JP2003001752A - Laminate and multilayered wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate having metal foil/adhesive layer/polyimide film/adhesive constitution having high heat resistance, a narrow pitch wiring pattern, a small diameter via, uniform insulating layer thickness, the properly low coefficient of linear expansion and excellent surface smoothness. SOLUTION: The laminate is constituted by providing a metal foil on one surface of a polymeric film and providing an adhesive layer on the other surface thereof. The polymeric film comprises a polyimide film and the metal foil is a metal foil with a thickness of 5 μm or less having a release carrier and the hot flowability of the adhesive layer at the time of lamination processing is 1-100%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate, and more specifically, it has high heat resistance, a narrow pitch wiring pattern, small-diameter vias, a uniform insulating layer thickness, and an appropriately low linear expansion coefficient. The present invention relates to a laminate capable of providing a multilayer wiring board having excellent surface smoothness.

[0002]

2. Description of the Related Art As electronic devices are becoming smaller, higher in performance, and higher in functionality, printed wiring boards are required to be compatible with high-density mounting. In order to meet the demand, multilayer wiring boards, thinner insulating layers, adoption of inner via holes instead of conventional through holes, smaller via diameters, narrower circuit pitches, etc. are underway. As a technology for realizing these, there is a build-up method for manufacturing a multilayer printed wiring board. This build-up wiring board is manufactured by various manufacturers by various methods, but it is easy to handle the material, and because the conductor layer is already formed, the process can be shortened drastically. A method using copper foil is adopted by many wiring board manufacturers. This 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 in which a solution adhesive is applied onto the copper foil and dried. An example of manufacturing a build-up multilayer board using this copper foil with an insulating adhesive is shown below. A circuit is formed in advance, and a copper cloth with a glass cloth that has been through-hole processed is laminated with a copper foil with an insulating adhesive by a method such as press processing or roll lamination, and then the copper foil at the place where the via is to be formed. After removing by an etching method using a photosensitive resin, the adhesive layer is further removed by laser drilling to form vias, and the vias are made conductive by electroless plating. Then, the copper foil of the insulating adhesive-attached copper foil is formed into a circuit pattern by an etching method, the insulating adhesive-attached copper foil is laminated again, and the same steps are repeated thereafter to manufacture a build-up multilayer board.

However, it has been pointed out that the demand for build-up wiring boards will further increase in the future and that the conventional copper foil with an insulating adhesive has some problems. That is,
In order to produce a circuit pattern with a narrow pitch by an etching method, it is advantageous in terms of yield that the conductor layer to be etched has a small thickness, but the copper foil thickness of a conventional copper foil with an insulating adhesive is generally Is 18 μm, and is 12 μm even at the thinnest, and there is a limit to the thickness for producing a circuit pattern with a narrow pitch. In addition, when a small diameter via is formed by laser drilling and then a conductor layer is formed in this via by electroless plating or the like to electrically connect to the lower layer circuit wiring, the smaller the aspect ratio of the via, the easier the processing. For that purpose, 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 insulating adhesive is reduced, it becomes difficult to make the thickness of each insulating layer even when laminated, and the insulating property also decreases, so that electrical reliability can be ensured. It had the problem of becoming difficult. Further, it is required to reduce the thickness and weight of the multilayer wiring board, but the glass-clad copper-clad laminate normally used as the core layer of the build-up wiring board has a thickness of about 400 μm. Since it uses glass, it is heavy and does not meet the above requirements as a material. Further, instead of this copper-clad laminate with glass cloth, even if a multilayer board is made only with a copper foil with an insulating adhesive, it is possible to reduce the thickness and weight, but sufficient rigidity cannot be obtained. It has a large coefficient of linear expansion derived from insulating adhesives, and none of them can withstand use because they lack mounting reliability.

Further, the unevenness of the inner layer circuit appearing on the surface of the outer layer material is a problem in forming a fine pattern of the build-up wiring board, such as impairing the adhesion of the etching resist when the outer layer material is processed into a circuit, and lowering the plating throwing power. However, in order to obtain sufficient surface smoothness with conventional copper foil with insulating adhesive, the thickness of the insulating adhesive must be several times thicker than the conductor layer thickness, which is not suitable for thinning. was there.

[0005]

Therefore, the problem to be solved by the present invention is to provide a laminate suitable for manufacturing a build-up wiring board, and more specifically, high heat resistance,
It is an object of the present invention to provide a laminated body having a narrow pitch wiring pattern, a small diameter via, a uniform insulating layer thickness, an appropriately low linear expansion coefficient, and a multilayer wiring board excellent in surface smoothness.

[0006]

The present invention provides a laminate having a conductor layer on one surface of a polymer film and an adhesive layer on the other surface, wherein the thickness of the adhesive layer is the thickness of the inner layer circuit. A laminate having a surface roughness of 2 μm or less, which is 1 time or less, and has a surface roughness of 2 μm or less corresponding to the roughness of the inner layer circuit after stacking the laminate and the inner layer circuit board. Provided is a multilayer wiring board using. The adhesive layer of the present invention has a heat fluidity of 1% to 100 when laminating the adhesive layer.
% Is preferable. In the present invention, the conductor layer is preferably bonded by adhering the polymer film and the metal foil via the adhesive layer. The conductor layer of the present invention is preferably a metal foil of 5 μm or less provided with a peeling carrier. The polymer film of the present invention is preferably a polyimide film.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The laminate of the present invention has a conductor layer having an adhesive layer on one side of a polymer film and an adhesive layer on the other side.

When a multilayer wiring board is produced by the build-up method using the laminate of the present invention, the polymer film forms an insulating layer together with the adhesive layer, so that the insulating layer is prevented from becoming extremely thin, Achieves excellent surface smoothness with a uniform insulating layer thickness and a thin insulating layer thickness.

As the polymer film used in the present invention,
A material excellent in dimensional stability, heat resistance and mechanical properties is preferable, and examples thereof include polyolefin such as polyethylene, polypropylene and polybutene, ethylene-vinyl alcohol copolymer, polystyrene, polyethylene terephthalate, polybutylene terephthalate, 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 of the film include polyphenylene ether resin and polyimide.

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

Further, the thickness of the polymer film is preferably 50 μm or less, more preferably 35 μm or less and 25 μm or less for forming the small-diameter vias, while sufficient electrical insulation is secured even when the thickness is thin. The polymer film to be used is desirable.

Further, since thermal stability is required when processing a built-up wiring board, the dimensional stability is 2.0.
^{X10 -5} / ° C or less, more preferably 1.5 x 10 ^-5 / ° C
A polymer film having a linear expansion coefficient of 1.0 × 10 ⁻⁵ / ° C. or less is more preferable, and a polymer having a low water absorption coefficient so that defects such as swelling do not occur due to heat during processing. Film is preferred. The water absorption of the polymer film measured according to ASTM-D570 depends on the thickness even with the same composition, but the water absorption of the film having a thickness of 25 μm is preferably 1.5% or less, more preferably 1.2%. A polymer film having the following composition is desirable.

A polyimide film is mentioned as a film satisfying the above-mentioned various characteristics. The polyimide film is obtained from a polyamic acid polymer solution which is its precursor, and this polyamic acid polymer solution can be produced by a known method. That is, one or more tetracarboxylic dianhydride components and one 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 in the production of polyimide films include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3'. 3 ', 4,4'-diphenylsulfone tetracarboxylic acid 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 -Aromatic tetracarboxylic dianhydrides such as phenylene bis (trimellitic acid monoester anhydride) and p-phenylenediphthalic anhydride.

Among these tetracarboxylic dianhydrides, the tensile elastic modulus is 5 GPa or more and the linear expansion coefficient is 2.0 ×.
As a preferred combination for obtaining a polyimide film having a water absorption of 10 ^-5 / ° C or less and a water absorption of 1.5% or less, pyromellitic dianhydride is used in an amount of 0 to 80 mol% of tetracarboxylic dianhydride, p -A case where phenylene bis (trimellitic acid monoester anhydride) is used in an amount of 100 to 20 mol% can be mentioned. Incidentally, the combination of the tetracarboxylic dianhydride described here is one 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 the ratio of the tetracarboxylic dianhydride used.

On the other hand, as the diamine component, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2-bis (4-aminophenoxyphenyl) propane, 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 ′ -Diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 9,9-bis (4-aminophenyl)
Fluorene, bisaminophenoxyketone, 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,
Aromatic diamines such as 4′-diaminobiphenyl, and other aliphatic diamines can be mentioned.

Of these diamine components, preferred is 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 rate of 1.5% or less. As an example of the combination, paraphenylenediamine and / or 4,4′-diaminobenzanilide is added in an amount of 20 to 80 mol% of the diamine component and 4,4′-
The case where 80 to 20 mol% of diaminodiphenyl ether is used is mentioned. Incidentally, the combination of diamine components described here is one specific example for obtaining a polyimide film suitable for the polymer film constituting the laminate of the present invention, not limited to these combinations, of the diamine components used The characteristics of the polyimide film can be adjusted by changing the combination and the use ratio.

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

Further, various organic additives to polyamic acid,
Alternatively, inorganic fillers or various reinforcing materials may be added to form a composite polyimide film.

Examples of the organic polar solvent used in the reaction for producing the polyamic acid copolymer include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and formamide such as N, N-dimethylformamide and N, N-diethylformamide. System solvents, acetamide-based solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone,
A pyrrolidone-based solvent such as N-vinyl-2-pyrrolidone,
Phenol-based solvents such as phenol, o-, m- or p-cresol, xylenol, halogenated phenol and catechol, hexamethylphosphoramide and γ-butyrolactone can be used, and these are used alone or as a mixture. However, it is also possible to partially use an aromatic hydrocarbon such as xylene or toluene.

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

To obtain a polyimide film from this polyamic acid copolymer solution, either a thermal method of thermally dehydrating or a chemical method using a dehydrating agent may be used. It is preferable because the 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 prepared by adding a stoichiometric or more stoichiometric dehydrating agent and a catalytic amount of a tertiary amine to the above polyamic acid polymer or a solution thereof is cast or coated on a drum or an endless belt to form a film. ℃
Dry at a temperature below for about 5 to 90 minutes to obtain a self-supporting polyamic acid film. Then, this is peeled off from the support and the end is fixed. After that, by gradually heating to about 100 to 500 ° C., imidization is performed, and after cooling, the fixing of the end portion is released to obtain a polyimide film. Examples of the dehydrating agent 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, and the like.
Heterocyclic tertiary amines such as pyridine, picoline, isoquinoline and the like can be mentioned.

Further, the polymer film may be subjected to various surface treatments for the purpose of improving the adhesion with the adhesive layer.

For example, on the surface of a polymer film, Cr, N
Method of forming metal oxide adhesive layer on polymer film surface by sputtering, plasma ion implantation, etc. of metal oxide such as i, Ti, Mo, thermosetting resin, thermoplastic resin, organic monomer, coupling The method of applying various organic substances such as agents as a primer, the method of surface treatment with metal hydroxide, organic alkali, etc., the method of plasma treatment, the method of corona treatment, the method of grafting the surface, etc. Examples thereof include a treatment method and the like, and the polymer film surface may be treated alone or in various combinations.

Next, the conductor layers forming the laminate of the present invention will be described. The conductor layer forming the laminate of the present invention is preferably a metal foil. The metal foil is not particularly limited, and a metal foil such as a copper foil, an aluminum foil, or a 42 alloy foil can be used, but a copper foil is preferably used. In addition, the thickness of the conductor layer is particularly preferably 5 μm or less in order to produce a sandwiched pitch circuit pattern.

The metal foil provided with a peeling carrier is
It is suitable for the present invention because it is excellent in handleability and the surface smoothness after press lamination is improved due to the thickness and elasticity of the peeling carrier. The carrier for peeling is not particularly limited, and polyester such as polyethylene terephthalate, polycarbonate, release paper, and metal foil such as copper foil, aluminum foil, and 42 alloy foil can be used. When using a copper foil suitable for the invention as a conductor layer,
It is preferable to use a copper foil as the peeling carrier. The thickness of the peeling carrier is not particularly limited, but preferably 5 to
The thickness is 100 μm, more preferably 10 to 50 μm.
Next, the adhesive layer constituting the laminate of the present invention will be described. The adhesive layer in the laminate of the present invention is laminated on both sides of the polymer film, and two adhesive layers, that is, the adhesive layer 1 on the side opposite to the conductor layer and the adhesive layer 2 for adhering the conductor layer are provided. is there. The adhesive layer 1 will be described. The adhesive layer 1 has a function of adhering each other when laminating the laminate of the present invention by a method such as hot pressing and roll heating to produce a multilayer board, whereby the inner layer circuit is embedded in the adhesive. It is firmly fixed in a bent shape. Therefore, the adhesive layer 1 must maintain a semi-cured state and maintain adhesiveness. Also,
In order to correspond to the fine patterning of the build-up wiring board, the adhesive layer 1 of the laminate of the present invention has a thickness of 1 time or less the thickness of the inner layer circuit, and the laminate and the inner layer circuit board are laminated. After that, the surface roughness of the laminate corresponding to the roughness of the inner layer circuit is 2 μm or less, more preferably 1.5 μm or less. The surface unevenness is smoothed by the adhesive flowing into the unevenness of the inner layer circuit due to heat flow during lamination processing. Therefore, the adhesive layer 1 is required to have thermal fluidity that satisfies the above-mentioned surface smoothness when laminated. There is a flattening rate as another index showing the surface unevenness. The flattening ratio as used herein means a level difference of the unevenness of the inner layer circuit, and after stacking the laminate of the present invention and the inner layer circuit substrate having the inner layer circuit, the flatness of the laminate corresponding to the unevenness of the inner layer circuit When the surface unevenness is b, it is a value obtained by the following equation. Flattening rate (%) = (1-b / a) × 100 In the laminated body of the present invention, the flattening rate after laminating the laminated body and an inner layer circuit board having an inner layer circuit is preferably 70% or more. , And more preferably 80% or more. Furthermore, from the viewpoint of high reliability, which is compatible with lead-free high-melting-point solder that has occurred due to environmental consideration in recent years, correspondence with rise in board temperature accompanying rise in conductor resistance due to narrow pitch of circuit patterns, and high reliability, Moisture resistance and heat resistance are mentioned as properties required of the adhesive. Therefore, the resin composition of the adhesive layer 1 is also required to have high Tg, high humidity and heat resistance, and high mechanical strength.
As the resin composition of the adhesive layer 1 that satisfies the above requirements, a curable adhesive that utilizes the curing reaction of a thermosetting resin is suitable. Hereinafter, a curable adhesive that utilizes the curing reaction of the thermosetting resin will be described.

As the thermosetting resin, bismaleimide resin, bisallylnadiimide resin, phenol resin, cyanate resin, epoxy resin, acrylic resin, methacrylic resin, triazine resin, hydrosilyl curing resin, allyl curing resin, unsaturated polyester resin, etc. These can be used alone or in combination as appropriate. Further, in addition to the 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 at the side chain or terminal of the polymer chain It is also possible to use the molecule as a thermosetting component. Furthermore, it is preferable to mix a heat-resistant engineering plastic such as a polyphenylene ether resin, a polyether sulfone resin, a polyphenylene sulfide resin, or a polyetherimide resin, a polyimide resin, or the like, because the characteristics such as heat resistance are improved. Above all, it is preferable to mix the thermoplastic polyimide resin with the thermosetting resin from the viewpoint of excellent heat resistance, electric reliability, high humidity resistance and the like. High adhesiveness, low temperature processability, a resin composition obtained by mixing an epoxy resin excellent in heat fluidity, heat resistance, electric reliability, and a thermoplastic polyimide resin excellent in high humidity resistance is a laminate of the present invention. It is suitable as a resin composition for the adhesive layer. The thermoplastic polyimide resin and epoxy resin that compose this resin composition will be described below. Soluble polyimide is preferably used as the thermoplastic polyimide resin, and this thermoplastic polyimide resin is obtained by reacting an acid dianhydride component and a diamine component. The acid dianhydride component preferably contains an ester acid dianhydride represented by the general formula (1).

[0029]

[Chemical 1] (In the formula, _{X, - (CH 2) k -} , or a divalent group containing an aromatic ring, k is an integer of from 1 to 10.) The use of an ester acid dianhydride of the general formula (1) A polyimide resin having a low water absorption rate is obtained. Therefore, the acid dianhydride component is represented by the general formula (1)
It is preferable to contain the ester dianhydride represented by, and it is particularly preferable to contain 50 mol% or more of the acid dianhydride component.

The ester dianhydride represented by the general formula (1) is 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'-.
Tetracarboxylic acid dianhydride, 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 may be combined and used as a part or all of the acid dianhydride component. When 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride is used among the above ester dianhydrides, solubility in solvent and processing characteristics It is preferable because a polyimide resin having a good balance in heat resistance and heat resistance can be obtained.

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

[0032]

[Chemical 2] (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 diamine represented by the general formula (2) can be used alone or in combination of two or more kinds. Here, in the general formula (2), a plurality of Ys may be the same or different in each repeating unit, and each benzene ring has a hydrocarbon group such as a methyl group or an ethyl group or Br or A halogen group such as Cl may be introduced.

Further, in the diamine compound represented by the general formula (2), the diamine compound having an amino group at the meta position is a thermoplastic polyimide resin having a higher solubility than the diamine compound having an amino group at the para position. It is preferable because it gives.

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

Examples of the diamine compound represented by the general formula (2) include bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-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-dimethyl) Benzil)
Phenoxy] benzophenone, 4,4'-bis [4-
(4-amino-α, α-dimethylbenzyl) phenoxy] diphenyl sulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone,
1,4-bis [4- (4-aminophenoxy) -α, α
-Dimethylbenzyl] benzene, 1,3-bis [4-
(4-Aminophenoxy) -α, α-dimethylbenzyl
Examples of the diamine compound having an amino group at the meta position in the diamine compound represented by the general formula (2) include 1,1-bis [4- (3-aminophenoxy) phenyl]. Ethan, 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
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 Examples thereof include-(3-aminophenoxy) benzoyl] benzene and 4,4'-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether. In addition to the diamine compound represented by the general formula (2), m-phenylenediamine, o-phenylenediamine, 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′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,
4'-diaminodiphenyl ether, bis [4- (3-
It is also possible to use aminophenoxy) phenyl] sulfoxide, bis [4- (aminophenoxy) phenyl] sulfoxide and the like.

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

The polyimide resin is obtained by dehydration ring closure of the corresponding precursor polyamic acid polymer. The polyamic acid polymer is obtained by reacting the acid dianhydride component and the diamine component in substantially equimolar amounts as described above.

As the method for imidizing the polyamic acid, there are usually a thermal method of thermally dehydrating and a chemical method using a dehydrating agent, but the imidizing method preferably applied to the polyamic acid polymer of the present invention is It is a method of heating under reduced pressure for imidization. According to this imidization method, water generated by imidization can be positively removed to the outside of the system, so that hydrolysis of polyamic acid can be suppressed and a high molecular weight polyimide can be obtained. Further, according to this method, the ring-opened product on one side or both sides present as an impurity in the acid dianhydride as the raw material is re-closed, so that a further improvement effect of the molecular weight can be expected.

The heating condition of the method of heating and imidizing under reduced pressure is preferably 80 to 400 ° C., but more preferably 100 ° C. or higher, more preferably 120 ° C., which enables efficient imidization and efficient removal of water. That is all. The maximum temperature is preferably equal to or lower than the thermal decomposition temperature of the intended polyimide, and the normal imidization completion temperature, that is, 250 to 350.
℃ degree is usually applied.

The pressure reduction condition is preferably as small as possible, specifically, 9 × 10 ⁴ to 1 × 10 ² Pa, preferably 9 × 10 ⁴ to 1 × 10 ² Pa, more preferably 7 × 1.
It is 0 < ⁴ > -1 * 10 < ² > Pa.

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

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 novolac epoxy resin, halogenated phenol novolac epoxy resin, alkylphenol novolac epoxy resin, polyphenol epoxy resin, polyglycol epoxy resin, cycloaliphatic epoxy resin,
A cresol novolac epoxy resin, a glycidyl amine epoxy resin, a urethane modified epoxy resin, a rubber modified epoxy resin, an epoxy modified polysiloxane, etc. can be used, and these can also be used in combination of 2 or more types.

The mixing ratio of the epoxy resin is preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, and further preferably 20 to 100 parts by weight with respect to 100 parts by weight of the polyimide resin. If it is too small, the adhesive strength or heat fluidity will decrease, and if it is too large, the flexibility or heat resistance will decrease.

As described above, the surface irregularities of the multilayer wiring board are smoothed by the adhesive flowing into the irregularities of the inner layer circuit due to heat flow during lamination processing. In order to have excellent surface smoothness, it is preferable that the adhesive layer 1 constituting the laminate of the present invention has a heat fluidity of 1% to 100% during lamination processing.
In the present invention, an adhesive layer having excellent surface smoothness can be obtained by combining the above-mentioned polyimide resin and the above-mentioned epoxy resin. Here, the thermal fluidity of the adhesive layer is 50 mm in length and width, and a polyimide film with a single-sided adhesive in which punch holes with a diameter of 1 mm are formed at 5 locations (adhesion of 9 μm in thickness, which is applied, dried, and kept in a semi-cured state). Adhesive layer of polyimide film with adhesive)
After pressing for 1 hour at a temperature of 200 ° C. and a pressure of 3 MPa so that the shine surface of the rolled copper foil of 0 mm is in contact, the diameter is 1
The average value of 5 points of the area of the adhesive layer flowing out into the punch hole of mm is a, and the average value of 5 points of the area of the punch hole of 1 mm in diameter is b.
Is a value obtained by the following equation.

Thermal fluidity of the adhesive layer (%) = (a / b) × 100 In the present invention, low water absorption and low temperature adhesion are possible by combining the above-mentioned polyimide resin and the above-mentioned epoxy resin. An excellent adhesive layer can be obtained. 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. It is possible to develop an excellent low water absorption rate of not more than%.

In a preferred embodiment, the resin composition of the adhesive layer of the laminate used in the present invention contains at least 1
A seed solvent is included. The solvent is not particularly limited as long as it dissolves the polyimide resin and the epoxy resin, but a type and amount capable of suppressing the residual volatile content after curing of the resin composition to 3% by weight or less are preferable. Further, in view of economy and workability, a low boiling point solvent having a boiling point of 160 ° C. or lower is preferable. 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.degree. C.) can be used. These may be used alone or in combination of two or more.

In a preferred embodiment, used in the present invention
The insulating layer of the laminated body has a water absorption of 1.0% or more after curing.
To be below. The cured product for measuring the water absorption rate is, for example,
Make as follows. Synthetic resin film such as polyimi
Adhesive is applied to both sides of the film and dried to a thickness of 5 μm
To form an adhesive layer. The obtained double-sided adhesive-coated poly
Copper with a thickness of 5 μm and 18 μm on both sides of the mid film
The foil is temporarily press-bonded at 200 ° C. and a pressure of 3 MPa for 5 minutes. further
Heat cure at 200 ° C. for 60 minutes to prepare a laminate,
The copper foil on both sides of the layered body is removed by etching, and both sides are bonded.
A polyimide film with a cured product is prepared. This file
The water absorption of rum can be measured by any known method. An example
For example, by calculation based on ASTM D570
Wear. Specifically, for example, the above film at 3
The weight of the product dried for 0 minutes is W ₁And then distilled for 24 hours
After soaking it in water and wiping the surface, weigh W₂age,
The following formula: Water absorption rate (%) = (W₂-W₁) ÷ W₁× 100 Can be calculated by

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, if necessary, such as water absorption, heat resistance, adhesiveness, heat fluidity. , Commonly used epoxy curing agents such as amine-based and imidazole-based curing agents, accelerators and various coupling agents may be used in combination. Further, a thermosetting resin other than an epoxy resin, a phenol resin, a cyanate resin or the like may be used in combination.

Next, the adhesive layer 2 of the laminate of the present invention will be described. The adhesive layer 2 is not particularly limited as long as it firmly adheres to the metal foil. However, from the point of view of high reliability, which is compatible with lead-free high-melting-point solder that has occurred due to environmental considerations in recent years, increase in substrate temperature due to increase in conductor resistance due to narrow pitch of circuit patterns, and high reliability, Moisture resistance is mentioned as a required characteristic. Therefore,
The resin composition of the adhesive layer 2 also has high Tg, high humidity resistance and heat resistance,
High mechanical strength is required. Adhesive layer 2 that meets the above requirements
It is preferable in the present invention to use a resin composition obtained by mixing a thermoplastic polyimide resin and an epoxy resin, as in the adhesive layer 1, as the resin composition. Here, the mixing ratio of the thermoplastic polyimide resin of the adhesive layer 2 and the epoxy resin may be the same as or different from the mixing ratio of the thermoplastic polyimide resin of the adhesive layer 1 and the epoxy resin. The thickness of the adhesive layer 2 is not particularly limited, but is preferably 0.1 to 1.5 of the thickness of the adhesive layer 1.
Times, more preferably 0.3 to 1.0 times. If the thickness of the adhesive layer 2 is less than 0.1 times the thickness of the adhesive layer 1, the adhesion to the metal foil and the curling of the laminate become problems. Further, the thickness of the adhesive layer 2 is 1.
If it is thicker than 5 times, the curl of the laminate becomes a problem. Also,
In the laminate of the present invention, the adhesive layer 1 is in a semi-cured state. Here, the adhesive layer 1 needs to be in a semi-cured state, but the adhesive layer 2 may be in a cured state or in a semi-cured state. However, when the adhesive layer 2 is in a cured state, the laminate may curl, so that the adhesive layer 2 is preferably in a semi-cured state.

Next, a method for manufacturing the laminate of the present invention will be described. In the laminated body of the present invention, the conductor layer is bonded by adhering the polymer film and the metal foil via the adhesive layer. Further, as described above, it is preferable that both the adhesive layers 1 and 2 are in a semi-cured state. Therefore, the preferred method for producing a laminate of the present invention is to apply an adhesive to one side of a polymer film, dry the adhesive on one side to a semi-cured state, then temporarily fix the metal foil, and further to the opposite of the metal foil. On the surface of, the adhesive is applied under the condition that the adhesive layers on both sides can maintain a semi-cured state,
A method of drying, or applying an adhesive agent to each side or each side of the polymer film, and drying, after semi-curing the adhesive agent on both sides, in laminating the metal foil only on one side,
In this method, the metal foils are temporarily fixed to one surface under the condition that the adhesive layers on both surfaces can maintain a semi-cured state.

The method for applying the adhesive may be any method within the 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.

The conditions for drying the adhesive layer are as long as the adhesive layers on both sides can maintain a semi-cured state and the heat fluidity at the time of laminating the adhesive 2 is 1 to 100%. However, it should be noted that the optimum drying conditions may differ depending on the resin used, the composition ratio of the resin, the type of curing agent, and the like. When the resin composition containing the above-mentioned polyimide resin and epoxy resin is used, the drying temperature is preferably 120 to
It is 250 degreeC. 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 layer can maintain a semi-cured state. As a method of temporarily fixing the metal foil, any method within a range that can be carried out by those skilled in the art, such as hot pressing and roll heating, can be used. Temporary fixing of the metal foil may be performed with the adhesive layers already present on both sides of the polymer film, or with only the adhesive layer 1 present.

A protective film may be used in the laminate of the present invention for the purpose of protecting the surface.

Next, an example of manufacturing a multilayer wiring board using the laminate of the present invention will be described. The laminate of the present invention is laminated on both sides of a polyimide film having a first layer circuit formed on both sides by heat lamination or heat pressing. The conditions at this time are set appropriately depending on the type of the adhesive layer, but when the conductor layer is a copper foil, it is preferably 300 ° C. or lower in order to suppress oxidative deterioration. Further, from the viewpoint of surface smoothness, it is preferable to bond them with the carrier for peeling provided. Next, the peeling carrier is peeled off to form a via hole on the conductor layer immediately above the land of the first layer circuit of the metal foil. Examples of the forming method include various lasers, plasma etching, chemical etching and the like. After forming the via hole, the via shape is adjusted by a desmearing process if necessary.
Next, the via holes are electrically connected by a method such as embedding a conductive paste and plating. Subsequently, the conductor layer of the laminate of the present invention is patterned and then etched to form a new circuit. By repeating the steps up to, a multilayer wiring board can be obtained.

Although the laminate of the present invention and the method for manufacturing a multilayer wiring board using the laminate have been described above, the present invention is not limited to these and is within a range not departing from the spirit of the present invention. , Various improvements based on the knowledge of those skilled in the art,
It can be implemented in a modified or modified form.

[0057]

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

(Example 1) In a glass flask having a volume of 2000 ml, dimethylformamide (hereinafter referred to as DMF), 0.95 equivalent of 1,3-bis (aminophenoxy) benzene (hereinafter referred to as APB) and 0 were added. .05
An equivalent amount of 3,3′-dihydroxy-4,4′-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) was charged and dissolved under stirring in a nitrogen atmosphere. Furthermore, under a nitrogen substitution atmosphere in the flask,
The solution was stirred while cooling with ice water and 1 equivalent of 2,2-bis (4-hydroxyphenyl) propanedibenzoate-
3,3 ′, 4,4′-Tetracarboxylic acid dianhydride (hereinafter referred to as ESDA) was added. Thus, a polyamic acid polymer solution was obtained. The amount of DMF used is APB, 3,3′-dihydroxy-4,4′-
The monomer charge concentration of diaminobiphenyl and ESDA was adjusted to 30% by weight.

300 g of this polyamic acid solution was placed in a vat coated with Teflon (R) and placed in a vacuum oven for 2 hours.
The mixture was heated at 00 ° C for 180 minutes under reduced pressure at 665 Pa to obtain 80 g of a thermoplastic polyimide resin having a hydroxyl group.

The polyimide resin powder obtained above, a novolac 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 70:
The mixture was mixed at 30: 9 to obtain an adhesive solution.

Next, DMF, 4,4'-diaminobenzanilide (3 equivalents) and 4,4'-diaminodiphenyl ether (1 equivalent) were placed in a glass flask having a volume of 2000 ml, and the mixture was allowed to stand at room temperature until the diamine compound was completely dissolved. Stir and then cool with ice. Next, 4 equivalents of p-phenylene bis (trimellitic acid monoester anhydride) was added, and the mixture was cooled and stirred for 1 hour to obtain a DMF solution of polyamic acid. The amount of DMF used was 18% by weight as the monomer charge concentration of the diamine compound and the aromatic tetracarboxylic acid compound.
So that To 100 g of the above polyamic acid, 10 g of acetic anhydride and 8 g of isoquinoline were added and uniformly stirred, followed by defoaming and casting and coating on a glass plate to give about 11
After drying at 0 ° C for about 5 minutes, the polyamic acid coating was peeled off from the glass plate, and the content of volatile components was 40% by weight and the imidization rate was 85%.
A gel film having self-supporting property was obtained. Fix this gel film on the frame and then at about 200 ℃ for about 10 minutes.
Heating for about 10 minutes at about 300 ° C., about 10 minutes at about 400 ° C., about 10 minutes at about 500 ° C., dehydration ring closure drying,
A polyimide film having a thickness of about 12 μm was obtained. This film has a tensile modulus of 10 GPa and a linear expansion coefficient of 4.0 ×.
The water absorption was 10 ⁻⁶ / ° C. and 1.1%. The adhesive solution is applied to one surface of the polyimide film by a gravure coater and dried at a temperature of 170 ° C. for 1 minute and 30 seconds to give a thickness of 5
An adhesive layer having a thickness of μm was formed. The obtained polyimide film with a single-sided adhesive layer was laminated with a hot roll laminator at 200 ° C. so that the surface of the adhesive layer was in contact with the matte surface of a 5 μm electrolytic copper foil with a 35 μm carrier copper foil. Further, the above adhesive was applied to the surface opposite to the copper foil by a gravure coater and dried at a temperature of 170 ° C. for 1 minute and 30 seconds to form an adhesive layer having an adhesive layer thickness of 9 μm to obtain a laminate. . The heat fluidity of the adhesive layer was 61%. On the adhesive layer on the opposite side of the conductor layer of this laminate, a matte surface of 18 μm thick rolled copper foil is thermocompression-bonded at a temperature of 200 ° C. and a pressure of 3 MPa for 60 minutes to cure the adhesive layer, and then laminate with this copper foil. The peel strength from the body was measured and found to be 9.2 N / cm. The copper foil of the FR-4 board was patterned to give a conductor layer thickness of 9 μm and a line and space of 100 μm and 100 μm.
An inner layer circuit board having the circuit pattern of No. 1 was produced. With the carrier copper foil attached, a temperature of 20 was applied so that the pattern surface of this inner layer circuit board and the adhesive layer of the above-mentioned laminate contact each other.
It was thermocompression bonded at 0 ° C. and a pressure of 3 MPa for 60 minutes to produce a laminated plate. The carrier copper foil is peeled off, and the line and space is 100 μm and 100 μm with a stylus type surface roughness meter.
The surface unevenness on the circuit pattern of No. 1 was measured and found to be 1 μm or less. The flattening rate was 90%.

Example 2 Epicoat 1 of Epoxy Resin
032H60 is 1032H60 and urethane modified epoxy resin (EPU-73: Asahi Denka Co., Ltd.), polyimide,
Epicoat 1032H60, EPU-73, 4, 4'-
A laminate was obtained in the same manner as in Example 1 except that the DDS weight ratio was 50: 30: 20: 15. The heat fluidity of the adhesive layer was 95%. When the peel strength between the 18 μm thick rolled copper foil and the laminate was measured in the same manner as in Example 1, it was 8.7 N / cm. In addition, Example 1
A laminated plate was prepared in the same manner as in, and the line and space was 100 μm and 100 μm using a stylus surface roughness meter
The surface unevenness on the circuit pattern of No. 1 was measured and found to be 1 μm or less. The flattening rate was 90%.

Example 3 Patterning was performed on the copper on both sides of the laminated board obtained in Example 1 to form a circuit having a line and space of 100 μm and 100 μm. The adhesive layer of the laminate obtained in Example 1 was laminated again with the carrier copper foil attached so that both pattern surfaces of the laminate were in contact with each other, and thermocompression bonding was performed at a temperature of 200 ° C. and a pressure of 3 MPa for 60 minutes to form a wiring board. Was produced. U just above the land of the inner layer circuit of this wiring board
Via holes were formed with a V laser, the via hole shape was adjusted by desmear treatment, and the via holes were electrically connected by electroless copper plating and electrolytic copper plating. Further, patterning was performed on both surfaces of the wiring board to form a circuit, and a multilayer wiring board was produced. When the surface roughness on the inner layer circuit pattern with a line and space of 100 μm and 100 μm was measured with a stylus type surface roughness meter, it was 1 μm.
When the thickness was m or less, the flattening rate was 90%. Further, the inner layer circuit of the multilayer wiring board had no short circuit or disconnection, and the adhesion between the laminate and the inner layer circuit board or between the laminates was high.

Example 4 A multilayer wiring board was produced in the same manner as in Example 3 using the laminate and the laminate obtained in Example 2. The surface roughness on the inner layer circuit pattern having a line and space of 100 μm and 100 μm was measured with a stylus type surface roughness meter, and it was 1 μm or less and the flattening rate was 90%. Further, the inner layer circuit of the multilayer wiring board had no short circuit or disconnection, and the adhesion between the laminate and the inner layer circuit board or between the laminates was high.

(Example 5) The thickness of the adhesive layer opposite to the copper foil of the laminated body was 12 μm, and the thickness of the conductor layer of the inner layer circuit board was 12 μm.
A laminated board was produced in the same manner as in Example 1 except that m was changed to
Line and space is 10 with a stylus type surface roughness meter
The surface roughness on the circuit pattern of 0 μm and 100 μm was measured and found to be 1 μm or less. The flattening rate was 92%.

Example 6 The thickness of the adhesive layer opposite to the copper foil of the laminate was 18 μm, and the thickness of the conductor layer of the inner layer circuit board was 18 μm.
A laminated board was produced in the same manner as in Example 1 except that m was changed to
Line and space is 10 with a stylus type surface roughness meter
The surface roughness on the circuit pattern of 0 μm and 100 μm was measured and found to be 1 μm or less. The flattening rate was 95%.

(Example 7) A laminated board was prepared and touched in the same manner as in Example 2 except that the thickness of the adhesive layer opposite to the copper foil of the laminate was 5 µm and the thickness of the conductor layer of the inner layer circuit board was 9 µm. Line and space is 100μ with needle type surface roughness meter
The surface irregularities on the circuit pattern of m and 100 μm were measured and found to be 1 μm or less. The flattening rate is 90
%Met.

(Comparative Example 1) APB (0.
95 equivalent) and 3,3'-dihydroxy-4,4'-
Diaminobiphenyl (0.05 equivalent) was added to 3,3'-bis (3-aminophenoxyphenyl) sulfone (1 equivalent)
A polyamic acid polymer solution was obtained in the same manner as in Example 1 except that the above was used to obtain a polyimide resin powder.

An adhesive solution was obtained from the above-obtained polyimide resin powder in the same manner as in Example 1.

Using the adhesive solution obtained above, a laminate was obtained in the same manner as in Example 1. The thermal fluidity of the adhesive layer was less than 1%. When the peel strength between the 18 μm thick rolled copper foil and the laminate was measured in the same manner as in Example 1, 6.
It was 1 N / cm. Further, a laminated plate was prepared in the same manner as in Example 1, and the surface roughness on the circuit pattern having a line-and-space of 100 μm and 100 μm was measured with a stylus type surface roughness meter, and it was 3 μm. The flattening rate was 67%.

(Comparative Example 2) A multilayer wiring board was produced in the same manner as in Example 3 using the laminate and the laminated board obtained in Comparative Example 1, and the inner layer circuit of the obtained multilayer wiring board was short-circuited or disconnected. There was no. On the other hand, when the surface roughness on the inner layer circuit pattern with a line and space of 100 μm and 100 μm was measured with a stylus type surface roughness meter, it was 3 μm.
The flattening rate was 67%. Moreover, the inner layer circuit of the multilayer wiring board had no short circuit or disconnection, but the laminated body and the inner layer circuit board,
In addition, the adhesion between the laminates was low.

(Comparative Example 3) A two-layer printed wiring board wiring board was produced in the same manner as in Example 1 except that the carrier copper foil was removed from the carrier copper foil. Line and space = 100μ with a stylus type surface roughness meter
The surface roughness on the circuit pattern of m and 100 μm was 3 μm. The flattening rate was 67%.

The tensile modulus was determined according to the method of ASTM D882. Regarding the linear expansion coefficient, heating and cooling at room temperature to 400 ° C. were repeated under a nitrogen stream at an ascending / descending speed of 10 ° C./min, and the average linear expansion coefficient at 100 ° C. to 200 ° C. at the second rise was measured. The measuring equipment is Rigaku Denki TMA814
0 was used.

The water absorption was measured according to the method of ASTM D-570. Specifically, the film is heated at 150 ° C. for 30 minutes.
The weight of the _one dried for minutes was W _1, and the weight of the _one wiped on the surface after soaking in distilled water for 24 hours was W _2, and calculated by the following formula. Water absorption rate (%) = (W ₂ −W ₁ ) ÷ W ₁ × 100 The peel strength was measured according to JIS C 6481.

The heat fluidity of the adhesive layer is 50 mm in length and width.
Then, a polyimide film with a single-sided adhesive in which punch holes with a diameter of 1 mm were made at 5 locations (application, hot air oven 17
An adhesive layer of a polyimide film with an adhesive having a thickness of 9 μm) dried at 0 ° C. for 5 minutes and kept in a semi-cured state, and the length and width are 1
After pressing for 1 hour at a temperature of 200 ° C. and a pressure of 3 MPa so that the shine surface of the rolled copper foil of 00 mm was in contact, the five-point average value of the area of the adhesive layer that flowed out into the punch hole of 1 mm in diameter was a, and the diameter was 1 mm. When the five-point average value of the area of the punched holes in (1) was defined as b, it was calculated by the following formula. Thermal fluidity of the adhesive layer (%) = (a / b) × 100 The flattening ratio is the unevenness of the inner layer circuit c, and the laminate of the present invention and the inner layer circuit board having the inner layer circuit are laminated. rear,
When the surface unevenness of the laminate corresponding to the unevenness of the inner layer circuit is d, it was calculated by the following formula.

Flattening rate (%) = (1-d / c) × 100

[0077]

INDUSTRIAL APPLICABILITY The laminate of the present invention can be widely used in the production of multilayer wiring boards and is industrially extremely useful as a material for electronics which requires high reliability, heat resistance and excellent surface smoothness. It has the advantage of high utility value.

Continued front page    F-term (reference) 4F100 AB17 AB33B AH02H AH03H                       AH04H AK01A AK49A AK49G                       AK53 AK53G AL05 AL05G                       AR00B AR00C BA03 BA05                       BA10B BA10C CA02 CB00                       DD07B GB43 JA06C JG01B                       JJ03 JK15 JL11C YY00B                       YY00C                 5E346 AA12 AA15 AA16 CC02 CC10                       CC32 DD02 DD12 DD32 EE31                       EE38 GG02 GG28 HH18 HH21                       HH26

Claims (6)

[Claims] 1. A conductor layer on one surface of a polymer film,
In a laminate having an adhesive layer on the other surface, the thickness of the adhesive layer is not more than 1 time the thickness of the inner layer circuit, and after the laminate and the inner layer circuit board are laminated, the unevenness of the inner layer circuit is formed. The surface roughness of the laminate corresponding to the above is 2 μm or less. 2. A conductor layer on one surface of the polymer film,
2. The laminate having an adhesive layer on the other surface, wherein the adhesive layer has a heat fluidity of 1% to 100% during lamination processing. 3. A conductor layer on one surface of the polymer film,
3. A laminate having an adhesive layer on the other surface, wherein the conductor layer is bonded by adhering the polymer film and the metal foil via the adhesive layer. The laminate described. 4. The conductor layer has a peeling carrier of 5 μm.
It is the following metal foil, The laminated body of Claim 1 thru | or 3 characterized by the above-mentioned. 5. The laminate according to claim 1, wherein the polymer film is a polyimide film. 6. A multilayer wiring board using the laminate according to any one of claims 1 to 5.