KR102039341B1 - Manufacturing method of copper clad laminate - Google Patents

Abstract

The copper clad laminated board is manufactured by superimposing copper foil on the heat-sealing polyimide layer in a heat-sealing polyimide film. The heat sealable polyimide film includes a heat sealable polyimide layer and a heat resistant polyimide layer. The polyimide which comprises a heat-sealable polyimide layer is obtained from a tetracarboxylic acid component and a diamine component. The tetracarboxylic acid component contains 10 to 30 mol% of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and 70 to 90 mol% of pyromellitic dianhydride. The diamine component comprises more than 50 mol% of 2,2-bis [4- (4-aminophenoxy) phenyl] propane. The polyimide which comprises a heat resistant polyimide layer is obtained from a tetracarboxylic-acid component and a diamine component. The tetracarboxylic acid component contains more than 50 mol% of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride. The diamine component contains more than 50 mol% of p-phenylenediamine.

Description

Manufacturing method of copper clad laminate

The present invention relates to a method for producing a copper clad laminate using a heat sealable polyimide film.

Polyimide films are widely used as substrate materials such as flexible printed wiring boards (hereinafter also referred to as "FPC (Flexible Printed Circuit)") and tape automated bonding (hereinafter also referred to as "TAB (Tape Automated Bonding")).

In manufacture of FPC and TAB, the method of using an adhesive, such as an epoxy resin and an acrylic resin, is mentioned as a method of sticking a polyimide film and copper foil.

The polyimide film which can stick with copper foil, without using an adhesive agent is also proposed. For example, Patent Documents 1 and 2 disclose a polyimide film having a heat sealability, in which a heat sealable polyimide layer is laminated on a heat resistant polyimide layer, and a method for producing a copper clad laminate using the same.

WO2011 / 087044 WO2013 / 157565

However, with the high functionalization of FPC and TAB, the improvement of the heat resistance of a heat-sealing polyimide film, and the adhesiveness of metal layers, such as copper foil which is a heat-adhesive polyimide film and a to-be-adhered body, was desired further.

Therefore, an object of this invention is to provide the manufacturing method of the copper clad laminated board using the heat-sealing polyimide film which is excellent in heat resistance and excellent in adhesiveness with a metal layer.

The present invention relates to the following terms.

1.A method for producing a copper clad laminate having a step of overlapping and thermocompression bonding copper foil on a heat-sealing polyimide film,

The heat sealable polyimide film includes a heat sealable polyimide layer and a heat resistant polyimide layer laminated in contact with the heat sealable polyimide layer,

The polyimide which comprises the said heat-sealing polyimide layer is obtained from a tetracarboxylic-acid component and a diamine component,

The tetracarboxylic acid component contains 10 to 30 mol% of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and 70 to 90 mol% of pyromellitic dianhydride,

The diamine component contains more than 50 mol% of 2,2-bis [4- (4-aminophenoxy) phenyl] propane,

The polyimide which comprises the said heat resistant polyimide layer is obtained from a tetracarboxylic-acid component and a diamine component,

The tetracarboxylic acid component contains more than 50 mol% of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride,

The diamine component comprises more than 50 mol% of p-phenylenediamine,

The copper clad laminated board manufacturing method of laminating | stacking copper foil on the said heat-sealing polyimide layer, and carrying out thermocompression bonding at the temperature range of 350 degreeC or more and 420 degrees C or less.

2. The manufacturing method of the copper clad laminated board of said claim | item 1 whose peeling strength measured by the method of JIS C6471 is 0.5 N / mm or more.

[Heat sealable polyimide film]

The heat-sealable polyimide film used in the present invention is a heat-sealable polyimide layer (hereinafter referred to simply as a "heat-sealed layer"), and a heat-resistant polyimide layer laminated in contact with the heat-sealable polyimide layer (hereinafter "core" Layer ”, also called " layers "). The heat sealable polyimide film is at least a two-layer structure having at least one heat seal layer and at least one core layer. The heat sealable polyimide film may have a three-layer structure in which the same or different heat seal layers are disposed on each side of the core layer.

Here, "heat sealing property" means that the softening point of the surface of a polyimide film is less than 350 degreeC. The softening point is a temperature at which an object is softened rapidly during heating, the glass transition temperature (Tg) is a softening point in amorphous polyimide, and the melting point is a softening point in crystalline polyimide.

<Heat sealable polyimide layer>

The heat sealable polyimide layer (heat seal layer) consists of a heat sealable polyimide obtained from a tetracarboxylic acid component and a diamine component.

The heat-sealable polyimide preferably has a tetracarboxylic acid component of 80 mol% or more of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride in their total. In particular, it is more preferable that the tetracarboxylic acid component consists of these compounds. It is preferable that the content rate of these components is 10-30 mol%, especially 15-25 mol% of 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride among all the tetracarboxylic-acid components, It is preferable that pyromellitic dianhydride is 70-90 mol%, especially 75-85 mol%.

Moreover, it is preferable that the said heat-sealing polyimide contains more than 50 mol% of 2, 2-bis [4- (4-amino phenoxy) phenyl] propane in a diamine component. The content of 2,2-bis [4- (4-aminophenoxy) phenyl] propane in the total diamine component is preferably 70 mol% or more, more preferably 80 mol% or more, most preferably 90 mol%. It is more than 100%.

As said tetracarboxylic-acid component, the said two tetracarboxylic-acid component and another tetracarboxylic-acid component can be used together. As another tetracarboxylic-acid component used together, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, bis (3, 4- dicarboxyphenyl) ether 2 anhydride, bis ( 3,4-dicarboxyphenyl) sulfite 2 anhydride, bis (3,4-dicarboxyphenyl) sulfone 2 anhydride, bis (3,4-dicarboxyphenyl) methane 2 anhydride, 2,2-bis (3,4 -Dicarboxyphenyl) propane dianhydride, and 1,4-hydroquinone dibenzoate-3,3 ', 4,4'- tetracarboxylic dianhydride, etc. are mentioned. The tetracarboxylic-acid component used together can be used individually or in combination of 2 or more types.

As a diamine component, 2, 2-bis [4- (4-aminophenoxy) phenyl] propane and another diamine component can be used together. As another diamine component used together, 1, 3-bis (4-amino phenoxy) benzene, 1, 3-bis (3-amino phenoxy) benzene, 1, 4-bis (4-amino phenoxy) Benzene, 3,3'-diaminobenzophenone, 4,4'-bis (3-aminophenoxy) biphenyl, 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 Cs) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether , Bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, and the like. The diamine component used together can be used individually or in combination of 2 or more types.

It is preferable that the heat-sealing polyimide constituting the heat-sealing layer is amorphous in view of the improvement of the peel strength of the heat-sealing layer and the heat-resistant polyimide layer and the improvement of the peel strength of the heat-sealing layer and the copper foil. The fact that the heat-sealable polyimide is amorphous means that it has a glass transition temperature but no melting point is observed. What is necessary is just to employ | adopt the method, such as using the compound which has an ether bond as a tetracarboxylic-acid component or a diamine component, in order to manufacture the heat-sealing layer which consists of amorphous heat-sealable polyimide.

In addition, it is preferable that the glass transition temperature of the heat-sealing polyimide which comprises a heat-sealing layer is 250 degreeC-320 degreeC, and is 270 degreeC-300 degreeC from a viewpoint of improving the heat resistance of the obtained heat-sealing polyimide film. More preferred. The measuring method of glass transition temperature is described in detail in the Example mentioned later.

<Heat resistant polyimide layer>

The heat resistant polyimide layer (core layer) consists of heat resistant polyimide obtained from a tetracarboxylic acid component and a diamine component.

It is preferable that the said heat resistant polyimide contains more than 50 mol% of 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride as a tetracarboxylic-acid component in all the tetracarboxylic-acid components. Moreover, the said heat resistant polyimide may also contain other tetracarboxylic-acid component other than 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride as a tetracarboxylic-acid component. For example, more than 50 mol% of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride is contained, and further, pyromellitic dianhydride and 1,4-hydroquinone dibenzoate-3, It is preferable to include at least 1 type of acid component chosen from 3 ', 4,4'- tetracarboxylic dianhydride. It is preferable that the total amount of this other tetracarboxylic-acid component is 70 mol% or more in all the tetracarboxylic-acid components, It is more preferable that it is 80 mol% or more, It is more preferable that it is 90 mol% or more.

It is preferable that the said heat resistant polyimide contains more than 50 mol% of p-phenylenediamine as a diamine component in all the diamine components. Moreover, the said heat resistant polyimide may also contain other diamine component other than p-phenylenediamine as a diamine component. For example, p-phenylenediamine contains more than 50 mol% of the total diamine component, and also 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, m-tridine and It is preferred to include at least one diamine component selected from 4,4'-diaminobenzanilide. It is preferable that the total amount of the said other diamine component is 70 mol% or more in all the diamine components, It is more preferable that it is 80 mol% or more, It is more preferable that it is 90 mol% or more.

As a combination of the tetracarboxylic-acid component and the diamine component which can obtain a heat resistant polyimide, the following is mentioned, for example.

(1) 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (hereinafter also referred to as "s-BPDA"), p-phenylenediamine (hereinafter also referred to as "PPD"), and Thus a combination comprising 4,4-diaminodiphenylether (hereinafter also referred to as "DADE"). In this case, it is preferable that PPD / DADE (molar ratio) is 100/0-85/15.

(2) 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) and pyromellitic dianhydride (hereinafter also referred to as "PMDA"), and p-phenylenediamine (PPD) And the combination containing 4, 4- diamino diphenyl ether (DADE) as needed. In this case, it is preferable that s-BPDA / PMDA is 55 / 45-90 / 10. When using PPD and DADE together, it is preferable that PPD / DADE is 55/45-90/10, for example.

(3) A combination consisting of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) and p-phenylenediamine (PPD).

A fine inorganic or organic filler (hereinafter also referred to as "additive") can be mix | blended with a heat resistant polyimide layer as needed. As an inorganic additive, inorganic fillers, such as a particulate form or a flat form, are mentioned. Specifically, for example, inorganic oxide powders such as fine titanium dioxide powder, silicon dioxide (silica) powder, magnesium oxide powder, aluminum oxide (alumina) powder, zinc oxide powder, silicon nitride powder of fine particles, titanium nitride powder, etc. And inorganic salt powders such as inorganic carbide powders such as inorganic nitride powders and silicon carbide powders, fine particulate calcium carbonate powders, calcium sulfate powders and barium sulfate powders. As an organic additive, polyimide particle | grains, the particle | grains of a thermosetting resin, etc. are mentioned, for example. You may use these additives in combination of 2 or more type. It is preferable to select the usage-amount and shape (size, aspect ratio) of an additive according to a use purpose. Moreover, a means known per se can be applied to uniformly disperse these additives.

Although the thickness of the heat-sealing polyimide film used by this invention is not specifically limited, In the case of the heat-sealing polyimide film of the 3-layered structure which has a heat-sealing polyimide layer in each of both surfaces of a heat-resistant polyimide layer, heat-resistant polyimide It is preferable that it is 3-70 micrometers, and, as for the thickness of a mid layer, it is more preferable that it is 8-50 micrometers. It is preferable that it is 0.5-15 micrometers, and, as for the thickness of a heat | fever adhesive polyimide layer, it is more preferable that it is 1-12.5 micrometers. It is preferable that it is 1-30 micrometers, and, as for the thickness of the whole heat | fever adhesive polyimide film, it is more preferable that it is 2-25 micrometers.

It is preferable that the heat-sealing polyimide film used by this invention is excellent in heat resistance, for example, it is preferable that solder heat resistance is 280 degreeC or more, especially 300 degreeC or more. Moreover, it is preferable that the tearing strength of a heat-sealing polyimide film is 1.7 N / mm or more, especially 1.9 N / mm or more. In addition, the measuring method of solder heat resistance and tear strength is demonstrated in the term of an Example.

[Manufacturing method of heat sealable polyimide film]

Next, as an example of the manufacturing method of the heat-sealing polyimide film used in the present invention, heat-sealing property having a heat-sealing polyimide layer (heat-sealing layer) on one side or both sides of the heat-resistant polyimide layer (core layer) The manufacturing method of a polyimide film is demonstrated.

(Manufacturing method by coating method)

The heat-sealing polyimide film used in the present invention is a heat-sealing polyimide on one side or both sides of a self-supporting film obtained from a polyimide precursor solution (polyamic acid solution) (a) that imparts a heat-resistant polyimide. It can obtain by heating, drying, and imidizing the multilayer self-supporting film obtained by coating the polyimide precursor solution (polyamic-acid solution) (b) which imparts (b).

The self-supporting film obtained from the polyimide precursor solution (a) which imparts a heat resistant polyimide is substantially equimolar in the tetracarboxylic acid component and the diamine component, or slightly in excess of one component relative to the other component. The polyimide precursor solution (a) obtained by making it react in an organic solvent can be cast on a support body, and a cast material can be obtained by heating and drying.

On the other hand, the polyimide precursor solution (b) which imparts a heat-sealable polyimide also has an organic solvent in which the tetracarboxylic acid component and the diamine component are substantially equimolar, or one component is slightly excess compared to the other component. It is obtained by making it react in the inside.

The polyimide precursor solution (b) which provides a heat-sealable polyimide is a tetracarboxylic-acid component, and it is 10- containing 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride among all the tetracarboxylic-acid components. 30 mol%, 70-90 mol% of pyromellitic dianhydride, and the said diamine component contains 2, 2-bis [4- (4-amino phenoxy) phenyl] propane more than 50 mol% in all diamines. It is desirable to.

The polyimide precursor solution (a) imparting heat resistant polyimide contains more than 50 mol% of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride as the tetracarboxylic acid component in the total tetracarboxylic acid component. It is preferable to contain more than 50 mol% of p-phenylenediamine as a diamine component in the whole diamine.

The polyimide precursor solution (b) and / or the polyimide precursor solution (a) may contain a phosphorus stabilizer such as triphenyl phosphite or triphenyl phosphate for the purpose of limiting the gelation of the polyamic acid (polyimide precursor). It can add in 0.01-1 mass% with respect to solid content (polymer) concentration at the time of superposition | polymerization.

In view of the surface state and productivity of the film, it is preferable to add a phosphate ester or salts of tertiary amine and phosphate ester to the polyamic acid solution. It is preferable that these addition amounts are 0.01-5 mass parts with respect to 100 mass parts of polyimides or a polymer. As a specific example of phosphate ester, distearyl phosphate ester, monostearyl phosphate ester, etc. are mentioned. Moreover, as a salt of a tertiary amine and a phosphate ester, a monostearyl phosphate ester triethanolamine salt etc. are mentioned, for example. About the imidation in this invention, thermal imidation (thermal imidation) or chemical imidation (chemical imidation) can be applied. Among these, thermal imidation can be preferably applied.

A basic organic compound can be added to the polyimide precursor solution (b) and / or the polyimide precursor solution (a) for the purpose of promoting imidization. For example, imidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, benzimidazole, isoquinoline, substituted pyridine, and the like are added to polyamic acid (polyimide precursor). It is preferably 0.05 to 10% by mass, more preferably 0.05 to 5% by mass, particularly preferably at a ratio of 0.1 to 2% by mass. By using these basic organic compounds, since imidation of a polyimide precursor is accelerated | stimulated at a comparatively low temperature, and a polyimide film is formed, these basic organic compounds can be used for the purpose of avoiding insufficient imidation.

Organic solvents for preparing the polyimide precursor solution include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, Amides such as N-diethylformamide and hexamethylsulfonamide, sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide, and sulfones such as dimethyl sulfone and diethyl sulfone. These solvents may be used alone or in combination.

The density | concentration of the all monomers in the organic solvent at the time of performing the polymerization reaction of a tetracarboxylic-acid component and a diamine component can be suitably selected according to the objective to be used. For example, as for the polyimide precursor solution (a) and (b), it is preferable that the density | concentration of the whole monomer in an organic solvent is 5-40 mass%, It is more preferable that it is 6-35 mass%, 10-30 mass% Is particularly preferred.

As an example of the preparation example of a polyimide precursor solution (a) and a polyimide precursor solution (b), the tetracarboxylic-acid component and the diamine component are substantially equimolar, or one component (acid component or diamine component) Compared to the other components, the mixture is mixed in a little excess, and is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and even more preferably, polyimide is reacted at a reaction temperature of 0 to 60 ° C. for about 0.2 to 60 hours. A precursor (polyamic acid) solution can be obtained.

The solution viscosity of a polyimide precursor solution (a) and a polyimide precursor solution (b) can be suitably selected according to the objective (coating, casting, etc.) etc. to be used. For example, the polyimide precursor solution (a) and the polyimide precursor solution (b) have a rotational viscosity measured at 30 ° C. in terms of workability in handling the polyimide precursor solution when they are used in casting, and the polyimide precursor solution (a) and the polyimide precursor solution (b) are about 100 to 5000. It is preferable that it is poise, It is more preferable that it is 500-4000 poise, It is especially preferable that it is about 1000-3000 poise. In addition, when using a polyimide precursor solution (a) and a polyimide precursor solution (b) for coating, it is preferable that the rotational viscosity measured at 30 degreeC is 1-100 centipoise from the workability which handles a polyimide precursor solution. It is more preferable that it is 3-50 centipoise, and it is especially preferable that it is 5-20 centipoise. Therefore, it is preferable to perform the said polymerization reaction to the extent to which the polyamic acid (polyimide precursor) which produces | generates exhibits the above-mentioned viscosity. The organic solvent may also be added to the prepared polyamic acid solution to adjust the solution viscosity.

The self-supporting film obtained from the polyimide precursor solution (a) which gives a heat resistant polyimide, for example, uses the polyimide precursor solution (a) as a suitable support body (for example, metal, ceramic, plastic roll, or metal). On the surface of the belt or the like) to form a film having a uniform thickness, and then, using a heat source such as hot air or infrared light, is preferably heated to 50 to 210 ° C, more preferably to 60 to 200 ° C, thereby It can remove by gradually removing and drying until it becomes self-supporting (for example, to the extent that it can peel from a support body).

It is preferable that the said weight loss of the said self-supportive film which imparts a heat resistant polyimide exists in the range of 20-40 mass%, and it is preferable that an imidation ratio exists in the range which is 8-40%. If the heating loss and imidation ratio are in the said range, the mechanical property of a self-supporting film will become enough, and the polyimide film obtained after imidation will become easy to coat a polyimide precursor solution (b) on the upper surface of a self-supporting film cleanly. Foaming, cracking, craze, cracking, cracking, etc. are less likely to occur, and the adhesive strength of the heat-resistant polyimide layer and the heat-sealable polyimide layer becomes sufficient.

The heating loss of the self-supporting film is a value obtained by drying the film to be measured for 30 minutes at 400 ° C. from the weight (W ₁ ) before drying and the weight (W ₂ ) after drying by the following equation.

Heating loss (mass%) = {(W ₁ -W ₂ ) / W ₁ } × 100

The imidation ratio of a self-supporting film can respectively measure the IR spectrum of a self-supporting film and its full cure product (polyimide film) by ATR method, and can calculate it using the ratio of a shake table peak area. As a shake table peak, the asymmetrical stretching shake table of an imide carbonyl group, a benzene ring skeletal stretch shake table, etc. can be used. Moreover, about the imidation ratio measurement, there also exists a method of using the Karl Fischer moisture meter of Unexamined-Japanese-Patent No. 9-316199.

Next, the polyimide precursor solution (b) which gives a heat-sealable polyimide to one or both surfaces of the said self-supporting film is coated. The polyimide precursor solution (b) may be coated on the self-supporting film peeled from the support, or may be coated on the self-supporting film on the support before peeling from the support. It is preferable that coating coats the polyimide precursor solution (b) uniformly on one or both surfaces of a self-supporting film. Therefore, it is preferable that the self-supporting film of a polyimide precursor solution (a) has a surface which can coat a polyimide precursor solution (b) uniformly.

Although it does not specifically limit as a method of coating a polyimide precursor solution (b) on the self-supporting film obtained from a polyimide precursor solution (a), For example, the gravure coat method, the spin coat method, the silk screen method, the dip coat Known coating methods, such as a method, a spray coating method, the bar coating method, the knife coating method, the roll coating method, the blade coating method, and the die coating method, are mentioned.

Next, the self-supporting film of the polyimide precursor solution (a) which coated the said polyimide precursor solution (b) is heated and imidated, and a heat-sealing polyimide film is obtained. 350 degreeC-600 degreeC is preferable, as for the maximum heating temperature of the heat processing for imidation, 380-520 degreeC is more preferable, 390-500 degreeC is more preferable, 400-480 degreeC is still more preferable.

It is preferable to perform the heat processing for imidation stepwise, and first, after 1st-60 minutes of 1 minute-60 minutes at the temperature of 200 degreeC or more and less than 300 degreeC, 1 minute-at the temperature of 300 degreeC or more and less than 350 degreeC Second heat treatment for 60 minutes, after that, preferably 350 ° C to 600 ° C, more preferably 450 to 590 ° C, more preferably 490 to 580 ° C, still more preferably 500 to 580 ° C. It is preferable to perform a 3rd heat processing at heating temperature for 1 minute-30 minutes. This heat treatment can be performed using well-known apparatuses, such as a hot stove and an infrared heating furnace, for example. Moreover, it is preferable to perform this heat processing by fixing the self-supporting film of the polyimide precursor solution (a) which coated the polyimide precursor solution (b) with a pin tenter, a clip, etc.

(Manufacturing method by coextrusion-flexible film forming method)

The heat-sealing polyimide film used in the present invention is a dope liquid (polyamic acid solution, polyimide precursor solution) to impart a heat-resistant polyimide layer by a coextrusion-flexible film forming method (hereinafter also referred to simply as "coextrusion method"). ) And the dope liquid which gives a heat-sealable polyimide layer can also be manufactured by the method of laminating | stacking, drying, and imidating. As this coextrusion method, the method described in Unexamined-Japanese-Patent No. 3-180343 (Japanese Unexamined-Japanese-Patent No. 7-102661) can be used, for example.

More specifically, in this coextrusion method, an extrusion molding machine having a die for extrusion molding of two or more layers is first used. The dope liquid which provides a heat resistant polyimide layer and the dope liquid which provides a heat-sealable polyimide layer are cast on the support body from the discharge port of the said die, and the laminated thin film form body is formed thereby. The thin film on the support is dried to form a multilayer self-supporting film. Next, the multilayer self-supporting film is peeled off from the support, and finally, the multilayer self-supporting film is heat treated. In this step, the dope liquid in contact with the support may be any of a dope liquid giving a heat resistant polyimide layer and a dope liquid giving a heat sealable polyimide layer. At this time, in the drying, it is preferable to form a self-supporting film by heating to a temperature exceeding 135 ° C, specifically 140 ° C or higher, preferably 145 ° C or higher.

As a two-layer extrusion die, it has a supply port of dope liquid, for example, the passage of a dope liquid is formed toward each manifold from each supply port, and the flow path of the bottom part of the manifold is at the confluence point. After the confluence, the passage (lip part) of the dope liquid after joining is connected to the slit-shaped discharge port so that the dope liquid is discharged onto the support in a thin film form (multi-manifold type two-layer die). It can be mentioned. The said lip part can adjust the space | interval by a lip adjustment bolt.

Moreover, the space | interval of the clearance gap of the flow path of the bottom part (part near a confluence point) of each manifold is adjusted by each choke bar. It is preferable that each said manifold has the shape of a hanger coat type. The die for two-layer extrusion has a supply port for each dope liquid on the left and right sides of the upper die, and the passage of the dope liquid is immediately joined at the confluence point provided with the partition plate. A flow path of the dope liquid is continuously connected to the manifold from the confluence point, and a passage (lip) of the dope liquid at the bottom of the manifold is connected to the slit discharge port. It may be a structure (feed block type 2-layer dice or single manifold type 2-layer dice) in which the dope liquid is discharged onto the support body in the form of a groove film from the discharge port. In addition, the description of the above-mentioned "manufacturing method by the coating method" can be applied as it is to the form of drying conditions, heating conditions, and the like after the continuous extrusion on the support in the coextrusion-flexible film forming method.

In addition to the two-layer extrusion, a multilayer extruded polyimide film may be produced by the same molding method as the two-layer extrusion by using a die for three or more layers of extrusion molding. That is, when the dope liquid which gives a heat resistant polyimide layer and the dope liquid which gives a heat-sealing polyimide layer are used, two layers of heat-sealable polyimide films can be obtained. In addition, when it is set as the structure of the 1st dope liquid which gives a heat-sealable polyimide layer, the dope liquid which gives a heat-resistant polyimide layer, and the 2nd dope liquid which gives a heat-sealable polyimide layer, 3 layers of heat fusion You can also obtain a polyimide film. The first dope liquid and the second dope liquid may be the same or different.

Copper Clad Laminates

Next, the manufacturing method of the copper clad laminated board using the said heat-sealing polyimide film is demonstrated.

A copper clad laminated board consists of laminating | stacking copper foil on the heat-sealing polyimide layer of the said heat-sealing polyimide film. Copper foil may be laminated | stacked on both surfaces of a heat-sealable polyimide film, and copper foil may be laminated | stacked only on one side of a heat-sealable polyimide film. When laminating | stacking copper foil on one side of a heat-sealing polyimide film, the said heat-sealing polyimide film which has a heat-sealing polyimide layer on one side or both surfaces is used. In addition, when laminating | stacking copper foil on both surfaces, the said heat-sealing polyimide film which has a heat-sealing polyimide layer on both surfaces is used.

As a specific example of the said copper foil, a rolled copper foil, an electrolytic copper foil, etc. are mentioned. Although the thickness of copper foil does not have a restriction | limiting in particular, 2-35 micrometers is preferable and 5-18 micrometers is especially preferable. As copper foil whose thickness is 5 micrometers or less, copper foil with a carrier, for example, copper foil with an aluminum foil carrier, can be used.

In the present invention, the copper foil is coated on both sides of the heat-sealing polyimide film by laminating copper foil on both sides of the heat-sealing polyimide film formed on both sides of the heat-sealing polyimide layer and thermo-compressing the heat-sealing polyimide film and the copper foil. A laminated copper clad laminate can be obtained. In addition, heat-sealing by heat-sealing a heat-sealing polyimide film and a copper foil by laminating a copper foil on the heat-sealing polyimide layer on one side of the heat-sealing polyimide film having a heat-sealing polyimide layer formed on at least one side thereof The copper clad laminated board in which copper foil was laminated | stacked on one side of the sexual polyimide film can be obtained.

It is preferable that a heat-sealable polyimide film and copper foil are continuously thermocompressed under heating by at least one pair of pressure members. It is preferable that the temperature of a press part is 50 degreeC or more higher than the glass transition temperature of a heat-sealing polyimide, It is more preferable that it is 60 degreeC or more high, It is further more preferable that it is 70 degreeC or more high. By employ | adopting such a heating temperature, the advantageous effect that a heat | fever sealing polyimide film and copper foil are laminated | stacked firmly is exhibited. Moreover, it is preferable that heating temperature is 420 degrees C or less from the point which prevents thermal deterioration of a heat-sealing polyimide film and copper foil. As described above, the glass transition temperature of the heat-sealable polyimide is preferably 250 ° C. or higher, and specifically, thermocompression bonding is preferably performed in a temperature range of 300 ° C. or higher and 420 ° C. or lower, and 350 ° C. or higher and 420 ° C. or lower. It is more preferable to thermo-compress in the range of temperature, and it is more preferable to thermo-compress in the range of the temperature of 360 degreeC or more and 420 degrees C or less.

As a press member, a pair of crimping metal rolls (any crimping part may be a metal and a ceramic sprayed metal may be sufficient), a double belt press, and a hot press are mentioned. In particular, a pressing member capable of thermocompression bonding and cooling under pressure is preferable, and a hydraulic double belt press is particularly preferred. Moreover, a copper clad laminated board can be obtained simply also by the roll lamination by a pair of crimping metal rolls.

In the present invention, by using the pressing member, for example, a metal roll or preferably a double belt press, the heat-sealing polyimide film, the copper foil, and the reinforcing material are laminated and pressed under continuous heating to produce a long copper clad laminate. Can be.

The use of such a pressing member is particularly preferable when the heat-sealing polyimide film and the copper foil are used in the roll winding state, and are respectively supplied to the pressing member continuously to obtain the copper clad laminate in the roll winding state.

The copper clad laminated board obtained by the manufacturing method of this invention becomes a thing by which the heat-sealing polyimide film and copper foil were firmly laminated | stacked. According to the present invention, for example, a copper clad laminate having a peel strength of 0.5 N / mm or more, preferably 0.7 N / mm or more, measured by the method of JIS C6471 can be obtained. On the other hand, in the copper clad laminated board in which copper foil was laminated | stacked on the heat-sealable polyimide layer among three heat-sealable polyimide films in which the heat-sealable polyimide layer was laminated on both surfaces of the heat-resistant polyimide layer, the peeled state (peel mode) ) May be peeled off at the interface between the heat-resistant polyimide layer and the heat-sealable polyimide film, or peeled off at the interface between the heat-sealable polyimide layer and the copper foil. Therefore, the peeling strength measured by the method mentioned above is the peeling strength of the interface with weaker adhesive force. The measuring method of peeling strength is demonstrated in the term of an Example.

The copper clad laminate obtained by the present invention has good moldability, and can be punched, bent or squeezed, metal wiring, or the like as it is. Therefore, the copper clad laminated board obtained by this invention can be used suitably as a raw material of electronic components, such as a printed wiring board, a flexible printed circuit board, and a TAB tape, and electronic equipment.

Example

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on an Example. However, the present invention is not limited by the following examples.

[Measurement method of each evaluation]

1. Peel test of copper clad laminate

Peeling strength of the copper clad laminate was measured by the method of JIS C6471.

2. Solder Heat Resistance

A resist is printed on part of one side of the copper-clad laminate and the entire surface of the other side, and the metal layer on one side is partially etched by being immersed in an etchant at 30 ° C. for 20 to 30 minutes, and the other side is left with copper foil on the entire side. A laminated board was obtained. The obtained laminated board was dried at 80 degreeC for 30 minutes, and humidity was adjusted for 24 hours or more in the environment of 85 degreeC-85% RH. This sample was floated for 60 seconds in the solder bath of various temperature, and the presence or absence of foaming of the sample was confirmed. The maximum temperature at which foaming was not confirmed was made into the solder heat-resistant temperature.

3. tear strength

The tear strength of the heat sealable polyimide film was measured by the method of IPC-TM-6502.4.17.1.

4. Chemical resistance test

A resist was printed on a part of one side of the obtained copper clad laminated board, and it was immersed in etching liquid at 30 degreeC for 20 to 30 minutes, and the laminated board by which the copper foil of one side was partially etched was obtained. The obtained laminated board was dried at 80 degreeC for 30 minutes. After immersing this laminated board in 10 mass% sodium hydroxide aqueous solution heated at 50 degreeC for 30 minutes, it washed with water and confirmed the external appearance. The case where there was no change in an external appearance was made into (circle), and when peeling generate | occur | produced between a polyimide layer and copper foil, or when the crack generate | occur | produced in the polyimide layer was made into x.

5. Glass transition temperature of heat sealable polyimide

The polyamic acid solution which gives a heat-sealable polyimide was cast on the glass plate using the coater, and it dried in 120 degreeC in the drying furnace for 15 minutes, and obtained the self-supporting film. The obtained self-supporting film was stuck to a tenter on all sides, and it heated up, maintaining it for 2 minutes in 150 degreeC, 200 degreeC, 250 degreeC, and 350 degreeC in a heating furnace, and the single-layer film which consists of a 20 micrometers heat-sealable polyimide Got it.

The obtained film was subjected to dynamic viscoelasticity measurement under conditions of a temperature rising rate of 10 ° C./min and a frequency of 1 Hz using a RSA G2 type dynamic viscoelasticity measuring device manufactured by TA INSTRUMENTS, and the peak temperature of tan δ was defined as the glass transition temperature.

[Synthesis of Polyamic Acid Solution A Imparting Heat Resistant Polyimide]

N, N-dimethylacetamide (hereinafter also referred to as "DMAc") is added to the reaction vessel equipped with a stirrer and a nitrogen introduction tube, and also 3,3 ', 4,4'-ratio with paraphenylenediamine (PPD). Phenyl tetracarboxylic dianhydride (s-BPDA) was made to react substantially equimolarly, and the polyamic-acid solution A whose monomer concentration is 1500 mass and the solution viscosity in 25 degreeC is 1500 poise was obtained.

[Synthesis of polyamic acid solution B imparting heat resistant polyimide]

DMAc was added to the reaction vessel provided with a stirrer and a nitrogen inlet tube, and as a diamine component, PPD, 4,4'-diaminodiphenyl ether (DADE), and 2,2-bis [4- (4-amino Phenoxy) phenyl] propane (hereinafter also referred to as "BAPP") was added. Then, pyromellitic dianhydride (PMDA) and benzophenone tetracarboxylic dianhydride (hereinafter also referred to as "BTDA") as tetracarboxylic dianhydride components are added to react the tetracarboxylic dianhydride component with the diamine component. The polyamic-acid solution B whose monomer density | concentration is 18 mass% and the solution viscosity in 25 degreeC is 1800 poise was obtained. The molar ratio of BTDA and PMDA was 10:90 and the molar ratio of PPD, DADE and BAPP was 75:10:15.

[Synthesis of polyamic acid solution C giving a heat sealable polyimide]

DMAc was added to the reaction container provided with the stirrer and the nitrogen inlet tube, and 2, 2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) was further added. Next, s-BPDA and PMDA were added, and the polyamic-acid solution C whose monomer concentration is 850 poise was 18 mass% and 25 degreeC. The molar ratio of s-BPDA and PMDA was 10:90.

[Synthesis of polyamic acid solution D imparting heat sealable polyimide]

DMAc was added to the reaction container provided with the stirrer and the nitrogen inlet tube, and BAPP was further added. Subsequently, s-BPDA and PMDA were added and the monomer concentration was 18 mass%, and the polyamic-acid solution D whose solution viscosity in 25 degreeC is 850 poise was obtained. The molar ratio of s-BPDA and PMDA was 20:80.

[Synthesis of polyamic acid solution E imparting heat sealable polyimide]

DMAc was added to the reaction container provided with the stirrer and the nitrogen inlet tube, and BAPP was further added. Next, s-BPDA and PMDA were added, and the polyamic-acid solution E whose monomer concentration is 850 poise was 18 mass% and 25 degreeC. The molar ratio of s-BPDA and PMDA was 22.5: 77.5.

[Synthesis of polyamic acid solution F imparting heat sealable polyimide]

DMAc was added to the reaction container provided with the stirrer and the nitrogen inlet tube, and BAPP was further added. Subsequently, s-BPDA and PMDA were added, and the polyamic-acid solution F whose monomer viscosity is 850 poise was 18 mass% and 25 degreeC. The molar ratio of s-BPDA and PMDA was 25:75.

[Synthesis of polyamic acid solution G imparting heat sealable polyimide]

DMAc was added to the reaction container provided with the stirrer and the nitrogen inlet tube, and BAPP was further added. Next, s-BPDA and PMDA were added, and the polyamic-acid solution G whose monomer viscosity is 850 poise was 18 mass% and 25 degreeC. The molar ratio of s-BPDA and PMDA was 30:70.

[Synthesis of polyamic acid solution H imparting heat sealable polyimide]

DMAc was added to the reaction container provided with the stirrer and the nitrogen inlet tube, and BAPP was further added. Next, PMDA was added to obtain a polyamic acid solution H having a monomer concentration of 18 mass% and a solution viscosity of 850 poise at 25 ° C.

[Synthesis of Polyamic Acid Solution I Imparting Heat-Adhesive Polyimide]

DMAc was added to the reaction container provided with the stirrer and the nitrogen inlet tube, and BAPP was further added. Subsequently, s-BPDA and PMDA were added, and the polyamic-acid solution I whose monomer concentration is 18 mass% and the solution viscosity in 25 degreeC is 850 poise was obtained. The molar ratio of s-BPDA and PMDA was 40:60.

[Synthesis of polyamic acid solution J imparting heat sealable polyimide]

DMAc was added to the reaction container provided with the stirrer and the nitrogen inlet tube, and BAPP and PPD were further added. Subsequently, s-BPDA was added to obtain a polyamic acid solution J having a monomer concentration of 18 mass% and a solution viscosity of 850 poise at 25 ° C. The molar ratio of BAPP and PPD was 70:30.

[Synthesis of polyamic acid solution K imparting heat sealable polyimide]

DMAc was added to the reaction container provided with the stirrer and the nitrogen inlet tube, and BAPP was further added. Next, s-BPDA was added to obtain a polyamic acid solution K having a monomer concentration of 18% by mass and a solution viscosity of 850 poise at 25 ° C.

(Thermal Adhesive Polyimide Film and Copper Clad Laminate)

Example 1

From the three-layer extrusion die, the polyamic acid solution A and the polya so as to be polyamic acid solution C (heat seal layer)-polyamic acid solution A (core layer)-polyamic acid solution C (heat seal layer) on the upper surface of the smooth metal support. The mixed acid solution C was extruded and cast to form a thin film. The thin film flexible material was continuously dried with hot air at 145 ° C to form a self-supporting film. After peeling a self-supporting film from a support body, it heats gradually from 200 degreeC to 460 degreeC in a heating furnace (maximum heating temperature is 460 degreeC), removes a solvent and imidizes it, and is 12.5 micrometers in thickness (two heat bonding layers) The thickness of was 2.5 micrometers, respectively, and the thickness of the core layer was 7.5 micrometers), and the heat | fever adhesive polyimide film of the three-layered structure was obtained. The tear strength of this heat-sealing polyimide film is shown in a table.

Next, copper foil (Mitsui Metal Co., Ltd. product, 3EC-M3S-HTE, thickness 12 micrometers) was laminated | stacked on both surfaces of the obtained heat-sealing polyimide film, and the temperature was 370 degreeC, the heat of 5 minutes, press pressure 3MPa, press time 1 minute. The copper clad laminated body by which copper foil was laminated | stacked on both surfaces of the heat | fever adhesive polyimide film by thermocompression bonding was obtained. Each evaluation of peeling strength, solder heat, and chemical resistance of this copper clad laminate was performed. The results are shown in the table.

[Examples 2-5, Comparative Examples 1-4]

Except having changed the kind of polyamic acid to what is shown in a table | surface, it carried out similarly to Example 1, and obtained the heat-sealable polyimide film and the copper clad laminated board. Table 1 shows the results of each evaluation.

As is apparent from the results shown in Table 1, it is understood that the copper clad laminate produced by the method of each example has a higher peel strength and superior solder heat resistance and chemical resistance than the copper clad laminate produced by the method of the comparative example.

As mentioned above, according to this invention, according to this invention, the copper clad laminated board which is excellent in heat resistance and high in peeling strength of a polyimide film and copper foil can be obtained by thermocompression bonding a specific heat-sealing polyimide film and copper foil on specific conditions.

Claims (5)

A heat sealable polyimide film in which a heat resistant polyimide layer and a heat sealable polyimide layer are laminated,
The polyimide which comprises the said heat-sealing polyimide layer is obtained from a tetracarboxylic-acid component and a diamine component,
The tetracarboxylic acid component contains 10 to 30 mol% of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and 70 to 90 mol% of pyromellitic dianhydride,
The diamine component contains more than 50 mol% of 2,2-bis [4- (4-aminophenoxy) phenyl] propane,
The polyimide constituting the heat resistant polyimide layer is obtained from a tetracarboxylic acid component and a diamine component,
The tetracarboxylic acid component is 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride,
The diamine component is p-phenylenediamine,
The tear strength of the heat-sealing polyimide film is 1.7 N / mm or more, the solder heat resistance temperature is 280 ° C. or more,
The heat-sealing polyimide film whose peeling strength measured by the method of JIS C6471 of the copper clad laminated board in which the copper foil was laminated | stacked on the heat-sealing polyimide layer side surface of the said heat-sealing polyimide film is 0.5 N / mm or more. The method of claim 1,
The heat-sealing polyimide film whose peeling part is an interface of a heat-sealing polyimide layer and copper foil. The copper clad laminated board in which copper foil was laminated | stacked on the heat-sealing polyimide layer side surface of the heat-sealing polyimide film of Claim 1 or 2. Copper foil is laminated | stacked on the heat-sealing polyimide layer side surface of the heat-sealing polyimide film of Claim 1, or 2 and thermocompression bonding is carried out at the temperature range of 350 degreeC or more and 420 degrees C or less, The manufacture of the copper clad laminated board Way. delete