JP3379977B2 - Manufacturing method of flexible double-sided metal laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to the field of the electronic industry.
Manufacturing method of flexible double-sided metal laminate which is becoming popular
With no heat-resistant adhesive layer.
Long, all-polyimide flexible double-sided metal laminate
The present invention relates to a method for manufacturing a plate. [0002] 2. Description of the Related Art Flexible metal laminates are mainly
Used as a substrate for flexible printed wiring boards
However, other surface heating elements, electromagnetic wave shielding materials, flat
Used for cables, packaging materials, etc. In recent years,
Electronic equipment using printed wiring boards is becoming smaller and more dense
As a result, efficient densification can be achieved.
Therefore, the use of flexible double-sided metal laminates is increasing. However, conventional flexible double-sided gold
The metal laminate is made of epoxy resin using an adhesive such as epoxy resin.
By attaching metal foil to both sides of the mid film
Because it is manufactured, it has heat resistance, chemical resistance, flame retardancy,
The properties such as air quality are governed by the properties of the adhesive used.
The advantages of polyimide are fully utilized
, Especially heat resistance, copper migration resistance, radiation resistance
It was not enough in point. A conventional flexible vehicle having this adhesive
To overcome the shortcomings of surface metal laminates,
Directly on the polyimide layer of a single-sided metal laminate
Metal foil or all polyimide flexible single-sided metal product
By laminating the polyimide layer of the layer plate by heating and pressing
All polyimide flexible adhesive without adhesive
Attempts have been made to obtain surface metal laminates.
Low strength, or blisters occur when immersed in a solder bath
Have not been satisfied with
You. [0005] The object of the present invention is to provide an excellent
Flexibility, bending workability, heat resistance, chemical resistance, flame retardancy
・ Enhance the characteristics of polyimide film with electrical characteristics
To make the best use of it, there is no adhesive layer such as epoxy resin.
To provide flexible polyimide double-sided metal laminates
Is what you do. [0006] Means for Solving the Problems The present inventors have developed various characteristics.
Does not include an adhesive layer such as epoxy resin, which is the cause of
Manufactures all polyimide flexible double-sided metal laminates
As a result of intensive studies on the method of
An organic solvent is applied on the substrate directly coated with the polyamic acid varnish.
Polymerization and imidization reaction completed in a medium
The polyimide powder obtained by isolating and grinding the polyimide
Directly apply polyimide varnish obtained by dissolving in solvent
Solvent and / or polyamic acid as a substrate
All obtained by completing the imidation reaction of
Polyimide layer of polyimide single-sided metal laminate
In addition, metal foil or similar all-poly obtained by the above method
Add polyimide layer of imide flexible single-sided metal laminate
Flexi with excellent heat resistance by laminating under heat and pressure
And found that a double-sided metal laminate can be obtained.
Was completed. [0007] That is, the present invention provides a method of manufacturing a device on a metal foil or
Polyamic acid varnish applied directly on metal foil in advance
Polymerization reaction and imidization reaction in an organic solvent
Apply the polyimide varnish that has completed the reaction directly,
Removed and / or pre-applied on the substrate
By completing the imidization reaction of polyamic acid
Obtain an all-polyimide single-sided flexible metal laminate,
A polyimide layer, a metal foil, or obtained by the above method
Another all-polyimide flexible single-sided metal laminate
Characterized by laminating polyimide layers by heating and pressing
A method of manufacturing a flexible double-sided metal laminate,
Preferably, the secondary transition point of the polyimide layer is 160 ° C. or higher.
Manufacture of flexible double-sided metal laminates at 270 ° C or lower
And the polymer ends of the polyimide layer
Is sealed with dicarboxylic anhydride and / or monoamine
To manufacture flexible double-sided metal laminates
Law. Hereinafter, the present invention will be described in detail. Of the present invention
The most distinctive feature is the polymerization reaction in organic solvents and
Complete the imidization reaction and preferably cap the ends
Once the polyimide is isolated and crushed,
Powder, and dissolve the polyimide powder in the organic solvent again.
Polyimide varnish obtained on a metal foil or gold
Apply a polyamic acid varnish directly on the foil
Directly onto the substrate, and remove the solvent and / or
After completing the imidization reaction of a certain polyamic acid,
Thermocompression bonding and all polyimide flexible double-sided metal lamination
The point is to form a plate. In addition, the polyimide layer polymer
-The terminal is carboxylic anhydride and / or monoamine
The varnish is sealed with
Polymer flow above the second transition temperature
The point is that the mobility is improved and the bonding performance is improved. In addition, the polyimide for the polyimide layer
Completes the polymerization reaction and imidation reaction in an organic solvent.
After isolating and crushing the polyimide,
Can be stored in the form of polyimide powder.
Compared to mid varnish and polyamic acid varnish,
It is also characterized by good storage stability. In the present invention
The polyimide used for the polyimide varnish used is
For example, when the terminal of the polymer molecule is represented by the following formula (1): [0010] Embedded image (Wherein Z is a monocyclic aromatic group, a condensed polycyclic aromatic group,
Non-condensed aromatic groups directly or interconnected by a bridging member
Shows a divalent group selected from the group consisting of polycyclic aromatic groups.
Is sealed with a dicarboxylic anhydride represented by
2] Equation (2) [0011] Embedded image[0012] Embedded image And X is a direct bond, -CO- or -O-
Having a repeating unit represented by the following formula:
It is. Dissolve and contain this polyimide in a solvent that dissolves it
To form a polyimide varnish, apply and dry the varnish
A imide layer is obtained. In addition, or without dicarboxylic acid
Instead of the hydrate, the terminal of the polymer molecule is represented by the formula
(4) [0013] ## STR4 ## Q-NH_Two                (4) (Wherein Q is a monocyclic aromatic group, a condensed polycyclic aromatic group,
Non-condensed aromatic groups directly or interconnected by a bridging member
Shows a divalent group selected from the group consisting of polycyclic aromatic groups.
Is sealed with a monoamine represented by the formula (2) and represented by the formula (2).
Polyimide having repeating units
Polyimide varnish dissolved and contained in a solvent that dissolves
It may be applied and dried to form a polyamide layer. The polyimide according to the present invention comprises a diamine component.
1,3-bis (3-
Aminophenoxy) benzene (hereinafter abbreviated as APB)
) And 3,3 ', 4,
4'-diphenylethertetracarboxylic dianhydride
(Hereinafter abbreviated as ODPA), 3,3 ′, 4,4′-benzophen
Enone tetracarboxylic dianhydride (hereinafter abbreviated as BTDA)
Or 3,3 ', 4,4' biphenyltetracarboxylic acid
From the group consisting of dianhydrides (hereinafter abbreviated as BPDA)
At least one selected tetracarboxylic dianhydride and
Is a polymer obtained by polycondensation of
Dicarboxylic acid having a terminal reactive terminal group represented by the formula (1)
Polyimide encapsulated with an anhydride; and / or
Alternatively, the reactive terminal group at the terminal of the polymer molecule is represented by the formula (4).
Is a polyimide sealed with a monoamine. [0015] Embedded image The polyimide of the present invention has an aromatic diamine component
Aromatic tetracarbonsane dianhydride as main component
However, a range that does not impair the heat-resistant adhesion in the present invention.
[Formula 6] Formula (6) [0016] Embedded image (Where W is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group,
Monocyclic aromatic group, condensed polycyclic aromatic group, aromatic group directly
Or non-fused polycyclic aromatics interconnected by bridging members
Represents a tetravalent group selected from the group consisting of
Part, preferably 50 mol of tetracarboxylic dianhydride
% Or less, there is no problem. That is, tetracarboxylic acid which can be partially substituted
Examples of dianhydrides include ethylene tetracarboxylic acid
Hydrate, butanetetracarboxylic dianhydride, cyclopentane
Tetracarboxylic dianhydride, cyclohexanetetraca
Rubonic dianhydride, 1,2,3,4-benzenetetracarboxylic
Acid dianhydride, pyromellitic dianhydride, 2,3,6,7-naph
Tallentetracarboxylic dianhydride, 1,4,5,8-naphthale
Tetracarboxylic dianhydride, 1,2,5,6-naphthalene
Tracarboxylic dianhydride, 3,4,9,10-perylenetetraca
Rubonic anhydride, 2,3,6,7-anthracenetetracar
Bonic acid dianhydride, 1,2,7,8-phenanthrene tetracar
Boronic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarbo
Dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic
Acid dianhydride, 3,3 ', 4,4'-benzophenonetetracarbo
Dianhydride, 2,2 ', 3,3'-benzophenonetetracal
Boric acid dianhydride, 2,2-bis (3,4-dicarboxy
Nyl) propane dianhydride, 2,2-bis (2,3-dicarbo)
Xyphenyl) propane dianhydride, bis (3,4-dical)
Boxyphenyl) ether dianhydride, bis (2,3-dica)
Ruboxyphenyl) ether dianhydride, bis (3,4-di
Carboxyphenyl) sulfone dianhydride, bis (2,3-
Dicarboxyphenyl) sulfone dianhydride, 1,1-bis
(2,3-dicarboxyphenyl) ethane dianhydride, bis
(2,3-dicarboxyphenyl) methane dianhydride, bis
(3,4-dicarboxyphenyl) methane dianhydride, 4,4 ′
-(P-phenylenedioxy) diphthalic dianhydride, 4,
4 '-(m-phenylenedioxy) diphthalic anhydride
These may be used alone or in combination of two or more.
Used as Also, the present invention uses APB as a diamine.
Used as long as the heat resistance of the present invention is not impaired.
Partially preferably not more than 50 mol% of an aromatic diamine
But there is no problem. As a diamine compound which can be partially substituted
Is, for example, o-phenylenediamine, m-phenylenediamine
Amine, p-phenylenediamine, m-aminobenzyl
Amine, p-aminobenzylamine, 2-chloro-1,2
-Phenylenediamine, 4-chloro-1,2-phenylene
Diamine, 2,3-diaminotoluene, 2,4-diaminoto
Ruene, 2,5-diaminotoluene, 2,6-diaminotoluene
Ene, 3,4-diaminotoluene, 2-methoxy-1,4-
Phenylenediamine, 4-methoxy-1,2-phenylene
Diamine, 4-methoxy-1,3-phenylenediamine,
Benzidine, 3,3'-dichlorobenzidine, 3,3'-dimethyl
Rubenzidine, 3,3'-dimethoxybenzidine, 3,3'-di
Aminodiphenyl ether, 3,4'-diaminodiphenyl
Ether, 4,4'-diaminodiphenyl ether, 3,3'-
Diaminodiphenyl sulfide, 3,4'-diaminodife
Nyl sulfide, 4,4'-diaminodiphenyl sulfide
3,3'-diaminodiphenylsulfoxide, 3,4'-di
Aminodiphenyl sulfoxide, 4,4'-diaminodife
Nyl sulfoxide, 3,3'-diaminodiphenyl sulfo
3,4'-diaminodiphenyl sulfone, 4,4'-diamine
Nodiphenyl sulfone, 3,3'-diaminobenzopheno
3,4'-diaminobenzophenone, 4,4'-diaminoben
Nzophenone, 3,3'-diaminodiphenylmethane, 3,4 '
-Diaminodiphenylmethane, 4,4'-diaminodiphenyl
Methane, bis [4- (3-aminophenoxy) phenyl
Methane, bis [4- (4-aminophenoxy)
Nil] methane, 1,1-bis [4- (3-aminophenoxy
C) phenyl] ethane, 1,1-bis [4- (4-amino
Phenoxy) 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] p
Lopan, 2,2-bis [4- (4-aminophenoxy) furan
Enyl) propane, 2,2-bis [4- (3-aminophen
Noxy) phenyl] butane, 2,2-bis [4- (4-A
Minophenoxy) phenyl] butane, 2,2-bis [4-
(3-aminophenoxy) phenyl] -1,1,1,3,3,3-
Hexafluoropropane, 2,2-bis [4- (4-amido
Nophenoxy) phenyl] -1,1,1,3,3,3-hexafur
Olopropane, 1,3-bis (3-aminophenoxy)
Senzen, 1,3-bis (4-aminophenoxy) benze
1,4-bis (3-aminophenoxy) benzene,
4-bis (4-aminophenoxy) benzene, 4,4'-bis
(3-aminophenoxy) biphenyl, 4,4'-bis (4
-Aminophenoxy) biphenyl, bis [4- (3-
Minophenoxy) phenyl] ketone, bis [4- (4-
Aminophenoxy) phenyl] ketone, bis [4- (3
-Aminophenoxy) phenyl] sulfide, bis [4
-(4-aminophenoxy) phenyl] sulfide,
[4- (3-aminophenoxy) phenyl] sulfoxy
Sid, bis [4- (4-aminophenoxy) phenyl]
Sulfoxide, bis [4- (3-aminophenoxy)
Phenyl] sulfone, bis [4- (4-aminophenoxy)
C) phenyl] sulfone, bis [4- (3-aminophen
Noxy) phenyl] ether, bis [4- (4-amino
Phenoxy) phenyl] ether, 1,4-bis [4-
(3-aminophenoxy) benzoyl] benzene, 1,3
-Bis [4- (3-aminophenoxy) benzoyl] be
Senzen, 4,4'-bis [3- (4-aminophenoxy)
Nzoyl] diphenyl ether, 4,4'-bis [3-((3
-Aminophenoxy) benzoyl] diphenylate
4,4'-bis [4- (4-amino-α, α-dimethyl
Benzyl) phenoxy] benzophenone, 4,4'-bis
[4- (4-amino-α, α-dimethylbenzyl)
Noxy] diphenylsulfone, [bis4- ｛4- (4-
Aminophenoxy) phenoxy｝ phenyl] ketone, bi
[4- {4- (4-aminophenoxy) phenoxy}
Phenyl] sulfone, 1,4-bis [4- (4-aminophenyl
Enoxy) -α, α-dimethylbenzyl] benzene, 1,
3-bis [4- (4-aminophenoxy) -α, α-di
Methylbenzyl] benzene and the like.
Are used alone or in combination of two or more. The polyimide of the present invention comprises
A rubonic acid component and a diamine component of the above group
The secondary transition point is 160
The temperature can be controlled in the range of ℃ to 270 ℃. Further
In addition, this polyimide layer is a multilayer having different secondary transition points.
There is no problem with the structure. Also, flexible double-sided metal lamination
When laminating boards by thermocompression bonding, thermosetting between polyimide layers
Polyimide inherently has no chemical reaction
Loss properties such as softness, flexibility and bending processability
I won't sleep. The polyimide terminal of the present invention is sealed with a polymer terminal.
The carboxylic anhydride used for the purpose of stopping
Water phthalic acid, 2,3-benzophenodicarboxylic anhydride,
3,4 benzophenodicarboxylic anhydride, 2,3-dicarbo
Xylphenyl phenyl ether anhydride, 2,3-biphe
Nyldicarboxylic anhydride, 3,4-biphenyldicarboxylic
Acid anhydride, 2,3-dicarboxyphenyl phenyl sulfone
Acid anhydride, 3,4-dicarboxyphenyl phenyl sulfone
Acid anhydride, 2,3-dicarboxylphenylphenylsul
Foyd anhydride, 3,4-dicarboxylphenyl
Nyl sulfoic anhydride, 1,2-naphthalenedicarbo
Acid anhydride, 2,3-naphthalenedicarboxylic acid anhydride, 1,
8-naphthalenedicarboxylic anhydride, 1,2-anthracene
Dicarboxylic anhydride, 2,3-anthracene dicarboxylic acid
Acid anhydride, 1,9-anthracene dicarboxylic anhydride, etc.
No. These dicarboxylic anhydrides are amine or
Is substituted with a group having no reactivity with dicarboxylic anhydride.
No problem. The polyimide layer of the present invention is sealed with a polymer terminal.
Monoamines used for the purpose of stopping
, O-toluidine, m-toluidine, p-toluidine
2,3-xylidine, 2,4-xylidine, 2,5-xylidine
Lysine, 2,6-xylidine, 3,4-xylidine, 3,5-
Xylidine, o-chloroaniline, m-chloroanili
, P-chloroaniline, o-bromoaniline, m-butane
Lomoaniline, p-bromoaniline, o-nitroanili
, M-nitroaniline, p-nitroaniline, o-a
Minophenol, m-aminophenol, p-aminophenol
Enol, o-anisidine, m-anisidine, p-anis
Cydin, o-phenetidine, m-phenetidine, p-fu
Enethidine, o-aminobenzaldehyde, m-amino
Benzaldehyde, p-aminobenzaldehyde, o-
Aminobenznitrile, m-aminobenznitrile, p
-Aminobenznitrile, 2-aminobiphenyl, 3-
Aminobiphenyl, 4-aminobiphenyl, 2-amino
Phenol phenol ether, 3-aminophenol
Phenol ether, 4-aminophenol phenol
Ether, 2-aminobenzophenone, 3-aminobenzo
Phenone, 3-aminobenzophenone, 2-aminopheno
Phenyl sulfide, 3-aminophenol phenyl
Rusulfide, 4-aminophenol phenyl sulfa
Id, 2-aminophenol phenyl sulfone, 3-amino
Phenolphenyl sulfone, 4-aminophenolfe
Nyl sulfone, α-naphthylamine, β-naphthylami
, 1-amino-2-naphthol, 2-amino-1-na
Phthal, 4-amino-1-naphthol, 5-amino-
1-naphthol, 5-amino-2-naphthol, 7-a
Mino-2-naphthol, 8-amino-2-naphthol, 1
 -Aminoanthracene, 2-aminoanthracene, 9
-Aminoanthracene and the like. These aromatic molybdenum
Noamine may be used alone or in combination of two or more.
There is no title. In addition, dicarboxylic anhydrides of the above group and aromatic
Noamine may be used in combination. The reaction for producing polyimide is usually carried out using an organic solvent.
Implemented in As a solvent used for this reaction, N-meth
Tyl-2-pyrrolidone, N, N-dimethylacetamide
, N, N-dimethylformamide, 1,3-dimethyl-
2-imidazolidinone, N, N-dimethylacetamido
, N, N-dimethyl methoxyacetamide, dimethyl
Sulfoxide, pyridine, dimethyl sulfone, hexame
Tylphosphoramide, tetramethylurea, N-methylca
Prolactam, Petyrolactam, Tetrahydrofuran,
m-dioxane, p-dioxane, 1,2-bis (2-me
Toxiethoxy) ethane, bis 2- (2-methoxyethoxy)
B) Ethyl ether, tetrahydrofuran, 1,4-dithio
Xane, picoline, o-cresol, m-cresol,
p-cresol, cresylic acid, p-chlorophenol
Phenol, anisole and the like. These
Solvent may be used alone or as a mixture of two or more.
You. The polyimide according to the present invention is a diamine compound.
APB mainly as a compound component and tetracarboxylic dianhydride
BTDA and / or BTDA and / or
And / or ODPA as a terminal blocking component
Organic solution in the presence of acid anhydride and / or monoamine
Synthesized in a medium. The terminal is mainly sealed with a dicarboxylic anhydride.
The amount of tetracarboxylic dianhydride used in
The molar ratio is preferably 0.8 to 0.999.
If the amount is less than 0.8 mol, the degree of polymerization of the polymer is not sufficient.
Heat resistance is impaired, and if it exceeds 0.999,
It becomes difficult to seal the polymer end, and polyimide varnish
No longer available. Also, a diamine compound component, tetraca
Addition and reaction of rubonic acid dianhydride component and terminal blocking component
There is no limitation on the method.
Even after adding, only specific components are added and reacted later.
There is no problem. Manufacture this polyamic acid
The reaction temperature at this time is usually preferably 70 ° C. or lower. Also react
The pressure is not limited and can be manufactured at normal pressure. The reaction time is
Depends on polyimide type, solvent type and reaction temperature
But in 1.5 to 48 hours, preferably 3 to 24 hours
Is enough. When the terminal is mainly sealed with a monoamine,
The amount of the diamine compound used is tetracarboxylic dianhydride.
A molar ratio of 0.8 to 0.999 is preferred. 0.8 m
If the molecular weight is less than 100, the degree of polymerization of the polymer is not sufficient,
Is impaired, and when it exceeds 0.999, the polymer powder
Edge sealing becomes difficult and polyimide varnish cannot be obtained
Become. In addition, a diamine compound component,
Restriction on addition and reaction method of anhydride component and terminal blocking component
No, even if they are added at the same time,
Even if only specific components are added and reacted later,
No problem. Reaction temperature when producing this polyamic acid
The degree is usually preferably 70 degrees or less. Also limited to reaction pressure
And can be manufactured at normal pressure. Reaction time is polyimide
Depends on the type of solvent, the type of solvent, and the reaction temperature.
48 hours, preferably 4 to 24 hours, is sufficient. By this reaction, the polyimide precursor
Certain polyamic acid varnishes are obtained. Like this
The obtained polyamic acid is further heated to 100 to 350 ° C.
The imidation reaction is performed by heating to obtain a polyimide. Imide
The water generated by the oxidation reaction reacts with azeotropic substances such as toluene.
In addition to the reaction system, it may be removed by azeotropic distillation. Up
In addition to the thermal imidization reaction, an imidizing agent such as acetic anhydride is used.
And a polyimide may be obtained chemically. At this time,
Pyridine, γ-picoline, imidazole, trie
Tertiary amines such as tylamine may be added as a catalyst.
No. When chemically imidizing, the reaction temperature is usually room temperature.
Temperature to 200 ° C or lower, preferably 100 ° C or lower
It is. The reaction is preferably carried out at normal pressure for 0.2 to 48 hours.
In other words, 0.5 to 24 hours is sufficient. The reaction mixture containing the polyimide is
Discharge to poor polyimide solvent or add poor solvent to reaction system
To deposit the polyimide by either
Solvent or catalyst present in the polyimide-containing mixture
Etc. are removed by heating or / and reducing
Is isolated. This isolated polyimide is crushed and
Obtain flour. Dissolved in a solvent that dissolves this polyimide powder
To obtain a polyimide varnish. Solvent used here
Is an example of the above-mentioned organic solvent. Thus formed
Polyimide powder is used as a polyamic acid varnish or polyimide.
Good storage stability compared to Dowanis. Also, this port
The limide powder was subjected to IR analysis (measurement instrument: JASCO Corporation I
As a result of the measurement in RA-1),
No imprint was observed, and completion of the imidization reaction was confirmed. The type of metal foil used in the present invention is particularly
There is no limitation, usually copper, nickel, aluminum, stainless steel
Stainless steel, beryllium-copper alloy foil, nickel-copper alloy foil
Etc. are often used, and in the case of copper foil, rolled copper
Both foil and electrolytic copper foil can be used. The thickness of the metal foil is
Usually 4 to 105 μm, preferably 9 to 70 μm
is there. In addition, polyimide and metal directly in contact with the metal foil
In order to increase the adhesion to the foil, the metal
Oxide or alloy, for example, when the metal foil is copper foil, copper alone
And inorganic substances such as copper oxide, nickel-copper alloy and zinc-copper alloy
May be formed.
, Epoxysilane, mercaptosilane, etc.
The agent may be formed on the metal foil. Also, degreasing,
Chemical treatment with acid or alkali, heat treatment, corona treatment
Processing, plasma processing, sandblasting, honing
Treatment, ultraviolet irradiation, radiation irradiation and the like are also possible. Further, a polyamid is formed on these metal foils.
Cinic acid varnish is applied directly, and further according to the invention
A polyimide varnish may be applied. This polyamic
The acid is a set of the tetracarboxylic acid group and the diamine group described above.
There is no particular limitation as long as it consists of mating.
Or copolymerization. In addition, the above carvone
The terminal of the acid anhydride group and / or the monoamine group
There is no problem even if it is sealed. Also, this polyamic
Acid varnish is usually produced in an organic solvent,
Single or two or more solvents included in the solvent group
Even if mixed and used, there is no problem in varnish formation. This
The production conditions for the polyamic acid varnish of
Same as polyamic acid production process
Polypropylene that can be manufactured under conditions and is currently commercially available
Amic acid varnish may be used. Furthermore, this polyamide
The acid layer has different secondary transition points even in a single layer
Multi-layer structure may be used and also changes the properties of polyimide
It may contain additives, ferrers and the like. The polyimide varnish of the present invention is placed directly on a metal foil.
Direct application of polyamic acid varnish on metal foil
Contact coating method and polyamic acid varnish on metal foil
A polyimide varnish of the present invention is directly applied on a substrate directly coated with
There is no limitation on the method of contact coating, and a conventionally known
Tar, T die, roll coater, knife coater, river
Coating such as base coater, bar coater, gravure coater, etc.
What is necessary is just to apply using a cloth apparatus. Also screen sign
It is also possible to selectively apply polyimide varnish using the printing method
good. Solvent removal of polyimide varnish layer, polyamide
Reaction of Polyamic Acid Varnish Layer and Polyamic Acid Varnish
The method of removing the solvent of the varnish layer includes heating the organic solvent above its boiling point.
I hope I can do it. Nitrogen, Al
Heating in an inert gas such as gon is preferred. This inert
When considering gas sealing, the heating temperature should be less than 600 ° C.
It is practical. For the heating time,
Depending on the type, type of solvent and heating temperature, usually 1
A range from 0 seconds to 24 hours is sufficient. The substrate obtained by the above method or the substrate
Double-sided metal laminate consisting of coated substrate and metal
(1) Polyimide varnish on metal foil 1 as shown in FIG.
Is directly applied, the solvent is removed and the polyimide layer 2 is formed.
Both sides obtained by heat-pressing the material and metal foil 1
Metal laminate, (2) Polyimi on metal foil 1 as shown in FIG.
The polyimide of the base material from which the solvent has been removed after directly applying the varnish
Flexible double-sided surface obtained by heat-pressing the surfaces of layer 2
(3) Polyamide on metal foil 1 as shown in FIG.
Varnish 4 is applied directly, and then polyimide
After applying varnish directly to form polyimide layer 2, polyimide
Solvent removal of varnish layer and imide of polyamic acid varnish layer
Reaction and group removed from solvent of polyamic acid varnish layer
Both sides obtained by heat-pressing the material and metal foil 1
(4) Polyamide on metal foil as shown in Fig. 4
The varnish 4 was directly applied, and then a polyimide varnish was further applied.
After the varnish is directly applied to form the polyimide layer 2, the polyimide
Solvent removal of varnish layer and imidization of polyamic acid varnish layer
Substrate with solvent removed from reaction and polyamic acid varnish layer
Flexib obtained by thermocompression bonding polyimide surfaces
(5) Poly-metal on metal foil as shown in Fig. 5
Amic acid varnish 4 was directly applied,
After applying the varnish directly, remove the solvent from the polyimide varnish layer.
Reaction of polyamic acid varnish layer
Remove the solvent from the amic acid varnish layer
Immediately after applying the polyimide varnish, remove the solvent
Flexible layers obtained by heating and pressing the surfaces of
Surface metal laminates,
This is an embodiment, but of course is not limited to this.
No. Further, these flexible double-sided metal laminates
In, the type and thickness of the metal foil on both sides of the polyimide layer,
There is no problem if the surface treatment conditions are the same or different. This
Here, the product of the heat-press bonding of the flexible double-sided metal laminate
The layer method is not particularly limited, a conventionally known vacuum press,
What kind of hot roll press, autoclave press, etc.
A method may be used. The vacuum press method and the autoclave press method
In this case, the pressing temperature is preferably from 100 ° C. to 400 ° C.
Is 350 ° C. from the second order transition temperature, and the pressing pressure is 1
From 1000kgf / cm^TwoPreferably 7 in practice
200kgf / cm^TwoAnd another 20 seconds to 48 hours
Thermocompression bonding. Thus, good flexible double-sided metal
A laminate can be obtained. In the case of the hot roll press method, the press temperature
Is between 100 ° C and 400 ° C, preferably the second order transition temperature
At 350 ° C. and press line pressure from 0.05 to 20
00 kgf / cm, practically preferably 0.5 to 300
In kgf / cm, the speed is 0.005 to 50 m / min.
Flexible double-sided gold
A metal laminate can be obtained. Also, the laminated base before pressing
Degreasing treatment, chemical treatment with acid or alkali
Treatment, heat treatment, corona treatment, plasma treatment, sand bra
Strike treatment, honing treatment, ultraviolet irradiation, radiation irradiation, etc.
Is also possible. [0036] The present invention will be described in more detail with reference to the following examples.
I do. Example 1 APB 29.2 g (0.1 mol) N, N-dimethylacetate
245.6 g of toamide was stirred and dissolved at room temperature under a nitrogen atmosphere.
I understand. To this, 31.87 g of BTDA (0.099
Was added in portions and stirred at room temperature for 24 hours. That
Thereafter, 1.184 g (0.008 mol) of phthalic anhydride was added.
Then, the mixture was stirred at room temperature for 3 hours. Polyamide thus obtained
Acid was 0.75 dl / g in logarithmic viscosity (measurement
Is 0.5% concentrated in N, N-dimethylacetamide solvent
At 35 ° C). None of the above polyamic acid solvents
40.8 g (0.4 mol) of aqueous acetic acid and triethylamine 2
0.2 g was added dropwise and the mixture was stirred at room temperature for 10 hours. Obtained anti
Reaction mixture into 1000 g of methanol under vigorous stirring.
Then, the precipitate was separated by filtration. The obtained powdery precipitate is
After further washing with methanol, drying at 180 ° C. for 12 hours
Thus, 56.9 g of a polyimide powder was obtained. The obtained polyimide powder has a secondary transition point
Temperature of 192 ° C. (measured by DSC), logarithmic viscosity of 0.1.
76 dl / g (measurement is p-chlorophenol / phenol)
0.5% concentration in a mixed solvent of 9/1 weight ratio, 35 ° C.
And the result of IR analysis showed that polyamic
No characteristic peak of the acid was identified. Thus obtained
The polyimide powder was N-methyl-2-pyrrolidone 80 g.
(Concentration: 20%) to obtain a polyimide varnish. This varnish was coated with a rolled copper foil (thickness: 35 μm)
Product name: BHY foil, hereinafter abbreviated as rolled copper foil
To a temperature of 250 ° C. for 30 minutes in a nitrogen atmosphere.
Heat dried. The thickness of the polyimide layer obtained after drying is 1
It was 3 μm. The obtained polyimide coated copper foil and thickness 3
A 5 μm rolled copper foil was heated and pressed by a vacuum press.
The pressing conditions at this time are 240 ° C., 50 kgf / cm^Two
For 30 minutes. Heat and pressure bonding of this double-sided metal laminate
The 180 degree peel strength of the surface (copper-polyimide interface)
It was 2.6 kgf / cm. Furthermore, this double-sided metal lamination
Even if the board is immersed in 260 ° C solder for 1 minute, it swells and peels off.
There was no change such as discoloration. FIG. 1 shows a schematic diagram of this configuration example.
You. Comparative Example 1 29.2 g (0.1 mol) of APB and N, N-dimethylamine
245.6 g of cetamide was stirred at room temperature under a nitrogen atmosphere.
Dissolved. To this, 31.87 g of BTDA (0.099
Mol) was added in portions and stirred at room temperature for 24 hours. Or
The polyamic acid thus obtained has a logarithmic viscosity of 0.76 d
1 / g (measurement was performed with N, N-dimethylacetamide).
0.5% concentration in solvent, 35 ° C). Poly above
40.8 g (0.4 mol) of acetic anhydride in amic acid solvent
20.2 g of triethylamine was added dropwise and stirred at room temperature for 10 hours.
Stirred. The obtained reaction mixture was diluted with 1000 g of methanol.
The mixture was discharged under strong stirring, and the precipitate was separated by filtration. Get
After washing the powdery precipitate further with methanol,
For 12 hours to obtain 55.7 g of a polyimide powder.
The obtained polyimide powder has a secondary transition temperature of 192.
° C (measured by DSC). This polyimide powder was treated with N-methyl-2-pi
Lolidone, N, N-dimethylacetamide, N, N-di
Methylformamide, m-cresol, p-phenol
Phenol, phenol and a mixture of p-phenol and phenol
Dissolve the mixture by adding temperature, pressure and stirring for 24 hours.
Tried to dissolve enough due to gelation
An imido varnish could not be obtained. Embodiment 2 The tetracarboxylic dianhydride component in Example 1 was changed to B
The same conditions as in Example 1 were changed from TDA to BPDA.
To obtain a polyimide varnish (logarithmic viscosity 0.77 dl / g)
Was. Then, under the same conditions as in Example 1, rolled to a thickness of 35 μm
Pressed with copper foil. Table 1 shows the evaluation results. Embodiment 3 The tetracarboxylic dianhydride component in Example 1 was changed to B
The same conditions as in Example 1 were changed from TDA to ODPA.
To obtain a polyimide varnish (logarithmic viscosity 0.82 dl / g)
Was. Then, under the same conditions as in Example 1, rolling was performed to a thickness of 35 μm.
Pressed with copper foil. Table 1 shows the evaluation results. Embodiment 4 1.184 g of phthalic anhydride in Example 1 (0.00
8 mol) instead of 3-naphthalenedicarboxylic anhydride
All except using 1.585 g (0.008 mol)
The same operation as in Example 1 was performed, and the logarithmic viscosity was 0.75 dl /
g of polyamic acid and its varnish, and logarithmic viscosity
0.76 dl / g polyimide powder (secondary transition point 192
° C). Further, N-methyl-2-pi
A polyimide varnish of lolidone was prepared. And examples
Pressed with rolled copper foil of 35 μm thickness under the same conditions as in 1.
Was. Table 1 shows the evaluation results. Embodiment 5 1.184 g of phthalic anhydride in Example 1 (0.00
8 moles) instead of maleic anhydride 0.656 g
(0.008 mol) except that Example 1 was used.
Operation, a polyamid with a logarithmic viscosity of 0.72 dl / g
Citric acid and its varnish, and logarithmic viscosity 0.72 dl /
g of polyimide powder (secondary transition point: 192 ° C.) was obtained. Further
As in Example 1, poly (N-methyl-2-pyrrolidone)
A mid varnish was prepared. Then, under the same conditions as in Example 1,
It was pressed with a rolled copper foil having a thickness of 35 μm. Table 1 shows the evaluation results.
Shown in Embodiment 6 32.2 g (0.1 mol) of BTDA and N, N-dimethyl
245.6 g of acetamide was stirred at room temperature under a nitrogen atmosphere.
・ Dissolved. To this, 28.9 g of APB (0.099
Was added in portions and stirred at room temperature for 24 hours. That
Thereafter, 0.745 g (0.008 mol) of aniline was added,
Stir at room temperature for 3 hours. Polyamic obtained in this way
The acid had a logarithmic viscosity of 0.73 dl / g. Acetic anhydride 4 is added to the above polyamic acid solvent.
0.8 g (0.4 mol) and 20.2 g of triethylamine
Was added dropwise and stirred at room temperature for 10 hours. The resulting reaction mixture
Was discharged into 1000 g of methanol under vigorous stirring,
The product was separated by filtration. The obtained powdery precipitate is further meta-
After washing with ethanol, it was dried at 180 ° C for 12 hours.
56.9 g of a mid powder was obtained. The obtained polyimide powder has a secondary transition point
Temperature: 191 ° C. (measured by DSC), logarithmic viscosity: 0.1.
It was 74 dl / g, and as a result of IR analysis,
Was not confirmed. Thus obtained,
Dissolve polyimide powder in 80 g of N-methyl-2-pyrrolidone
This was disassembled to obtain a polyimide varnish. And the same as in the first embodiment
And pressed with a rolled copper foil having a thickness of 35 μm. Evaluation
The results are shown in Table 1. Embodiment 7 The tetracarboxylic dianhydride component in Example 6 was changed to B
The same conditions as in Example 1 were changed from TDA to BPDA.
To obtain a polyimide varnish (logarithmic viscosity 0.84 dl / g)
Was. Then, under the same conditions as in Example 1, rolling was performed to a thickness of 35 μm.
Pressed with copper foil. Table 1 shows the evaluation results. Embodiment 8 The tetracarboxylic dianhydride component in Example 6 was changed to B
The same conditions as in Example 1 were changed from TDA to ODPA.
To obtain a polyimide varnish (logarithmic viscosity 0.78 dl / g)
Was. Then, under the same conditions as in Example 1, rolling was performed to a thickness of 35 μm.
Pressed with copper foil. Table 1 shows the evaluation results. Embodiment 9 Polyimide surface of the polyimide-coated copper foil obtained in Example 1
Lay each other, 240 ° C, 50kg by vacuum press
f / cm^TwoFor 30 minutes. This flexible frame
The peel strength of the Xibull double-sided metal laminate is also 2.5kgf /
cm. In addition, peeling at the thermocompression bonding interface was not measured.
It was firmly adhered to it. The obtained flexible cable
The flexible double-sided metal laminate is similar to Example 1 in appearance.
No change, and expansion even after immersion in 260 ° C solder for 1 minute
There was no change such as peeling or discoloration. FIG. 2 shows an example of this configuration.
FIG. Embodiment 10 Polyimide-coated copper foil obtained in Example 1 and 35 μm thick
Rolled copper foil was heated and pressed by an autoclave. This
The pressing conditions at the time are 250 ° C., 19 kgf / cm^Twoso
Hold for 30 minutes. Of this flexible double-sided metal laminate
The 180-degree peel strength at the interface of thermocompression bonding is 2.3 kgf /
cm. The resulting flexible flexible double-sided
The appearance of the metal laminate was not different from that of Example 1 in appearance.
Swelling, peeling and deformation even after immersion in solder at 260 ° C for 1 minute
There was no change in color or the like. Embodiment 11 Polyimide surface of the polyimide-coated copper foil obtained in Example 1
The pieces were overlapped and continuously laminated by a hot roll press.
Pressing conditions: 270 ° C, 50kgf / cm, running speed
It was 0.1 m / min. This flexible double-sided metal
180 degree peel strength of laminate (copper-polyimide interface)
It was 2.5 kgf / cm. The thermocompression bonding interface (Po
Peeling at the polyimide-polyimide interface)
It was firmly adhered. The resulting flexible double-sided metal
The appearance of the laminate was not different from that of Example 1 in appearance, and
Swelling, peeling, discoloration, etc. even when immersed in solder at 60 ° C for 1 minute
There was no change. Embodiment 12 Polyamid composed of p-phenylenediamine and BTDA
N-methyl-2-pyrrolidone varnish of citric acid (concentration 20
%, Ube Industries, Ltd .: 1
Coated on rolled copper foil of 8 μm thickness, 12 under nitrogen atmosphere
Dried at 0 ° C. for 5 minutes and further obtained in Example 1
Apply varnish and apply under nitrogen atmosphere at 250 ° C for 30 minutes.
Heat to remove solvent from both varnishes and imidize polyamic acid
The reaction was performed. The thickness of the polyimide layer obtained here is
13 μm, for a total of 26 μm. The resulting polyimide coating
Fabric copper foil and rolled copper foil with a thickness of 35μm are heated by vacuum press
Pressure bonding was performed. The pressing conditions at this time are 240 ° C., 50 ° C.
kgf / cm^TwoFor 30 minutes. This flexible
Heat compression interface of double-sided metal laminate (copper-polyimide interface)
Has a 180 degree peel strength of 2.4 kgf / cm.
Was. Furthermore, this flexible double-sided metal laminate is
Swelling, peeling, discoloration, etc.
Did not. FIG. 3 shows a schematic diagram of this configuration example. Embodiment 13 Polyimide of the polyimide coated copper foil obtained in Example 12
The surfaces are superimposed on each other and continuously laminated by a hot roll press.
Was. Press conditions: 270 ° C, 50kgf / cm, running
The speed was 0.1 m / min. Also, the thermocompression bonding interface
Peeling at (polyimide-polyimide interface) cannot be measured
It was so strongly bonded. The obtained flexible frame
The kibble double-sided metal laminate is different from Example 1 in appearance.
And no swelling even if immersed in 260 ° C solder for 1 minute.
There was no change such as peeling or discoloration. FIG. 4 shows an example of this configuration.
FIG. Embodiment 14 The polyimide-coated copper foil obtained in Example 1 and Example 12
Overlay the polyimide surfaces of the obtained polyimide coated copper foil
Combine and 220kg at 75kgf / cm by vacuum press^Two
For 20 minutes. Continuous lamination by hot roll press
Was. The thermocompression bonding interface (polyimide-polyimide interface)
The peeling on the side ()) was so strongly bonded that it could not be measured.
The resulting flexible flexible double-sided metal laminate is
No change in appearance from Example 1
No change such as swelling, peeling or discoloration even if immersed in a field for 1 minute
Was. FIG. 5 shows a schematic diagram of this configuration example. [0056] [Table 1] [0057] According to the present invention, heat resistance, adhesiveness, and heat resistance
All-polyimide flexible double-sided metal with excellent flexibility
Metal plate is easy to manufacture and its industrial applicability is outstanding
I have to say that it is expensive.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram of a laminated structure of the present invention. FIG. 2 is a schematic diagram of a laminated structure according to the present invention. FIG. 3 is a schematic diagram of a laminated structure according to the present invention. FIG. 4 is a schematic diagram of a laminated structure according to the present invention. FIG. 5 is a schematic diagram of a laminated structure according to the present invention. [Description of Signs] 1 Metal foil 2 Polyimide layer removed by solvent after polyimide varnish coating 3 Flexible single-sided metal laminate 4 Polyimide layer removed by imidization and solvent removal after polyamic acid varnish coating

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hideaki Oikawa 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside (72) Inventor Shigeki Kijima 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu (56) References JP-A-3-104185 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) H05K 3/00 B32B 15/08 H05K 1/03

Claims (1)

(57) [Claims 1] A polymerization reaction and an imidization reaction are completed in an organic solvent on a metal foil or on a substrate on which a polyamic acid varnish is directly applied in advance on a metal foil. The polyimide varnish was directly applied, and an all-polyimide single-sided flexible metal laminate was obtained by completing the solvent removal and / or the imidization reaction of the polyamic acid previously applied on the base material.
A metal foil, or a flexible double-sided metal laminate obtained by heating and pressurizing the polyimide layers of another all-polyimide flexible single-sided metal laminate obtained by the above method, and the secondary transition point of the polyimide layer is 160 ° C. A method for producing a flexible double-sided metal laminate, wherein the temperature is at least 270 ° C. and the polymer terminal of the polyimide layer is sealed with dicarboxylic anhydride and / or monoamine.