JP3151840B2 - Film carrier tape - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film carrier tape having excellent heat resistance, chemical resistance, dimensional stability, curl, and high adhesion without curling.

[0002]

2. Description of the Related Art Conventionally, a film carrier tape is manufactured by processing a sprocket hole and a device hole at a predetermined position on a side surface of a polyimide film with a punch, and then bonding the film portion excluding the hole portion and a metal foil with an adhesive. Have been. In such a film carrier tape, since the heat resistance of the adhesive is not sufficient, the excellent heat resistance, chemical resistance, electrical properties, mechanical properties, and the like inherent to the polyimide film are not fully utilized. It is. Further, there is a problem that the adhesive force of the adhesive itself is not always sufficient.

[0003] As a method of solving such a problem,
A method in which an organic polar solvent solution of the polyimide precursor is directly applied to the surface of the metal foil without using an adhesive, and then the solvent is dried and removed, or imidation is performed, or a method in which the polyimide film and the metal foil are bonded with an aromatic polyamic acid, etc. Has been proposed. However, the former has not yet been put to practical use because it is difficult to process a device hole for mounting an IC chip. On the other hand, the latter is superior in heat resistance, chemical resistance, electric properties, etc. to those using conventional adhesives, but after laminating copper foil and heat resistant resin film,
At present, it has not been put to practical use due to large curl.

[0004]

SUMMARY OF THE INVENTION The inventors of the present invention have been made in view of the above-mentioned drawbacks of the prior art, and the object thereof is to provide excellent heat resistance, chemical resistance, dimensional stability, and curl. It is an object of the present invention to provide a film carrier tape having a high adhesive force without any problem.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problem described above, wherein the surface is
A film carrier tape obtained by laminating and integrating a low-temperature plasma-treated heat-resistant insulating film and a metal foil via an adhesive layer, wherein the adhesive layer has an aromatic tetracarboxylic dianhydride and a siloxane-based diamine. And a film carrier tape characterized by comprising a thin film of imidized polyamic acid obtained by reacting as a main component.

The heat-resistant insulating film of the present invention has a melting point of 280 ° C. or higher, or JIS C40.
The maximum allowable temperature for long-term continuous use specified in 03 is 121
A polymer resin film that satisfies the condition at any one of not less than ° C is used.

[0007] These polymer resin films include polyarylsulfones represented by condensates of dicarboxylic acids of bisphenols, polyallylsulfones represented by polysulfones or polyethersulfones, condensation of benzotetracarboxylic acids with aromatic isocyanates. Thermosetting polyimide, aromatic polyimide, aromatic polyamide, aromatic polyether amide, polyphenylene sulfide, polyallyl ether ketone, polyamide imide resin film obtained from the reaction of a product or bisphenols, aromatic diamine, nitrophthalic acid And the like. Among these polymer resin films, aromatic polyimides, aromatic polyamides, particularly pyromellitic dianhydride, or aromatic polyimides which are condensates of aromatic diamines such as biphenyltetracarboxylic dianhydride and diaminodiphenyl ether Resin films are particularly preferred.

The surface of such a heat-resistant resin film is preferably subjected to low-temperature plasma treatment. Here, the low-temperature plasma treatment means a treatment performed by exposing the surface of the heat-resistant resin film to a discharge which is started and maintained by applying a high DC or AC voltage between the electrodes. The pressure for the treatment is not particularly limited, and preferable conditions may be selected depending on the type of discharge of the treatment apparatus. The processing atmosphere may be a general atmosphere such as Ar, He, N ₂ , H ₂ O, O ₂ , air, etc., but may be an organic gas such as methanol, ethanol, glycidyl methacrylate, or the like.
Glycidyl methacrylate is particularly preferred. The organic gases can be used alone or in combination of two or more. Further, it may be diluted with a gas such as Ar, He, N ₂ and air.

As the metal foil, various conductive materials such as copper, aluminum and nickel can be used. The thickness is preferably from 10 to 100 μm.
The surface of the metal foil is preferably roughened,
What is necessary is just for a generally used film carrier tape, and there is no particular limitation.

As the aromatic tetracarboxylic dianhydride used in the present invention, pyromellitic acid, 3,3 ′, 4,
4' - biphenyltetracarboxylic dianhydride, 2,3
3 ′, 4′ - biphenyltetracarboxylic dianhydride,
3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic acid Dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride,
Bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 2,3,6,7 - naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,2 5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10 - perylenetetracarboxylic dianhydride, 2,3,6 7 - anthracene tetracarboxylic dianhydride, 1,2,7,8 -
Such as phenanthrene integrators tetracarboxylic acid dianhydride is used. These may be used alone or in combination of two or more.

The siloxane-based diamine used in the present invention includes those represented by the following general formula (1).

[0012]

Embedded image

(Wherein R1 and R2 each represent a lower alkylene group or a phenylene group, and R3, R4, R
5 and R6 each represent at least one selected from the group consisting of a lower alkoxy group, a phenyl group and a phenoxy group. n shows the integer of 1 or more. ).

[0014] Specific examples of the siloxane diamine represented by the general formula (1), 1,1,3,3-tetramethyl-1,3 - bis (4-aminophenyl) disiloxane, 1,1,3 , 3-tetraphenoxy-1,3 - bis (4-aminoethyl) disiloxane, 1,1,3,3,
5,5-hexamethyl-1,5 - bis (4-aminophenyl) trisiloxane, 1,1,3,3-tetraphenyl-1,3 - bis (2-aminoethyl) disiloxane,
1,1,3,3-tetraphenyl-1,3 - bis (3-
Aminopropyl) disiloxane, 1,1,5,5-tetraphenyl-3,3-dimethyl-1,5 - bis (3-aminopropyl) trisiloxane, 1,1,5,5-tetraphenyl-3, 3-dimethoxy-1,5 - bis (4-
Aminobutyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5 - bis (5-
Aminopentyl) trisiloxane, 1,1,3,3-tetramethyl-1,3 - bis (2-aminoethyl) disiloxane, 1,1,3,3-tetramethyl-1,3 - bis (3- Aminopropyl) disiloxane, 1,1,3,3
- tetramethyl - 1, 3 - bis (4-aminobutyl) disiloxane, 1,3-dimethyl-1,3 - dimethoxy -
1,3 - bis (4-aminobutyl) disiloxane, 1,
1,5,5-tetramethyl-3,3 - dimethoxy-1,
5 - bis (2-aminoethyl) trisiloxane, 1,
1,5,5-tetramethyl-3,3 - dimethoxy-1,
5 - bis (4-aminobutyl) trisiloxane, 1,
1,5,5-tetramethyl-3,3 - dimethoxy-1,
5 - bis (5-aminopentyl) trisiloxane, 1,
1,3,3,5,5-hexamethyl-1,5 - bis (3
-Aminopropyl) trisiloxane, 1,1,3,3
5,5-hexaethyl-1,5 - bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexapropyl-1,5 - bis (3-aminopropyl) trisiloxane and the like No. These siloxane-based diamines can be used alone or in combination of two or more.

The ratio of the siloxane-based diamine in all the diamine compounds can be used in an appropriate ratio, but from the viewpoint of the effect of preventing curling after imidization and the effect of improving the adhesiveness, it is preferably at least 50 mol%. Preferably, it is at least 75 mol%.

The reaction between the aromatic tetracarboxylic dianhydride and the siloxane-based diamine can be carried out according to a conventionally known method. For example, a substantially stoichiometric amount of an aromatic tetracarboxylic acid or an anhydride thereof and a siloxane-based diamine are mixed in an organic solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2 - pyrrolidone. The reaction may be performed at a temperature of 0 to 80 ° C. These solvents are used alone or as a mixture of two or more kinds, and benzene, toluene, hexane, cyclohexane, tetrahydrofuran, methyl ethyl ketone and the like may be added as long as the polyamic acid is not precipitated.

The concentration of the polyamic acid varnish is preferably from 5 to 60% by weight, particularly preferably from 10 to 40% by weight.

The heat-resistant insulating film and the metal foil are laminated and integrated via an adhesive layer comprising an imidized thin film of a polyamic acid obtained by reacting an aromatic tetracarboxylic dianhydride with a siloxane-based diamine. To do this,
For example, the following method can be used.

That is, a solvent solution containing 10 to 40% by weight of the above-mentioned polyamic acid varnish is discharged from the slit for film formation on the heat-resistant insulating film and uniformly coated. Examples of the coating method include a roll coater, a knife coater, a sealing coater, a comma coater, and a doctor blade float coater. Next, the solvent of the solution applied to the heat-resistant resin film as described above is removed by heating at 60 to 200 ° C. As for the conditions for heat removal, appropriate temperature and pressure may be selected according to the concentration and type of the solvent. Thus, an imidized thin film of polyamic acid having a thickness of 5 to 30 μm is formed on the heat-resistant resin film. After that, a protective film such as a polyester film or polypropylene having a thickness of 15 to 60 μm is laminated on the thin film as required for preventing contamination and preventing scratches. Furthermore, after slitting to the intended width, the sprocket hole and I
After punching a device hole for mounting C, the protective film on the coated surface of the polyamic acid varnish is peeled off, and the resultant is overlaid with a metal foil and heat-pressed at 150 to 280 ° C. Compression temperature and pressure are the composition of polyamic acid varnish,
What is necessary is just to select suitably according to a film thickness, the surface roughness of a copper foil, etc. In addition, a method using a heating roll is generally preferred as a method for thermocompression bonding. The ultimately to imidize the polyamic acid varnish preferably heated to a temperature of 200 to 400 ° C.. The atmosphere for imidization is preferably an atmosphere containing less oxygen from the viewpoint of preventing oxidation of the copper foil and deterioration of the film to be imidized.
It is preferably performed in an atmosphere of an inert gas such as e, Ar, or N ₂ .

[0020]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the following description, curl and adhesiveness are measured by the following methods.

[Measurement of Curl] After the imidized sample was cut into a width of 35 mm and a length of 100 mm, it was placed on a flat plate, and the lifted lengths of the four corners were measured.
The average value was shown.

[Adhesion] The adhesion between the copper foil of the imidized sample and the heat-resistant resin film was measured by the method of JIS C-6481.

Example 1 228 g of N, N-dimethylacetamide was placed in a 500 ml four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dry N ₂ inlet, and bis (3
-Aminopropyl) tetramethyldisiloxane 19.8
After dissolving 8 g (0.08 mol), 3,3 ',
4,4 '- benzophenone tetracarboxylic dianhydride 2
5.76 g (0.08 mol) was added, and stirring was continued at 10 ° C. for 1 hour. Thereafter, the mixture was stirred and reacted at 50 ° C. for 3 hours to obtain a polyamic acid varnish. The varnish was dried on a 50 μm polyimide film (“UPILEX” 50S (manufactured by Ube Industries, Ltd.)) previously subjected to low-temperature plasma treatment in a glycidyl methacrylate atmosphere to a film thickness of 10 μm.
m and dried at 80 ° C for 5 minutes.
Dried at 20 ° C. for 5 minutes, and further dried at 150 ° C. for 15 minutes.

The above-mentioned polyamic acid varnish coating film is slit into a width of 35 mm, and then sprocket holes and device holes are formed with a punch. Then, a 35 μm electrolytic copper foil (JLP 10z manufactured by Nikko Gould Foil Co., Ltd.) With a roll laminator heated to 220 ° C.
kg / cm ² , lamination at a speed of 1 m / min, and under nitrogen atmosphere at 80 ° C., 30 minutes + 150 ° C., 60 minutes + 250
After heating step curing at 120 ° C. for 120 minutes + 350 ° C. for 120 minutes, the film was gradually cooled to room temperature to obtain a film carrier tape. The obtained film carrier tape has almost no curl, an adhesive force of 2.0 kg / cm, 320
° C, solder heat resistance of 60 seconds and dielectric constant of 3.0 (1 kHz)
z) and was extremely excellent in practical performance.

Example 2 N, N-dimethylacetamide (216 g) was charged into the same reactor as in Example 1 and bis (3-aminopropyl) tetramethyldisiloxane (19.88 g) was added in a nitrogen stream.
08 mol) and p-phenylenediamine 2.163
g (0.02 mol), 3,3 ', 4,4
4' - benzophenonetetracarboxylic dianhydride
20 g (0.10 mol) was added, and stirring was continued at 10 ° C. for 1 hour. Thereafter, the mixture was stirred and reacted at 50 ° C. for 3 hours to obtain a polyamic acid varnish.

The varnish was treated with low-temperature plasma in the same manner as in Example 1 to obtain a 75 μm polyimide film (“Kapton”).
The film thickness after drying at 300K (manufactured by Toray DuPont) is 10
μm and dried at 80 ° C for 5 minutes.
Drying at 120 ° C. for 5 minutes and further drying at 150 ° C. for 15 minutes.

The above-mentioned polyamic acid varnish coating film was slit and perforated in the same manner as in Example 1, and then a copper foil (JLP 10z manufactured by Nikko Gould Foil Co., Ltd.) was drawn with a roll laminator heated to a surface temperature of 220 ° C. Pressure 5kg / c
The laminate was bonded at m ^{2 at} a speed of 1 m / min, and was heated and cured under the same conditions as in Example 1 under a nitrogen atmosphere. The resulting film carrier tape had almost no curl, and had the same adhesive strength, solder heat resistance and dielectric constant as in Example 1.

Example 3 N, N-dimethylacetamide (223 g) was charged into the same reactor as in Example 1 and bis (3-aminopropyl) tetramethyldisiloxane (14.91 g) was added in a nitrogen stream.
06 mol) and p-phenylenediamine 8.725
g (0.04 mol) after dissolving, 3,3 ', 4,4
4' - benzophenonetetracarboxylic dianhydride
20 g (0.10 mol) was added, and stirring was continued at 10 ° C. for 1 hour. Thereafter, the mixture was stirred and reacted at 50 ° C. for 3 hours to obtain a polyamic acid varnish.

The varnish was treated with low-temperature plasma in the same manner as in Example 1 to form a 75 μm polyimide film (“Kapton”).
The film thickness after drying at 300K (manufactured by Toray DuPont) is 10
μm and dried at 80 ° C for 5 minutes.
Drying at 120 ° C. for 5 minutes and further drying at 150 ° C. for 15 minutes.

After slitting and perforating the polyamic acid varnish coating film in the same manner as in Example 1, a copper foil (manufactured by Nikko Gould Foil Co., Ltd.) was drawn with a roll laminator heated to a surface temperature of 220 ° C. Pressure 5kg / c
The pieces were bonded together at m ^{2 at} a speed of 1 m / min, and were heated and cured in a nitrogen atmosphere in the same manner. The resulting film carrier tape had almost no curl, and had the same adhesive strength, solder heat resistance and dielectric constant as in Example 1.

Comparative Example 1 183 g of N, N-dimethylacetamide was placed in a 500 ml four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dry N ₂ inlet, and bis (3
-Aminopropyl) tetramethyldisiloxane 4.97
g (0.08 mol) and 8.652 g (0.08 mol) of p-phenylenediamine,
3 ', 4,4' - stirring was continued for 1 hour at 10 ° C. was added benzophenone tetracarboxylic dianhydride 32.20g (0.1mol). Thereafter, the mixture was stirred and reacted at 50 ° C. for 3 hours to obtain a polyamic acid varnish. The varnish is applied to a 50 μm polyimide film (“UPILEX” 50S (manufactured by Ube Industries, Ltd.)) so that the film thickness after drying becomes 10 μm, dried at 80 ° C. for 5 minutes, and further at 120 ° C. for 5 minutes. Drying Further, drying was performed at 150 ° C. for 15 minutes.

After slitting the polyamic acid varnish coating film to a width of 35 mm, forming a sprocket hole and a device hole by a punch, 35 μm electrolytic copper foil (JLP 10z manufactured by Nikko Gould Foil Co., Ltd.) With a roll laminator heated to 220 ° C.
kg / cm ^2, bonded together at a speed 1m / min, and heat curing in the same way further under a nitrogen atmosphere. Although the obtained film carrier tape had relatively good adhesive strength (1.7 kg / cm) and solder heat resistance, it had a large curl of 25 mm, making it impractical.

Comparative Example 2 99 g of N, N-dimethylacetamide was placed in a 200 ml four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dry N ₂ inlet, and 10.12 g of diaminodiphenyl ether (0. .05Mol) after dissolving 3,3 ', 4,4' - stirring was continued for 1 hour at 10 ° C. was added biphenyl dianhydride 14.71 g (0.05 mol). Thereafter, the mixture was stirred and reacted at 50 ° C. for 3 hours to obtain a polyamic acid varnish. The varnish was dried on a 50 μm polyimide film (“UPILEX” 50S (manufactured by Ube Industries, Ltd.)) to a film thickness of 10 μm.
m and dried at 80 ° C for 5 minutes.
Dried at 20 ° C. for 5 minutes, and further dried at 150 ° C. for 15 minutes.

The polyamic acid varnish-coated film was slit to a width of 35 mm, processed into a sprocket hole and a device hole by a punch, and then subjected to 35 μm electrolytic copper foil (JLP 10z manufactured by Nikko Gould Foil Co., Ltd.). With a roll laminator heated to 220 ° C.
^They were bonded together at a rate of 1 m / min at a rate of 1 kg / cm ² , and were similarly heated and cured under a nitrogen atmosphere. The obtained film carrier tape had an extremely low adhesive force of 0.4 kg / cm and a large curl of 40 mm.

Comparative Example 3 167.3 g of N, N-dimethylacetamide was placed in a 300 ml four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dry N ₂ inlet, and 20.23 g of diaminodiphenyl ether was placed under a nitrogen stream. (0.1mo
After dissolving l), pyromellitic dianhydride 21.8
12 g (0.1 mol) was added, and stirring was continued at 10 ° C. for 1 hour. Thereafter, the mixture was stirred and reacted at 50 ° C. for 3 hours to obtain a polyamic acid varnish. The varnish is coated with a 50 μm polyimide film (“UPILEX” 50S (Ube Industries, Ltd.)
To a thickness of 10 μm after drying.
Dried at 120 ° C. for 5 minutes, and further dried at 120 ° C. for 5 minutes.
Dried at 150 ° C. for 15 minutes.

The above-mentioned polyamic acid varnish coating film is slit to a width of 35 mm, processed into a sprocket hole and a device hole by a punch, and then subjected to 35 μm electrolytic copper foil (JLP 10z manufactured by Nikko Gould Foil Co., Ltd.). With a roll laminator heated to 220 ° C.
kg / cm ^2, bonded together at a speed 1m / min, and heat curing in the same way further under a nitrogen atmosphere. The resulting film carrier tape had an extremely low adhesive strength of 0.5 kg / cm and a large curl of 35 mm.

[0037]

The present invention has been configured as described above.
It is possible to reliably obtain a film carrier tape having excellent heat resistance, adhesiveness, electrical properties, and chemical resistance, as well as extremely excellent curl and adhesiveness.

Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) H01L 21/60 311

Claims (3)

(57) [Claims] 1. A film carrier tape obtained by laminating and integrating a heat-resistant insulating film whose surface has been subjected to low-temperature plasma treatment and a metal foil via an adhesive layer, wherein the adhesive layer is made of an aromatic tetracarboxylic acid diacid. A film carrier tape comprising an imidized thin film of a polyamic acid obtained by reacting an anhydride and a siloxane-based diamine as main components. 2. A siloxane-based diamine represented by the following general formula (1):
The film carrier tape according to claim 1, wherein the film carrier tape is represented by the following formula: Embedded image (Wherein R1 and R2 are each a lower alkylene group)
Or a phenylene group, R3, R4, R5 and R6
Represents a lower alkoxy group, a phenyl group and
At least one selected from the group of xyl groups, and n is 1
The following integers are shown. ) 3. The film carrier tape according to claim 1, wherein the surface of the heat-resistant resin film is subjected to low-temperature plasma treatment in an organic gas atmosphere.