JP4736389B2 - Polyimide film with improved slipperiness and substrate using the same - Google Patents

Description

  The present invention relates to an easy-sliding polyimide film having fine protrusions on the film surface, good slipperiness on the film surface, and a long and heat-fusible property that can be easily wound on a winding roll. The present invention relates to a copper-clad laminate used, and particularly to an easy-sliding polyimide film suitable as a material film for forming a fine pattern such as a flexible printed board and TAB, and a copper-clad laminate using the same.

  Polyimide films have been used for laminates, flexible printed boards, and the like because of their excellent heat resistance, chemical resistance, mechanical strength, electrical properties, and the like. However, the polyimide film has a problem in adhesion. As a method for improving the adhesiveness, a surface treatment such as alkali treatment, corona treatment, sand blasting, and low-temperature plasma treatment is performed. However, although these methods are effective in improving the adhesiveness, an adhesive other than polyimide, for example, an epoxy resin adhesive is required as an adhesive, and the heat resistance of the entire flexible substrate is lowered.

For this reason, as a polyimide film, a polyimide film having a thermoplastic polyimide layer such as a thermoplastic single layer polyimide film or a multilayer polyimide film having a thermoplastic thin layer in which a thin layer of thermoplastic polyimide is laminated on both sides of a heat resistant polyimide layer (Hereafter, it may be abbreviated simply as a thermoplastic polyimide film).
However, when the surface of these thermoplastic polyimide films is smooth, the friction with the roll or the like is large when the film is wound on the winding roll or when laminating with the copper foil, Troubles such as wrinkles and wrapping around the roll may occur, limiting the winding, and therefore it was necessary to improve the surface lubricity of the thermoplastic polyimide film.

  Conventionally, as a method for improving the surface smoothness of a polyimide film, a method of performing a surface treatment such as embossing or mixing inorganic powders such as calcium phosphate (Patent Document 1) and silica (Patent Document 2) with a polyimide film, A method has been adopted in which fine protrusions are formed on the film surface to reduce surface friction. Further, a method for producing a polyimide film by casting a polyamic acid solution in which fine inorganic fillers are dispersed and polymerized in a solvent has been proposed (Patent Document 3).

JP-A-62-68852 JP 62-68853 A JP-A-6-145378

However, the first surface treatment method has a drawback in that excessive unevenness occurs on the film surface and the appearance of the film is easily impaired. In the second method, the inorganic powder is mixed with the polyamic acid solution. However, if a special dispersing device is not used, the inorganic powder is difficult to uniformly disperse in the polyamic acid solution and becomes a lump without being dispersed. Large protrusions may be formed on the film surface. Similarly, in the third method, it is difficult to uniformly disperse the fine particle inorganic powder, and if an inorganic powder having a large particle size is used, there is no significant difference from the second method.
For this reason, in the method of adding these inorganic fillers, the projections on the surface of the thermoplastic polyimide film become an obstacle to the formation of fine pitches in the copper-clad laminated substrate used for COF, TAB, etc. that require a fine pattern. There is a case.

The problem to be solved is to improve the slipperiness of a polyimide film having a thermoplastic polyimide surface layer.
Another object is to obtain a polyimide film having a thermoplastic polyimide surface layer that improves slipperiness and suppresses the formation of large surface protrusions that hinder fine pitch formation.

This invention has a polyimide surface layer made of polyimide that is thermoplastic and has a glass transition temperature of 190 to 450 ° C., and contains at least about 80 μm of pyromellitic acid component and p-phenylenediamine component in about 1 μm of the polyimide surface layer. The ratio of about 0.5 to 10% by mass with respect to the polyimide of the polyimide surface layer of wholly aromatic polyimide particles composed of polyimide containing at least% and having a median diameter of 0.3 to 0.8 μm and a maximum diameter of 2 μm or less It is related with the polyimide film with which the slipperiness improved by disperse | distributing.
Further, the present invention is made of polyimide which is thermoplastic and has a glass transition temperature of 190 to 450 ° C., and has a median diameter of 0.3 to 0.8 μm and a maximum diameter of 2 μm or less in about 1 μm of the polyimide surface layer. It has a polyimide surface layer that does not contain inorganic powder formed by dispersing certain aromatic polyimide particles at a ratio of about 0.5 to 10% by mass with respect to the polyimide of the polyimide surface layer, and has a static friction coefficient of 0.05 to 0. 7. It relates to a polyimide film with improved slidability having a dynamic friction coefficient of 0.05 to 0.7.
In addition, the present invention provides a heat fusion that does not contain inorganic powder in which the total aromatic polyimide particles are dispersed at a ratio of about 0.5 to 10% by mass with respect to the polyimide of at least one surface of the heat-fusible polyimide surface layer. The present invention relates to an easy-sliding polyimide film having a conductive polyimide surface layer, heat-fusible, long and good winding properties.
In addition, the present invention has a heat-fusible polyimide surface layer containing no inorganic powder in which all aromatic polyimide particles are dispersed in polyimide of at least one side of the heat-fusible polyimide surface layer, and has a static friction coefficient of 0. The present invention relates to a slippery polyimide film having a heat fusion property of 05 to 0.7 and a dynamic friction coefficient of 0.05 to 0.7 and having a long and good winding property.
Furthermore, the present invention relates to a copper-clad laminate in which a copper layer is laminated via a polyimide surface layer of the heat-sealable polyimide film having improved lubricity.
In the above description, at least about 1 μm of the polyimide surface layer means that the polyimide surface layer is rounded off to a thickness of 1 μm or more, preferably 0.7 μm or more.

The polyimide film with improved slipperiness according to the present invention has an appropriate coefficient of friction and can be easily wound on a roll.
Moreover, according to this invention, it can laminate | stack with a copper foil directly, without interposing another resin layer.
In addition, the copper-clad laminate of the present invention does not have abnormal extra large protrusions on the polyimide surface and can be finely processed.

The preferred embodiments of the present invention are listed below.
1) Polyimide surface layer is composed of 1,3-bis (4-aminophenoxy) benzene and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-biphenyltetra The polyimide film with improved slipperiness as described above, comprising thermoplastic polyimide obtained by copolymerization at a ratio (molar ratio) of both components to carboxylic dianhydride of 10/90 to 90/10.
2) The above-described slippery material comprising a polyimide obtained by polymerizing 4,4′-diaminodiphenyl ether and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride. Improved polyimide film.

3) The polyimide film with improved slipperiness as described above, wherein the entire film has a thickness of about 10 to 50 μm.
4) The copper layer is formed by laminating a copper foil by a laminating method, or forming a metal thin film and a copper plating layer using a thin film deposition method and an electroplating method, and laminating the copper layer. Copper-clad laminated board.

The polyimide film with improved slipperiness according to the present invention satisfies the above conditions on the surface of a film made of polyimide having thermoplasticity and a glass transition temperature of 190 to 450 ° C., preferably 190 to 320 ° C. And a surface layer satisfying the above conditions on both sides of a heat-resistant polyimide layer.
The polyimide film with improved slipperiness according to the present invention includes, for example, a polyamic acid solution and pyromellitic acid which give a polyimide having thermoplasticity and a glass transition temperature of 190 to 450 ° C., preferably 190 to 320 ° C. The total aromatic polyimide particles containing 80% or more of the component and the p-phenylenediamine component, having a median diameter of 0.3 to 0.8 μm and a maximum diameter of 2 μm or less are 0.5 to 10 to the polyamic acid. A polyamic acid solution composition containing 5% by mass, preferably 0.5 to 5% by mass, is applied onto a support so that the thickness after drying is about 1 μm or more, dried and heated to remove the solvent. And by imidization.

  In addition, the polyimide film with improved lubricity according to the present invention is, for example, a polyamic acid solution that gives a polyimide core layer made of heat-resistant polyimide is cast on a support and dried to form a self-supporting film. A polyamic acid solution for a surface layer which gives a polyimide having thermoplasticity and a glass transition temperature of 190 to 450 ° C., preferably 190 to 320 ° C., a pyromellitic acid component and a p-phenylenediamine component on both sides % Of the total aromatic polyimide particles having a median diameter of 0.3 to 0.8 μm and a maximum diameter of 2 μm or less with respect to the polyamic acid for the surface layer, preferably 0.5 to 10% by mass, preferably 0 The surface layer polyamic acid solution composition contained at a ratio of 5 to 5% by mass is applied and dried so that the thickness after drying is about 1 μm or more. Applying another of said surface layer for a polyamic acid solution composition on a surface so that the thickness after drying of about 1μm or more, by dried and the solvent removal and imidization by heating, can be produced.

As the polyimide of the thermoplastic polyimide layer having the above thermoplasticity and a glass transition temperature of 190 to 450 ° C., preferably 190 to 320 ° C., 1,3-bis (4-aminophenoxy) benzene and 2,3 , 3 ′, 4′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride have a ratio (molar ratio) of both components of 20/80 to 80/20. It is obtained by polymerizing a heat-fusible polyimide obtained by copolymerization at a ratio of 4,4-diaminodiphenyl ether and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride. A polyimide is mentioned.
Further, as the polyimide of the thermoplastic polyimide surface layer, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane, bis (3 , 4-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) ether, 4,4′-diaminodiphenylether, 3,3′-diaminodiphenylether A polyimide having a monomer component having a flexible structure is exemplified.

  As the polyimide of the heat-resistant polyimide layer, 15 to 100 mol% or more of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 0 to 85 mol% of pyromellitic dianhydride and 15 Polyimide or pyromellitic dianhydride obtained by polymerization and imidization from ˜100 mol% or more of p-phenylenediamine and 0 to 85 mol% of 4,4′-diaminodiphenyl ether and 4,4 A polyimide obtained by copolymerizing '-diaminodiphenyl ether and p-phenylenediamine at a ratio of both components (molar ratio) of 90/10 to 10/90 is mentioned.

In the above method, the polyamic acid solution that gives heat-resistant polyimide can be obtained by polymerizing an aromatic diamine that gives heat-resistant polyimide and an aromatic tetracarboxylic dianhydride by an ordinary method in an organic polar solvent.
Examples of the organic polar solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam amide solvents, dimethyl sulfoxide, hexamethylphosphoramide, dimethyl sulfone. , Tetramethylene sulfone, dimethyltetramethylene sulfone, pyridine, ethylene glycol and the like.

  In the above-described method, it is preferable that the polyamic acid solution is cast-coated on a support surface such as a polyester film, a stainless steel mirror surface, or a belt surface to be semi-cured or dried at 100 to 200 ° C. When a cast film is processed at a high temperature exceeding 200 ° C., defects such as a decrease in adhesion tend to be caused in the production of thermoplastic polyimide films. This semi-cured state or an earlier state means that it is in a self-supporting state by heating and / or chemical imidization.

  In the above method, a polyamic acid solution for a surface layer which gives a polyimide having thermoplasticity and a glass transition temperature of 190 to 450 ° C., preferably 190 to 320 ° C., a pyromellitic acid component and a p-phenylenediamine component 0.5 to 10% by mass of the wholly aromatic polyimide particles containing 80% or more and having a median diameter of 0.3 to 0.8 μm and a maximum diameter of 2 μm or less with respect to the polyamic acid for the surface layer, preferably A polyamic acid solution composition containing 0.5 to 5% by mass is used.

  As said total aromatic polyimide particle, p-phenylenediamine and pyromellitic dianhydride are added to the above polar solvent in an amount of 80% or more in an amount of 3 to 10% by mass of polyimide in the mixture. If necessary, a dispersant is added, the temperature is raised to about 160 ° C. while stirring in an inert gas atmosphere such as nitrogen gas, the whole fragrance obtained by heating at this temperature for about 2 to 5 hours and then cooling. It is preferable to use the solution mixture containing the aromatic polyimide particles as it is, or, if necessary, remove or add the polar solvent as a wholly aromatic polyimide particle solvent mixture.

In the present invention, the wholly aromatic polyimide particles preferably use an aromatic diamine and an aromatic tetracarboxylic acid component in which p-phenylenediamine and pyromellitic dianhydride are 80% or more. When the aromatic diamine and the aromatic tetracarboxylic acid component are other than the two components, it is impossible to obtain wholly aromatic polyimide particles having a maximum diameter of 0.3 to 0.8 μm and a maximum diameter of 2 μm or less. Further, if the shape of the polyimide particles is of a particle size outside the above range, it is difficult to form fine protrusions on the surface of the thermoplastic polyimide layer, and a copper-clad laminate substrate that requires a fine pattern is required. Is not preferred.
The median diameter refers to a diameter corresponding to a 50% cumulative value of the cumulative distribution curve.
Accordingly, the polyimide particles in the present invention may be spherical, but may be columnar having a ratio of the minor axis to the major axis of 2 to 10, particularly about 3 to 6. In the case of a columnar shape, those having a minor axis of 0.05 to 0.5 μm and a major axis of 0.7 to 1.5 μm are preferable.
In addition, when a fine pattern is not required for the copper-clad laminate, fully aromatic polyimide particles having a median diameter of 0.3 to 10 μm can be used.

According to this invention, it has a polyimide surface layer that is made of polyimide that is thermoplastic and has a glass transition temperature of 190 to 450 ° C. and does not contain inorganic powder, and has a coefficient of static friction of 0.05 to 0.7, preferably Polyimide having 0.1 to 0.7, a coefficient of dynamic friction of 0.05 to 0.7, preferably 0.1 to 0.7, no large protrusions formed on the film surface, and improved slipperiness A film is obtained.
In particular, according to the present invention, at least one surface is heat-sealable and is a long and easy-sliding polyimide film that can be wound on a winding roll at a speed of 1 m / min or more, and a copper using the same A stretched laminated substrate can be obtained.

The copper-clad laminate of the present invention is obtained by laminating a copper layer via the polyimide surface layer of the polyimide film having improved lubricity.
The copper layer can be formed by laminating a copper foil by a laminating method or forming a metal thin film and a copper plating layer by using a thin film forming method and an electroplating method.
Lamination of the copper foil by the laminating method and thin film forming method and metal thin film using the electroplating method and the copper layer laminating method for forming the copper plating layer can employ all methods known per se. .

In this specification, the evaluation method of slipperiness [coefficient of static friction, coefficient of dynamic friction] is as follows.
In accordance with the method described in ASTM D1894, one side of a polyimide film held at 23 ° C., 60% RH for 24 hours and humidity-adjusted is used as a substrate, and is adhered to a thread metal so that the opposite side is rubbed together. (Sliding speed: 150 mm / min) was used to measure the friction coefficient.
The value when the chart starts to move is displayed as a static friction coefficient, and the value when the chart is stabilized as a dynamic friction coefficient.
In this specification, the method for evaluating the quality of winding is as follows.
In other words, whether the winding property is good or bad is that when a long polyimide film is wound on a winding roll (the outer diameter of the mandrel: 15 cm) at a speed of 2 m / min, wrinkles are generated or the roll is wound. The winding property is considered to be good when winding is not smooth and winding is not good, and when winding is possible without causing wrinkles.

The size of the particulate polyimide is analyzed as follows.
Using N, N-dimethylacetamide as a dispersion solvent, dispersing for 60 minutes with ultrasonic waves, measuring range of 0.02 to 1000 μm, volume as a particle size reference by laser diffraction-scattering particle size distribution measurement method It is measured by the standard. The slurry solution obtained by producing the particulate polyimide was dispersed for 60 minutes with an ultrasonic cleaner. A dispersion medium was placed in the measurement cell, and the slurry solution dispersed therein was dropped and diluted so that the transmittance of the laser light / lamp was 95 to 75%. Then, it measured by manual batch type cell measurement. Equipment: Laser diffraction-scattering type particle size distribution measuring device (Type: LA-910, manufactured by Horiba, Ltd.), Measurement mode: Manual batch cell measurement Shape analysis of particulate polyimide is performed on a glass plate The shape of the particulate polyimide was confirmed by SEM observation.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
The possibility of fine patterning was judged from the possibility of migration when forming a fine pattern of 20 μm: line 10 μm / space 10 μm.
○: Fine pattern possible, ×: Fine pattern not possible Reference Example 1
Preparation of particulate polyimide Particulate polyimide is prepared by dissolving p-phenylenediamine and pyromellitic dianhydride in N, N'-dimethylacetamide, and dispersing agent (Desper-Sant: 0.5% by mass relative to monomer). ) Was added, and the temperature was gradually raised to 160 ° C. with stirring (40 rpm) in a nitrogen atmosphere, and after reaching this temperature, stirring was performed for 3 hours. Analysis of the obtained particulate polyimide was performed by measuring the particle size distribution with a laser diffraction-scattering particle size distribution measuring device, and the median diameter was 0.3 μm and the distribution range was 0.1 to 1 μm. Moreover, as a result of confirming the shape of the particulate polyimide in SEM observation, the ratio of the minor axis to the major axis was a columnar particle having 3 to 6.

Mainly 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 1,3-bis (4-aminophenoxy) benzene Particulate polyimide is added to the obtained polyamic acid 18% by mass solution so as to be 0.5% by mass with respect to the monomer concentration, and cast onto a stainless steel substrate so that the film thickness after drying is 25 μm. The film was dried with hot air at 120 ° C. and peeled from the substrate to obtain a self-supporting film. The obtained self-supporting film was gradually heated from 140 ° C. to 330 ° C. in a heating furnace to remove the solvent and imidize, and wound up a long polyimide film on a winding roll. The windability during winding was good. Moreover, the friction coefficient of the obtained film was measured. Mainly 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 1,3-bis (4-aminophenoxy) benzene The Tg of the resulting polyimide was 240 ° C.
The result evaluated about the obtained polyimide film is shown next.
Film thickness (μm): 25
Surface lubricant concentration (%): 0.5
Type of lubricant: Totally aromatic particulate polyimide Static coefficient of friction: 0.51
Coefficient of dynamic friction: 0.47

Mainly 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 1,3-bis (4-aminophenoxy) benzene The obtained 18% by mass solution of polyamic acid was cast on a stainless steel substrate so that the film thickness after drying was 24 μm, and dried with hot air at 120 ° C. 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 1,3-bis (4- Aminophenoxy) A solution obtained by adding particulate polyimide to a 5% by mass solution of polyamic acid mainly obtained from benzene so as to be 2% by mass with respect to the monomer concentration is laminated so that the total film thickness after drying is 25 μm. Then, it was dried with hot air at 120 ° C. and peeled from the substrate to obtain a self-supporting film. The obtained self-supporting film was gradually heated from 140 ° C. to 330 ° C. in a heating furnace to remove the solvent and imidize, and wound up a long polyimide film on a winding roll. The windability during winding was good. Moreover, the friction coefficient of the obtained film was measured. 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 1,3-bis (4-amino) used for the surface layer The Tg of the polyimide obtained mainly from phenoxy) benzene was 240 ° C.
The result evaluated about the obtained polyimide film is shown next.
Film thickness (μm): 25
Surface lubricant agent concentration (%): 2.0
Easy lubricant type: Totally aromatic particulate polyimide Static coefficient of friction: 0.37
Coefficient of dynamic friction: 0.33

Mainly 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 1,3-bis (4-aminophenoxy) benzene The obtained 10% by mass solution of polyamic acid was cast on a stainless steel substrate so that the film thickness after drying was 3 μm, and was dried with hot air at 120 ° C. On the obtained dry film, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and p-phenylenediamine are mainly used to obtain an 18% by mass solution of polyamic acid so that the thickness after drying becomes 22 μm. And dried with hot air at 120 ° C., and then 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 2,3,3 ′, 4′-biphenyltetracarboxylic acid After drying a solution obtained by adding particulate polyimide to a 10% by mass solution of polyamic acid mainly obtained from anhydride and 1,3-bis (4-aminophenoxy) benzene so as to be 2% by mass with respect to the monomer concentration The film was laminated so that the total film thickness was 25 μm, dried with hot air at 120 ° C., and peeled from the substrate to obtain a self-supporting film. The obtained self-supporting film was heated in the same manner, and a long polyimide film was wound on a winding roll. The windability during winding was good. Moreover, the friction coefficient of the obtained film was measured. 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 1,3-bis (4-amino) used for the surface layer The Tg of the polyimide obtained mainly from phenoxy) benzene was 240 ° C.
The result evaluated about the obtained polyimide film is shown next.
Film thickness (μm): 25
Surface lubricant agent concentration (%): 2.0
Easy lubricant type: Totally aromatic particulate polyimide Static coefficient of friction: 0.45
Coefficient of dynamic friction: 0.40

Mainly 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 1,3-bis (4-aminophenoxy) benzene The obtained 10% by mass solution of polyamic acid was cast on a stainless steel substrate so that the film thickness after drying was 3 μm, and was dried with hot air at 120 ° C. On the obtained dry film, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and p-phenylenediamine are mainly obtained to obtain an 18% by mass solution of polyamic acid so that the thickness after drying becomes 21 μm. And dried with hot air at 120 ° C., and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 1,3-bis (4-aminophenoxy) benzene was laminated so that the thickness after drying a 10% by weight polyamic acid solution obtained mainly was 24 μm, and dried with hot air at 120 ° C. Subsequently, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 1,3-bis (4-aminophenoxy) benzene A solution obtained by adding particulate polyimide to a 5% by mass solution of polyamic acid obtained mainly so as to be 2% by mass with respect to the monomer concentration is laminated so that the total film thickness after drying is 25 μm, and 120 ° C. The film was dried with hot air and peeled from the substrate to obtain a self-supporting film. The obtained self-supporting film was heated in the same manner, and a long polyimide film was wound on a winding roll. The windability during winding was good. Moreover, the friction coefficient of the obtained film was measured. 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 1,3-bis (4-amino) used for the surface layer The Tg of the polyimide obtained mainly from phenoxy) benzene was 240 ° C.
The result evaluated about the obtained polyimide film is shown next.
Film thickness (μm): 25
Surface lubricant agent concentration (%): 2.0
Easy lubricant type: Totally aromatic particulate polyimide Static coefficient of friction: 0.33
Coefficient of dynamic friction: 0.31

The film thickness after drying an 18% by mass solution of polyamic acid obtained mainly from 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3′-diaminodiphenyl ether is 24 μm. The product was cast on a stainless steel substrate and dried with hot air at 120 ° C. 2 masses of polyamic acid obtained mainly from polyamic acid obtained mainly from 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3′-diaminodiphenyl ether on the obtained dry film A solution obtained by adding particulate polyimide to a solution of 2% by mass with respect to the monomer concentration is laminated so that the total film thickness after drying is 25 μm, and dried with hot air at 120 ° C. It peeled and the self-supporting film was obtained. The obtained self-supporting film was heated in the same manner, and a long polyimide film was wound on a winding roll. The windability during winding was good. Moreover, the friction coefficient of the obtained film was measured. Tg of the polyimide mainly obtained from 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3′-diaminodiphenyl ether used for the surface layer was 280 ° C.
The result evaluated about the obtained polyimide film is shown next.
Film thickness (μm): 25
Surface lubricant agent concentration (%): 2.0
Easy lubricant type: Totally aromatic particulate polyimide Static coefficient of friction: 0.42
Coefficient of dynamic friction: 0.31

Using each of the polyimide films obtained in Examples 1 to 4, a 12 μm thick copper foil (rolled copper foil or electrolytic copper foil) on one side and a protective material (Upilex 25S) on the other side, Continuously supplied to the double belt press, after preheating, heating zone temperature (maximum heating temperature) 330 ° C (setting), cooling zone temperature (minimum cooling temperature) 117 ° C), pressure bonding pressure 40 kg / cm ^{2. In} a crimping time of 2 minutes, it was possible to continuously obtain a roll wound product that was a single-sided copper-clad laminated substrate with a protective material by thermocompression-cooling and cooling under pressure.
Moreover, these single-sided copper clad laminated substrates were evaluated.
Peel strength between copper foil and polyimide film (90 degree peel): Either 1 kgf / cm or more Fine pattern propriety: ○
Using the polyimide film obtained in Example 5, copper was deposited on the Ni / Cr base metal by a conventional method, and then copper electroplating was performed to continuously roll the rolled product as a single-sided copper-clad laminate. Could get to.
Moreover, this single-sided copper-clad laminated substrate was evaluated.
Peel strength between copper foil and polyimide film (90 degree peel): 0.8 kgf / cm
Fine pattern availability: ○

(Reference Example 1)
Polyimide powder using p-phenylenediamine and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride instead of p-phenylenediamine and pyromellitic anhydride to produce particulate polyimide Got.
The shape of this polyimide powder was as follows.
The median diameter was 8.9 μm and the distribution range was 0.1 to 22.8 μm. Moreover, as a result of confirming the shape of the particulate polyimide in SEM observation, it was a spherical particle.
The same operation as in Example 4 was performed except that this polyimide powder was used. The winding property at the time of winding a long polyimide film on a winding roll was good.
The results were as follows.
Film thickness (μm): 25
Surface lubricant agent concentration (%): 2.0
Easy lubricant type: Totally aromatic particulate polyimide Static coefficient of friction: 0.35
Coefficient of dynamic friction: 0.29
The SEM observation result of the surface of the surface layer of the obtained polyimide film is shown in FIG.
Using the polyimide film obtained in Reference Example 1 , a roll wound product which is a single-sided copper-clad laminated substrate with a protective material could be obtained continuously.
Moreover, these single-sided copper clad laminated substrates were evaluated.
Peel strength between copper foil and polyimide film (90 degree peel): 1 kgf / cm or more Fine pattern propriety: x

(Reference Example 2)
To prepare particulate polyimide, 3,3′-diaminodiphenyl ether and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride instead of p-phenylenediamine and pyromellitic anhydride Was used to obtain polyimide powder.
The shape of this polyimide powder was as follows.
The median diameter was 7.7 μm, and the distribution range was 0.2 to 22.8 μm. Moreover, as a result of confirming the shape of the particulate polyimide in SEM observation, it was a spherical particle.
The same operation as in Example 4 was performed except that this polyimide powder was used. The winding property at the time of winding a long polyimide film on a winding roll was good.
The results were as follows.
Film thickness (μm): 25
Surface lubricant agent concentration (%): 2.0
Easy lubricant type: Totally aromatic particulate polyimide Static coefficient of friction: 0.38
Coefficient of dynamic friction: 0.32
The SEM observation result of the surface of the surface layer of the obtained polyimide film is shown in FIG.
Using the polyimide film obtained in Reference Example 2 , a roll wound product which is a single-sided copper-clad laminated substrate with a protective material could be obtained continuously.
Moreover, these single-sided copper clad laminated substrates were evaluated.
Peel strength between copper foil and polyimide film (90 degree peel): 1 kgf / cm or more Fine pattern propriety: x

Comparison 1
It implemented similarly to Example 1 except having used the silica filler (ST-ZL, the Nissan Chemical Co., Ltd. make, median diameter 0.13 micrometer) which is an inorganic filler instead of the particulate polyimide. The winding property when winding a long polyimide film on a winding roll was poor.
The results were as follows.
Film thickness (μm): 25
Surface lubricant concentration (%): 0.5

Comparison 2
It implemented similarly to Example 2 except having used the silica filler (ST-ZL, median diameter 0.13 micrometer) which is an inorganic filler instead of particulate polyimide. The winding property when winding a long polyimide film on a winding roll was poor.
The results were as follows.
Film thickness (μm): 25
Surface lubricant agent concentration (%): 2.0

FIG. 1 is a diagram showing SEM observation results (2000 times) of the surface of the surface layer of the polyimide film obtained in Example 4 of the present invention. FIG. 2 is a diagram showing SEM observation results (2000 times) of the surface layer of the polyimide film obtained in Example 6. FIG. 3 is a diagram showing SEM observation results (2000 times) of the surface layer of the polyimide film obtained in Example 7. FIG.

Claims (11)

Glass transition temperature A thermoplastic has a polyimide surface layer made of polyimide is 190-450 ° C., is obtained from at least a polyimide surface layer (1 [mu] m thick) pyromellitic acid component in the p- phenylenediamine component Columnar wholly aromatic polyimide particles made of polyimide having a median diameter of 0.3 to 0.8 μm, a maximum diameter of 2 μm or less, and a ratio of the short diameter to the long diameter of 2 to 10 are 0 with respect to the polyimide of the polyimide surface layer. A polyimide film with improved slipperiness which is dispersed at a ratio of 5 to 10% by mass. The polyimide surface layer is composed of a polyimide obtained from a pyromellitic acid component and a p-phenylenediamine component in a thickness of 0.7 μm or more of the polyimide surface layer, and has a median diameter of 0.3 to 0.8 μm and a maximum diameter of 2 μm or less. The columnar wholly aromatic polyimide particles having a ratio of the minor axis to the major axis of 2 to 10 are dispersed at a ratio of 0.5 to 10% by mass with respect to the polyimide of the polyimide surface layer. 2. A polyimide film with improved slipperiness according to 1. The polyimide surface layer is made of polyimide obtained from a pyromellitic acid component and a p-phenylenediamine component in a thickness of 0.7 μm or more of the polyimide surface layer, and has a median diameter of 0.3 to 0.8 μm and a particle diameter distribution range. Columnar wholly aromatic polyimide particles having a minor axis to major axis ratio of 2 to 6 of 0.1 to 1 μm are dispersed at a ratio of 0.5 to 10% by mass with respect to the polyimide of the polyimide surface layer. The polyimide film having improved slipperiness according to claim 1.   The polyimide surface layer according to any one of claims 1 to 3, wherein the polyimide surface layer does not contain an inorganic powder.   The polyimide film with improved slipperiness is used to laminate copper foil directly on the polyimide surface layer of the polyimide film with improved slipperiness by the lamination method, or the polyimide surface of the polyimide film with improved slipperiness The easy-sliding material according to any one of claims 1 to 4, which is used for producing a single-sided copper-clad laminated substrate obtained by depositing a Ni / Cr base metal directly on a layer, and then depositing copper and then electroplating copper. Improved polyimide film.   The polyimide film with improved slipperiness forms a self-supporting film that gives a polyimide core layer made of heat-resistant polyimide, and the total aromatic polyimide particle 0.5 on the polyamic acid of the polyimide surface layer on one or both sides It is manufactured by apply | coating and drying the polyamic acid solution composition for surface layers containing 10 mass%, heating, removing a solvent, and imidating, The easy in any one of Claims 1-5 characterized by the above-mentioned. Polyimide film with improved lubricity. The polyimide surface layer
1) 1,3-bis (4-aminophenoxy) benzene and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride And a thermoplastic polyimide obtained by copolymerization at a ratio (molar ratio) of both components of 10/90 to 90/10,
2) A polyimide obtained by polymerizing 4,4′-diaminodiphenyl ether and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride,
Or 3) 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) ether, 4,4'-diaminodiphenylether or polyimide having a flexible monomer component in the polyimide molecule of 3,3'-diaminodiphenylether The polyimide film with improved slipperiness according to any one of claims 1 to 5, wherein The heat-resistant polyimide is composed of 15 to 100 mol% or more of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 0 to 85 mol% of pyromellitic dianhydride and 15 to 100 mol% of p. A polyimide obtained by polymerization and imidization from phenylenediamine and 0-85 mol% of 4,4′-diaminodiphenyl ether, or pyromellitic dianhydride and 4,4′-diaminodiphenyl ether It is a polyimide obtained by copolymerizing the ratio (molar ratio) of both components with p-phenylenediamine in the ratio of 90/10 to 10/90, The improvement of the slipperiness of Claim 6 characterized by the above-mentioned. Polyimide film.   The thickness of the whole film is 10-50 micrometers, The polyimide film with improved slipperiness in any one of Claims 1-8 characterized by the above-mentioned.   The copper film is directly laminated by a laminating method on the polyimide surface layer of the polyimide film with improved slipperiness of the polyimide film with improved slipperiness according to any one of claims 1 to 9. Copper-clad laminated board.   After depositing a Ni / Cr base metal and then copper directly on the polyimide surface layer of the polyimide film with improved slipperiness of the polyimide film with improved slipperiness according to any one of claims 1-9. A copper-clad laminate that is electro-copper plated.

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