roll lamination.
After the copper foil at the place where the via is to be formed is removed by an etching method using a photosensitive resin, the adhesive layer is further removed by laser drilling to form the via, and the via is made conductive by electroless plating. Thereafter, the copper layer of the copper foil with an insulating adhesive is circuit-patterned by an etching method, the copper foil with an insulating adhesive is laminated again, and the same process is repeated to manufacture a build-up multilayer wiring board.

However, it has been pointed out that there are some problems when using a conventional copper foil with an insulating adhesive.

That is, when a small-diameter via is formed by laser drilling, and then a conductive layer is formed in the via by electroless plating or the like to be electrically connected to a lower circuit wiring, the smaller the via is, the smaller the aspect ratio is. Although it is easy to do so, it is necessary to reduce the thickness of the insulating layer. However, if the thickness of the insulating layer of the conventional copper foil with an insulating adhesive is reduced, it becomes difficult to make the thickness of each insulating layer uniform when laminated, and the insulating property also decreases, and the electrical reliability is secured. Had the problem of becoming difficult.

The use of a laminate composed of a conductor layer / polymer film / adhesive layer with a polymer film interposed between the conductor layer and the adhesive layer is one means for solving the above problem. It is valid.

That is, as one of the conductor layers at this time,
A thin film of metal is formed on the surface of a polymer film by a method such as vacuum evaporation or sputtering, and a metal layer of an arbitrary thickness is formed on the surface by a method such as electroplating. There is a problem that the adhesion strength between the surface and the metal thin film is low. In addition, the laminate having the above configuration has a problem of curling.

[0010]

The problem to be solved by the present invention is to provide a laminate suitable for the build-up method for efficiently producing a laminate under the condition that the adhesive layer has sufficient adhesiveness. It is to provide a manufacturing method and a laminate.

[0011]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the following problems can be solved by an efficient method for manufacturing a laminate, a laminate and a multilayer wiring board using the laminate as described below. The present invention led to the heading.

That is, according to the present invention, a metal foil is laminated on one surface of a polymer film via a thermosetting first adhesive layer, and the second surface of the polymer film is cured on the other surface of the polymer film. A method for producing a laminate in which an adhesive layer is laminated, wherein an adhesive is applied to both sides of the polymer film, dried, and the adhesive on both sides is semi-cured. The method is characterized in that a metal foil is laminated on an adhesive layer on one side under conditions that can maintain a semi-cured state.

[0013] In one embodiment, the polymer film is a polyimide film.

In one embodiment, the first and second thermosetting adhesive layers are made of a resin composition containing a polyimide resin and a thermosetting resin.

[0015] In one embodiment, the thermosetting resin is an epoxy resin.

In the laminate of the present invention, a metal foil is laminated on one side of a polymer film via a thermosetting first adhesive layer, and a thermosetting second adhesive layer is formed on the other side of the polymer film. A laminate in which two adhesive layers are laminated, wherein the first and second adhesive layers are in a semi-cured state. In one embodiment, the polymer film is a polyimide film.

In one embodiment, the first and second thermosetting adhesive layers are made of a resin composition containing a polyimide resin and a thermosetting resin.

In one embodiment, the thermosetting resin is an epoxy resin.

Further, a multilayer wiring board of the present invention is characterized by using the above-mentioned laminate.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As shown in FIG. 1, a laminate 1 of the present invention has a metal foil 13 laminated on one surface of a polymer film 10 with a thermosetting first adhesive layer 11 interposed therebetween. The thermosetting second adhesive layer 12 is laminated on the other surface.

When a multilayer printed wiring board is formed by a build-up method using the laminate of the present invention, the insulating layer is extremely thin because the polymer film 10 forms an insulating layer together with the second adhesive layer 12. And realizes a uniform thickness of the insulating layer.

The polymer film used in the present invention includes:
Materials excellent in dimensional stability, heat resistance and mechanical properties are preferable, for example, polyolefins such as polyethylene, polypropylene and polybutene, ethylene-vinyl alcohol copolymer, polystyrene, polyethylene terephthalate, polybutylene terephthalate, and ethylene-2,6.
-Polyester such as naphthalate, nylon-6, nylon-11, aromatic polyamide, polyamideimide resin, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyketone resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin,
Fluorine resin, polyarylate resin, liquid crystal polymer resin,
Examples include films of polyphenylene ether resin, polyimide, and the like.

The polymer film has a tensile modulus of 5 GPa in order to impart sufficient rigidity to the laminate of the present invention and a build-up wiring board obtained by using the laminate.
Or more, more preferably 6 GPa or more.

The thickness of the polymer film is preferably 50 μm or less, more preferably 35 μm or less, and even more preferably 25 μm or less for forming small-diameter vias. On the other hand, even if the thickness is small, sufficient electrical insulation is ensured. It is desirable to use a polymer film.

Further, since thermal stability is required at the time of processing a built-up wiring board, the dimensional stability is 2.0
× 10 ⁻⁵ / ° C. or less, more preferably 1.5 × 10 ⁻⁵ / ° C.
A polymer film having a linear expansion coefficient of preferably 1.0 × 10 ⁻⁵ / ° C. or less is desirable, and a polymer having a low water absorption rate is used so that defects such as swelling due to heat during processing do not occur. Film is preferred. Although the water absorption of a polymer film measured according to ASTM-D570 depends on the thickness even with the same composition, the water absorption of a 25 μm-thick film is preferably 1.5% or less, more preferably 1.2% or less. A polymer film having the following composition is desirable.

As a film satisfying the above-mentioned various properties, there is a polyimide film. The polyimide film is obtained from a polyamic acid polymer solution which is a precursor of the polyimide film, and the polyamic acid polymer solution can be produced by a known method. That is, one or two or more tetracarboxylic dianhydride components and one or two or more diamine components are used in substantially equimolar amounts and polymerized in an organic polar solvent to obtain a polyamic acid polymer solution.

Typical tetracarboxylic dianhydride components used for producing a polyimide film include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 1,4
5,8-naphthalenetetracarboxylic dianhydride, 2,
3,6,7-naphthalenetetracarboxylic dianhydride,
4,4′-oxydiphthalic anhydride, 3,3 ′, 4
4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 4,
4'-hexafluoroisopropylidene diphthalic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, p -An aromatic tetracarboxylic dianhydride such as phenylene bis (trimellitic acid monoester anhydride) and p-phenylenediphthalic anhydride.

Among these tetracarboxylic dianhydrides, the tensile modulus is 5 GPa or more and the linear expansion coefficient is 2.0 ×
10 ^-5 / ° C. or less, the water absorption illustrate preferred combinations for obtaining a polyimide film is not more than 1.5%, 0 to 80 mole% of pyromellitic dianhydride tetracarboxylic dianhydride, p A case where phenylene bis (trimellitic acid monoester anhydride) is used in an amount of 100 to 20 mol%. More preferably, the former is 30 to 70
In terms of mol%, the latter is 70 to 30 mol%, particularly preferably the former is 40 to 60 mol% and the latter is 60 to 40 mol%.
Incidentally, the combination of the tetracarboxylic dianhydride described here is a specific example for obtaining a polyimide film suitable for the polymer film constituting the laminate of the present invention, not limited to these combinations, The characteristics of the polyimide film can be adjusted by changing the combination and use ratio of the tetracarboxylic dianhydride used.

On the other hand, the diamine components include 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2-bis (4-aminophenoxyphenyl) propane, and 1,4-bis (4-aminophenoxy) Benzene, 1,3-bis (4-aminophenoxy)
Benzene, 1,3-bis (3-aminophenoxy) benzene, bis (4- (4-aminophenoxy) phenyl)
Sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) hexafluoropropane, 4,4 ' -Diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 9,9-bis (4-aminophenyl)
Fluorene, bisaminophenoxy ketone, 4, 4'-
(1,4-phenylenebis (1-methylethylidene))
Bisaniline, 4,4 '-(1,3-phenylenebis (1-methylethylidene)) bisaniline, metaphenylenediamine, paraphenylenediamine, 4,4'-diaminobenzanilide, 3,3'-dimethyl-4,4 '
-Diaminobiphenyl, 3,3'-dimethoxy-4,
Examples thereof include aromatic diamines such as 4'-diaminobiphenyl and other aliphatic diamines.

Among these diamine components, it is preferable to obtain a polyimide film having a tensile modulus of 5 GPa or more, a linear expansion coefficient of 2.0 × 10 ⁻⁵ / ° C. or less, and a water absorption of 1.5% or less. As an example of the combination, paraphenylenediamine and / or 4,4′-diaminobenzanilide may be used in an amount of 20 to 80 mol% of the diamine component, 4,4′-diamine.
A case where diaminodiphenyl ether is used in an amount of 80 to 20 mol% is exemplified. More preferably, the former is 30 to 70
In terms of mol%, the latter is 70 to 30 mol%, particularly preferably the former is 40 to 60 mol% and the latter is 60 to 40 mol%.
In addition, the combination of the diamine component described here shows one specific example for obtaining a polyimide film suitable for the polymer film constituting the laminate of the present invention, and is not limited to these combinations, and the diamine component to be used is not limited to these combinations. The characteristics of the polyimide film can be adjusted by changing the combination and the usage ratio.

When a polyimide film is used as the polymer film constituting the laminate of the present invention, the precursor polyamic acid has an average molecular weight of 10,000 to 1,000.
000 is desirable. Average molecular weight 10,000
If less than the finished film may be brittle,
On the other hand, if it exceeds 1,000,000, the viscosity of the polyamic acid varnish, which is a polyimide precursor, may be too high and handling may be difficult.

Various organic additives may be added to the polyamic acid,
Alternatively, an inorganic filler or various reinforcing materials may be added to form a composite polyimide film.

Examples of the organic polar solvent used for the reaction for producing the polyamic acid copolymer include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and formamides such as N, N-dimethylformamide and N, N-diethylformamide. Acetamide solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone,
A pyrrolidone solvent such as N-vinyl-2-pyrrolidone,
Phenols such as phenol, o-, m-, or p-cresol, xylenol, halogenated phenol, catechol, and the like, or hexamethylphosphoramide, γ-butyrolactone, and the like can be used alone or as a mixture. However, it is also possible to use a part of aromatic hydrocarbons such as xylene and toluene.

The polyamic acid copolymer is contained in the organic polar solvent in an amount of 5 to 40% by weight, preferably 10 to 3% by weight.
0% by weight is desirable from the viewpoint of handling.

In order to obtain a polyimide film from the polyamic acid copolymer solution, either a thermal method of thermally dehydrating or a chemical method using a dehydrating agent may be used. This is preferred because the resulting polyimide film has excellent mechanical properties such as elongation and tensile strength.

An example of producing a polyimide film by a chemical method will be described below.

A solution obtained by adding a dehydrating agent having a stoichiometric amount or more and a catalytic amount of a tertiary amine to the polyamic acid polymer or a solution thereof is cast or coated on a drum or an endless belt to form a film. The membrane is heated at a temperature of
After drying for 0 minutes, a self-supporting polyamic acid film is obtained.
Next, this is peeled off from the support and the end is fixed. Thereafter, it is imidized by gradually heating to about 100 to 500 ° C., and after cooling, the fixing of the end is released to obtain a polyimide film. Examples of the dehydrating agent mentioned here include aliphatic acid anhydrides such as acetic anhydride, and aromatic acid anhydrides such as benzoic anhydride. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, pyridine, picoline, and the like.
And heterocyclic tertiary amines such as isoquinoline.

The polymer film can be subjected to various surface treatments for the purpose of improving the adhesion to the adhesive layer.

For example, Cr, N
A method of forming a metal oxide adhesive layer on the surface of a polymer film by a method such as sputtering or plasma ion implantation of a metal oxide such as i, Ti, Mo, etc., thermosetting resin, thermoplastic resin, organic monomer, coupling Such as a method of applying various organic substances such as an agent as a primer, a method of surface treatment with a metal hydroxide, an organic alkali, etc., a method of plasma treatment, a method of corona treatment, a method of grafting the surface, etc. Treatment methods and the like may be mentioned, and these may be used alone or in various combinations to treat the surface of the polymer film.

Next, the conductor layer constituting the laminate of the present invention will be described.

The conductive layer constituting the laminate of the present invention is not particularly limited as long as it is a metal foil.
Although a metal foil such as a two-alloy foil can be used, it is preferable to use a copper foil. Although the thickness of the conductor layer is not particularly limited, it is 12 μm or less, more preferably 10 μm, for producing a narrow pitch circuit pattern.
The thickness is more preferably 8 μm or less.

Next, the adhesive layer constituting the laminate of the present invention will be described.

The first and second adhesive layers are laminated on both sides of the polymer film in a semi-cured state.
The second adhesive layer on the side opposite to the side on which the metal foil was temporarily press-bonded is formed by laminating the laminate of the present invention by a method such as hot press or roll heating, for example, a copper-clad laminate on which a circuit pattern is formed. ) Has a function of adhering to each other when a multilayer board is manufactured by laminating the layers thereon, whereby the inner layer circuit is firmly fixed in a form embedded in the adhesive.

Therefore, the adhesive layer on the surface opposite to the conductor layer via the adhesive layer of the polymer film must maintain a semi-cured state even after the metal foil is temporarily fixed, and maintain the adhesiveness. .

On the other hand, by setting the adhesive layer on the metal foil side in a semi-cured state, there is an effect of reducing the curl of the laminate of the present invention.

Here, the semi-cured state of the adhesive layer referred to in the present invention refers to a state in which the surface of the adhesive layer is dry, but the thermal fluidity and the adhesiveness to a metal or a polymer film are maintained. It is.

In addition, it is compatible with a lead-free high melting point solder which has been generated due to environmental considerations in recent years, a substrate temperature is increased with an increase in conductor resistance due to a narrow pitch of a circuit pattern, and high reliability has been achieved. From the viewpoint, the properties required for the adhesive include moisture resistance and heat resistance. Therefore, the resin composition of the adhesive layer also needs to have high Tg, high heat and moisture resistance, and high mechanical strength. The thickness is preferably such that the circuit pattern is embedded in the adhesive layer when the laminate of the present invention is laminated on the circuit pattern.

As the resin composition of the adhesive layer satisfying the above requirements, a curable adhesive utilizing a curing reaction of a thermosetting resin is preferable. Hereinafter, a curable adhesive utilizing a curing reaction of a thermosetting resin will be described.

Examples of the thermosetting resin include bismaleimide resin, bisallylnadiimide resin, phenol resin, cyanate resin, epoxy resin, acrylic resin, methacrylic resin, triazine resin, hydrosilyl cured resin, allyl cured resin, unsaturated polyester resin and the like. And these can be used alone or in appropriate combination.

Further, in addition to the above-mentioned thermosetting resin, a side-chain reactive group type thermosetting resin having a reactive group such as an epoxy group, an allyl group, a vinyl group, an alkoxysilyl group, or a hydrosilyl group on the side chain or terminal of the polymer chain. It is also possible to use curable polymers as thermosetting components.

Further, it is preferable to mix a heat-resistant engineering plastic such as polyphenylene ether resin, polyether sulfone resin, polyphenylene sulfide resin, polyetherimide resin, or a polyimide resin, since this leads to improvement in properties such as heat resistance. Among them, it is preferable to mix a thermoplastic polyimide resin with the thermosetting resin from the viewpoint of excellent heat resistance, electric reliability, high moisture resistance and the like. A resin composition obtained by mixing a high-adhesion, low-temperature processability epoxy resin and a heat-resistant, electrical-reliable, high-moisture-resistant thermoplastic polyimide resin is an adhesive layer of the laminate used in the present invention. It is suitable as a resin composition.
Hereinafter, the thermoplastic polyimide resin and the epoxy resin constituting the resin composition will be described.

As the thermoplastic polyimide resin, it is preferable to use a soluble polyimide, and this thermoplastic polyimide resin is obtained by reacting an acid dianhydride component with a diamine component. The acid dianhydride component preferably contains an ester dianhydride represented by the general formula (1).

[0053]

Embedded image (In the formula, X represents-(CH ₂ ) _k- or a divalent group containing an aromatic ring, and k is an integer of 1 to 10.) An ester dianhydride represented by the formula (1) When used, a polyimide resin having a low water absorption is obtained. Therefore, it is preferable that the acid dianhydride component contains the ester dianhydride represented by the formula (1), and it is particularly preferable that the acid dianhydride component contains 50 mol% or more of the acid dianhydride component.

The ester dianhydride represented by the formula (1) is 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride. Anhydride, p-phenylene bis (trimellitic acid monoester anhydride), 4,4′-biphenylene bis (trimellitic acid monoester anhydride), 1,4
-Naphthalene bis (trimellitic acid monoester anhydride), 1,2-ethylene bis (trimellitic acid monoester anhydride), 1,3-trimethylene bis (trimellitic acid monoester anhydride), 1,4- Tetramethylene bis (trimellitic acid monoester anhydride), 1,5-pentamethylene bis (trimellitic acid monoester anhydride), 1,6-hexamethylene bis (trimellitic acid monoester anhydride) and the like are preferable, These alone,
Alternatively, two or more kinds can be used as a part or all of the acid dianhydride component. When 2,2-bis (4-hydroxyphenyl) propane dibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride is used among the above ester dianhydrides, solubility in a solvent and processing characteristics are obtained. It is preferable because a polyimide resin having a good balance in heat resistance can be obtained.

The diamine component preferably contains a diamine represented by the general formula (2).

[0056]

Embedded image (Wherein, Y is, -C (= O) -, - SO 2 -, - O-,
_{-S -, - (CH 2)} m -, - NHCO -, - C (C
H ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —C (＝ O) O—, or a single bond. m and n are integers of 1 or more and 5 or less. The diamines represented by the formula (2) can be used alone or in combination of two or more. Here, in the formula (2), a plurality of Ys may be the same or different between each repeating unit, and each benzene ring has a hydrocarbon group such as a methyl group or an ethyl group, Br or Cl.
And the like, a halogen group may be introduced.

Further, among the diamine compounds represented by the formula (2), the diamine compound having an amino group at the meta position gives a thermoplastic polyimide resin having better solubility than the diamine compound having an amino group at the para position. It is preferred.

As described above, in the present invention, when a diamine compound having an amino group at the meta position is used, an effect of improving the solubility of the intended polyimide resin can be expected. It is more preferably 50 to 100 mol%, particularly preferably 8 to 100 mol% based on the components.
0 to 100 mol%.

The diamine compound represented by the formula (2) includes, for example, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, , 1-bis [4- (3
-Aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2- Bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4-
(3-aminophenoxy) phenyl] propane, 2,
2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [3- (3-aminophenoxy) phenyl ] -1,1,1,3,3,
3-hexafluoropropane, 2,2-bis [4-
(4-Aminophenoxy) phenyl] -1,1,1,
3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4′-bis (4-aminophenoxy) ) Benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4-
(3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone,
Bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-amino) Phenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4-
(4-aminophenoxy) phenyl] ether, 1,
4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4′-bis [3
-(4-Aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4'-
Bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis
[4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4- {4- (4
-Aminophenoxy) phenoxydiphenyl] sulfone, 1,4-bis [4- (4-aminophenoxy)-
α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, and the like. Further, among the diamine compounds represented by the formula (2), Examples of the diamine compound having an amino group at the meta position include 1,1-bis [4- (3-
Aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane,
2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [3- (3-
Aminophenoxy) phenyl] -1,1,1,3,
3,3-hexafluoropropane, 1,3-bis (3
-Aminophenoxy) benzene, 1,4-bis (3-
Aminophenoxy) benzene, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-
Aminophenoxy) phenyl] sulfide, bis [4
-(3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [ 4- (3-aminophenoxy) benzoyl] benzene, 4,4′-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether and the like. Also,

In addition to the diamine compound represented by the formula 2, m-phenylenediamine, o-phenylene diamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, bis (3-aminophenyl) sulfide , (3-aminophenyl) (4
-Aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, ( 3-aminophenyl) (4-aminophenyl) sulfone, bis (4aminophenyl) sulfone,
3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 3,4'-diaminodiphenylether, bis [4- (3-aminophenoxy) phenyl]
It is also possible to use sulfoxide, bis [4- (aminophenoxy) phenyl] sulfoxide and the like.

On the other hand, the use of a reactive diamine is also preferred. As a reactive diamine, 3,3′-
Dihydroxy-4,4'-diaminobiphenyl, 3,5
-Diaminobenzoic acid and the like. For example, since a hydroxyl group is introduced into a polyimide resin using 3,3′-dihydroxy-4,4′-diaminobiphenyl, the polyimide resin has reactivity with an epoxy compound. Therefore, in the resin composition containing the polyimide resin and the epoxy resin, which constitutes the adhesive layer of the laminate used in the present invention, the crosslinking progresses, and the provision of a laminate having excellent heat resistance and PCT resistance is provided. enable. If a large amount of reactive diamine is used, the solubility of the obtained polyimide resin may be impaired. Therefore, the amount is preferably 0 to 50 mol%, more preferably 0 to 20 mol%.

The polyimide resin is obtained by dehydrating and ring-closing the corresponding precursor polyamic acid polymer. The polyamic acid polymer is obtained by reacting the acid dianhydride component and the diamine component substantially equimolarly as described above.

The method of imidizing the polyamic acid generally includes a thermal method of thermally dehydrating and a chemical method using a dehydrating agent. The imidation method preferably applied to the polyamic acid polymer of the present invention is as follows. And imidization by heating under reduced pressure. According to this imidization method, water generated by the imidization can be positively removed from the system, so that hydrolysis of the polyamic acid can be suppressed, and a high-molecular-weight polyimide can be obtained. Further, according to this method, one or both ring-opened products present as impurities in the raw acid dianhydride are re-closed, so that a further improvement in molecular weight can be expected.

The heating conditions in the method of heat imidization under reduced pressure are preferably from 80 to 400 ° C., more preferably 100 ° C. or higher, at which the imidization is carried out efficiently and water is efficiently removed, more preferably 120 ° C. That is all. The maximum temperature is preferably equal to or lower than the thermal decomposition temperature of the target polyimide, and is usually the completion temperature of imidization, that is, 250 to 350.
C. is usually applied.

The condition of the pressure for reducing the pressure is preferably as small as possible, but specifically, 9 × 10 ⁴ to 1 × 10 ² Pa, preferably 9 × 10 ⁴ to 1 × 10 ² Pa, and more preferably 7 × 1 ⁴ Pa.
0 ⁴ to 1 × 10 ² Pa.

The polyimide resin thus obtained has a relatively low glass transition temperature. In the present invention, in order for the resin composition to obtain particularly good processing characteristics, the polyimide resin has a glass transition temperature of 350. C. or lower, more preferably 320.degree. C. or lower, particularly preferably 280.degree. C. or lower.

Next, the epoxy resin will be described.

As the epoxy resin, any epoxy resin can be used in the present invention. For example, bisphenol epoxy resin, halogenated bisphenol epoxy resin, phenol novolak epoxy resin, halogenated phenol novolak epoxy resin, alkylphenol novolak epoxy resin, polyphenol epoxy resin, polyglycol epoxy resin, cycloaliphatic epoxy resin Cresol novolak epoxy resin, glycidylamine epoxy resin, urethane-modified epoxy resin, rubber-modified epoxy resin, epoxy-modified polysiloxane, and the like.

The mixing ratio of the epoxy resin is preferably 1 to 80 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the polyimide resin. If the amount is too small, the adhesive strength decreases, and if the amount is too large, the flexibility or heat resistance decreases.

In the present invention, by combining the above-mentioned polyimide resin and the above-mentioned epoxy resin, it is possible to obtain an excellent adhesive layer which enables low water absorption and low temperature bonding. Therefore, when the resin composition of the adhesive layer of the laminate used in the present invention is cured, in a preferred embodiment, it is 1.5% or less, more preferably 1.3% or less, particularly preferably 1.0% or less. % Or less.

In a preferred embodiment, the resin composition of the adhesive layer of the laminate used in the present invention contains at least one resin.
Seed solvents are included. The solvent is not particularly limited as long as it can dissolve the polyimide resin and the epoxy resin, but is preferably of a type and an amount capable of suppressing the residual volatile matter of the resin composition after curing to 3% by weight or less. Further, a low boiling point solvent having a boiling point of 160 ° C. or less is preferred in view of economic efficiency and workability. A solvent having a boiling point of 130 ° C. or lower is more preferable, and a solvent having a boiling point of 105 ° C. or lower is more preferable. As such a low boiling point solvent,
Preferably, tetrahydrofuran (hereinafter abbreviated as THF).
Boiling point 66 ° C.), 1,4-dioxane (hereinafter abbreviated as dioxane, boiling point 103 ° C.), monoglyme (boiling point 84
° C) and dioxolane (boiling point 76 ° C). These may be used alone or in combination of two or more.

In a preferred embodiment, the
The insulating layer of the resulting laminate has a water absorption after curing of 1.0% or less.
It is assumed below. The cured product for measuring the water absorption is, for example,
Prepare as below. Synthetic resin film such as Polyimi
Apply adhesive on both sides of the film and dry, 5μm thick
To form an adhesive layer. Polyimide with double-sided adhesive obtained
5 μm and 18 μm thick copper on both sides of the mid film
The foil is temporarily pressed at 200 ° C. and a pressure of 3 MPa for 5 minutes. further
Heat cured at 200 ° C. for 60 minutes to produce a laminate,
Copper foil on both sides of the layer is removed by etching, and both sides are bonded
A polyimide film with a cured agent is prepared. This file
The water absorption of the rum can be measured by any known method. An example
For example, it can be calculated by measurement based on ASTM D570.
Wear. Specifically, for example, the above film is heated at 150 ° C. for 3 hours.
After drying for 0 minutes, the weight is W ₁And distilled for 24 hours
After immersion in water, the surface was wiped off and the weight was changed to W_Twoage,
The following formula: Water absorption (%) = (W_Two-W₁) ÷ W₁× 100 can be calculated.

Further, the resin composition of the adhesive layer of the laminate used in the present invention may contain an acid anhydride such as an acid dianhydride, an amine, etc., if necessary, such as water absorption, heat resistance and adhesiveness. Commonly used epoxy curing agents such as imidazoles, accelerators and various coupling agents can be used in combination. Further, a thermosetting resin other than the epoxy resin, a phenol resin, a cyanate resin, or the like may be used in combination.

Next, a method for producing a laminate of the present invention will be described.

In the method for producing a laminate according to the present invention, an adhesive is applied to both sides of a polymer film and dried to make the adhesive on both sides into a semi-cured state, and then the adhesive layers on both sides are maintained in a semi-cured state. It is characterized in that a metal foil is laminated on an adhesive layer on one side under conditions that can be performed.

As a method of applying the adhesive, any method within a range that can be carried out by those skilled in the art, such as a knife coater, a bar coater, a comma coater, and a gravure coater, can be used. The adhesive may be applied on one side at a time or on both sides at a time, as long as the conditions can maintain an optimal dry state.

The conditions for drying the adhesive layer may be any conditions under which the adhesive layers on both sides can maintain a semi-cured state, but the optimum drying conditions depend on the resin used, the composition ratio of the resin, the type of the curing agent, and the like. Note that may be different. When a resin composition containing the above-mentioned polyimide resin and epoxy resin is used, the drying temperature is preferably 120 to 250 ° C. The drying time is preferably about 1 to 30 minutes.

The temporary fixing of the metal foil must be performed under the condition that the adhesive layers on both sides can maintain the semi-cured state. As a method of temporarily fixing the metal foil, any method within a range that can be performed by those skilled in the art, such as hot pressing and roll heating, is possible, but a resin composition containing the above polyimide resin and epoxy resin was used. In the laminate having an adhesive layer, the temperature is 100 ° C. to 300 ° C. and the pressure is 0.05 to 5 MPa for 1 minute to
The heating press is preferably performed for 40 minutes, and the temperature is 150
It is particularly preferable to perform the heating press at 1 to 250 ° C and a pressure of 1 to 3 MPa for 1 to 20 minutes.

The conditions for curing the adhesive layer of the laminate used in the present invention may be any conditions that allow sufficient adhesion and curing. Examples of the curing method include curing by a hot press and curing by a hot air oven. When using a resin composition containing the above polyimide resin and epoxy resin,
For curing by hot pressing, the heating temperature is preferably 15
0-250 ° C. Pressure is preferably 0.1-10M
Pa. The heating time is preferably about 30 to 120 minutes. In the case of curing with a hot air oven, the heating temperature is preferably 150 to 250 ° C. The heating time is preferably about 30 to 120 minutes.

Further, a protective film can be used in the laminate of the present invention for the purpose of protecting the surface.

Next, an example of manufacturing a multilayer board using the laminate of the present invention will be described. As shown in FIGS. 2A and 2B, the present invention is applied to both sides of a polyimide film 20 having a first layer circuit 21 formed on both sides (for ease of explanation, the figure shows a case where a laminate is laminated on one side). Are laminated by heat lamination or hot press. The conditions at this time are set appropriately according to the type of the adhesive layer. However, when the conductor layer 13 is a copper foil, the temperature is preferably 300 ° C. or lower in order to suppress oxidative deterioration. Next, as shown in FIG. 2C, the via hole 14 is formed on the conductor layer of the metal foil 13 immediately above the land of the first layer circuit 21. As a forming method, various methods such as laser, plasma etching, chemical etching and the like can be mentioned. After the formation of the via hole 14, the via shape is adjusted as required by desmearing. Next, as shown in FIG. 2D, conduction of the via hole 14 is established by a method such as filling the conductive paste 15 and plating. Subsequently, the conductor layer 13 of the laminate of the present invention is patterned and etched to form a new circuit 16 (FIG. 2E). A multilayer board can be obtained by repeating the above steps (FIG. 2F).

Although the method for producing a laminate of the present invention has been described above, the present invention is not limited to these, and various improvements can be made based on the knowledge of those skilled in the art without departing from the spirit of the present invention. , Modifications and variations.

[0083]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but these Examples illustrate the present invention.
It is not meant to be limiting. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present invention.

Example 1 In a glass flask having a capacity of 2000 ml, dimethylformamide (hereinafter, referred to as DMF) and 0.95 equivalent of 1,3-bis (3-aminophenoxy) benzene (hereinafter, referred to as APB). And 0.
05 equivalents of 3,3'-dihydroxy-4,4'-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) were charged and dissolved by stirring under a nitrogen atmosphere. Further, the solution was stirred while cooling the solution with ice water under a nitrogen-substituted atmosphere in a nitrogen atmosphere.
Bis (4-hydroxyphenyl) propane dibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride (hereinafter referred to as ESDA) was added.

As described above, a polyamic acid polymer solution was obtained. The amount of DMF used was APB, 3, 3 '.
-Dihydroxy-4,4'-diaminobiphenyl and the monomer concentration of ESDA were adjusted to 30% by weight.

300 g of this polyamic acid solution was placed in a vat coated with Teflon (registered trademark) and heated in a vacuum oven at 200 ° C. for 180 minutes under reduced pressure at 665 Pa.
g of a thermoplastic polyimide resin having a hydroxyl group was obtained.

The polyimide resin powder obtained above, a novolak type epoxy resin (Epicoat 1032H60: manufactured by Yuka Shell Co., Ltd.), and 4,4′-diaminodiphenylsulfone (hereinafter, referred to as 4,4′-DDS) as a curing agent ) Was dissolved in dioxolane to obtain a solution having a concentration of 10% by weight. The weight ratio of each of the obtained solutions to polyimide, epoxy resin and 4,4′-DDS was 90:
The mixture was mixed at a ratio of 10: 3 to obtain an adhesive solution. The obtained adhesive solution was applied to a polyimide film (Apical 12.
5NPi, manufactured by Kanegabuchi Chemical Industry Co., Ltd.), and dried at 170 ° C. for 1 minute and 30 seconds to obtain a polyimide film with a double-sided adhesive having an adhesive layer thickness of 5 μm each. The obtained film and an electrolytic copper foil having a thickness of 5 μm were heat-temporarily pressed at a temperature of 200 ° C. and a pressure of 3 MPa for 5 minutes to obtain a laminate without curl. In order to check whether the adhesive layer of the laminate maintains a semi-cured state, that is, whether the adhesive layer maintains adhesiveness, the adhesive layer on the side opposite to the conductor layer of the laminate has a thickness of 18 μm. The temperature of the matte surface of the rolled copper foil
The adhesive layer was cured by heating and pressing at 60 ° C. and a pressure of 3 MPa for 60 minutes, and the peel strength between the copper foil and the laminate was measured to be 8.2 N / cm.

(Example 2) APB (0.
95 equivalents) and 3,3'-dihydroxy-4,4'-
Diaminobiphenyl (0.05 equivalent) was replaced with bis [4-
A polyamic acid polymer solution was obtained and a polyimide resin powder was obtained in the same manner as in Example 1, except that (3-aminophenoxy) phenyl] sulfone (1 equivalent) was used.

From the polyimide resin powder obtained above, an adhesive solution was obtained in the same manner as in Example 1.

Using the adhesive solution obtained above, a laminate without curl was obtained in the same manner as in Example 1. When the peel strength of this laminate was evaluated in the same manner as in Example 1, it was 5.2 N
/ cm.

Example 3 Both surfaces of an FR-E substrate were patterned to produce an inner circuit substrate having a circuit pattern with a conductor layer thickness of 9 μm. A wiring board was prepared by heating and pressing at a temperature of 200 ° C. and a pressure of 3 MPa for 60 minutes so that both pattern surfaces of the inner circuit board were in contact with the adhesive layer of the laminate of Example 1. Via holes were formed by a UV laser directly above the lands of the inner layer circuit of the wiring board, the via hole shape was adjusted by desmear treatment, and the via holes were conducted by electroless copper plating and electrolytic copper plating. Further, a circuit was formed by patterning both sides of the wiring board to form a four-layer wiring board. The inner layer circuit of this four-layer wiring board did not have any short circuit or disconnection, and the adhesion between the laminate and the inner circuit board and between the laminates was high.

Example 4 A four-layer wiring board was manufactured using the laminate obtained in Example 2 in the same manner as in Example 3.
The inner layer circuit of this four-layer wiring board did not have any short circuit or disconnection, and the adhesion between the laminate and the inner circuit board and between the laminates was high.

Comparative Example 1 Using the same adhesive, film, and copper foil as in Example 1, first apply an adhesive to one side of the film, and dry at 170 ° C. for 1 minute 30 seconds to obtain a 5 μm thick adhesive. A polyimide film with an agent was obtained.

A 5 μm electrolytic copper foil was applied to this film at a temperature of 20 ° C.
Temporarily press-fit at 0 ° C., pressure 3 MPa for 5 minutes, and further heat in an oven at 200 ° C. for 60 minutes to cure the adhesive layer,
A laminate was obtained. Further, an adhesive is applied to the surface of the laminate opposite to the conductor layer, dried at 170 ° C. for 1 minute 30 seconds, and
When a laminate having an adhesive layer in a semi-cured state of μm was prepared, it was greatly curled. When the peel strength was measured in the same manner as in Example 1, it was 7.5 N / cm.

(Comparative Example 2) A laminate was produced in the same manner as in Example 1 using the same adhesive, film and copper foil as in Example 2, and it was greatly curled. When the peel strength was evaluated, it was 3.9 N / cm.

From the above examples, in the method of the present invention, the adhesive is applied to one side of the film and dried to make the adhesive layer in a semi-cured state, and then the metal foil is heated and pressed to cure the adhesive layer. It can be seen that the curl is smaller than that of the method of the comparative example in which the adhesive layer is applied to the surface and dried to make the adhesive layer in a semi-cured state, and the peel strength is equal to or higher than that. That is, the adhesive layers on both sides of the method of the present invention maintain a semi-cured state.
Therefore, according to the method of the present invention, it is possible to efficiently manufacture a laminate having a structure of conductor layer / adhesive layer / polymer film / adhesive layer, which has a small curl and maintains adhesiveness.

The peel strength was measured according to JISC
6481.

[0098]

According to the method for producing a laminate of the present invention, a laminate maintaining the adhesiveness can be produced efficiently.
A multilayer wiring board using the same can be provided.

[Brief description of the drawings]

FIG. 1 is a sectional view of a laminate according to the present invention.

FIG. 2A is a part of a process diagram illustrating a method for manufacturing a multilayer printed wiring board according to the present invention.

FIG. 2B is a part of a process diagram illustrating the method for manufacturing a multilayer printed wiring board according to the present invention.

FIG. 2C is a part of a process view illustrating the method for manufacturing a multilayer printed wiring board according to the present invention.

FIG. 2D is a part of a process diagram illustrating the method for manufacturing a multilayer printed wiring board according to the present invention.

FIG. 2E is a part of a process diagram illustrating the method for manufacturing a multilayer printed wiring board according to the present invention.

FIG. 2F is a part of a process diagram illustrating the method for manufacturing a multilayer printed wiring board according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Laminated body 10 Polymer film 11 1st adhesive layer 12 2nd adhesive layer 13 Metal foil

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05K 3/00 H05K 3/00 R 3/38 3/38 D 3/46 3/46 BTF term ( reference) 4F100 AB01D AB33D AK01A AK01B AK01C AK49B AK49C AK53B AK53C AL05B AL05C AR00B AR00C BA04 BA07 BA10A BA10D EC182 EH462 EJ082 EJ172 EJ862 GB43 JB13B JB13C JL02 JL11B JL11C 5E343 AA02 AA13 AA17 AA18 AA33 AA38 BB05 BB24 BB67 CC03 DD80 EE22 GG02 5E346 AA05 AA06 AA12 AA15 AA16 AA32 BB01 CC10 CC32 CC41 DD02 DD03 DD32 EE31 GG02 GG15 GG28 HH11

Claims (9)

[Claims] A metal foil is laminated on one surface of a polymer film via a first thermosetting adhesive layer, and a second thermosetting adhesive layer is formed on the other surface of the polymer film. Is a method of manufacturing a laminated body, wherein an adhesive is applied to both sides of the polymer film, dried, and the adhesive on both sides is semi-cured, and then the adhesive layers on both sides are semi-cured. A method for producing a laminate, comprising laminating a metal foil on one side of an adhesive layer under conditions that can maintain the above conditions. 2. The method according to claim 1, wherein the polymer film is a polyimide film. 3. The production of a laminate according to claim 1, wherein said first and second thermosetting adhesive layers are made of a resin composition containing a polyimide resin and a thermosetting resin. Method. 4. The method according to claim 3, wherein the thermosetting resin is an epoxy resin. 5. A metal foil is laminated on one surface of a polymer film via a first thermosetting adhesive layer, and a second thermosetting adhesive layer is formed on the other surface of the polymer film. Is a laminated body, wherein the first and second adhesive layers are in a semi-cured state. 6. The laminate according to claim 5, wherein the polymer film is a polyimide film. 7. The laminate according to claim 5, wherein the first and second thermosetting adhesive layers are made of a resin composition containing a polyimide resin and a thermosetting resin. 8. The laminate according to claim 7, wherein the thermosetting resin is an epoxy resin. 9. A multilayer wiring board using the laminate according to any one of claims 5 to 8.