JP2002146306A - Heat-resistant bond ply having excellent alkali etching property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-resistant bond ply having excellent alkali etching property and free from significant difference between the alkali etching speeds of the base film layer and the thermoplastic polyimide layer of the heat-resistant bond ply. SOLUTION: The heat-resistant bond ply has a thermoplastic polyimide layer on at least one surface of a heat-resistant base film. The alkali etching speed of the thermoplastic polyimide layer is 1/10 to 10 times the alkali etching speed of the base film. A bond ply having excellent alkali etching property can be produced by using an ester acid dianhydride as the thermoplastic polyimide layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bond ply having a thermoplastic polyimide layer on at least one side of a base film, and more particularly to a bond ply having an alkali etching rate of 1/10 of the alkali etching rate of the base film. The present invention relates to a heat-resistant bond ply characterized in that the ratio is 10 to 10.

[0002]

2. Description of the Related Art In recent years, higher performance and higher functionality of electronic devices have been developed.
The miniaturization is rapidly progressing, and there is an increasing demand for miniaturization and weight reduction of electronic components used in electronic devices. Along with this, the heat resistance, mechanical strength,
Various physical properties such as electrical characteristics are further required, and a higher density, higher function, and higher performance are also required for a semiconductor element packaging method and a wiring board for mounting the same. In particular, flexible printed wiring boards (hereinafter FPCs)
Polyimide used as an insulating layer of HDD wireless suspension), thickness, adhesive strength, dimensional stability, alkali etching property, chemical resistance,
Various characteristics such as water absorption and electrical characteristics are required.

In recent years, the demand for heat resistance has increased, and a pseudo two-layer type using a polyimide resin as an adhesive or a two-layer type without an adhesive layer has been used.

[0004]

The above-mentioned FPC and HDD wireless suspension are manufactured through many steps. However, when the insulating layer is etched using an alkaline solution, the polyimide layer may have a strong alkali resistance. Difficult to process with alkaline solution. Further, when there is a large difference between the etching rates of the base film layer made of a heat-resistant resin and the thermoplastic polyimide (hereinafter, referred to as TPI) as in the present application, there arises a problem that the entire insulating layer cannot be uniformly etched.

In view of the foregoing, there is provided a heat-resistant bond ply which is excellent in alkali etching property and has no significant difference in the alkali etching rate between the base film layer and the thermoplastic polyimide layer of the heat-resistant bond ply. As a result of intensive research for the purpose of
This has led to the present invention.

[0006]

SUMMARY OF THE INVENTION The present invention provides a bond ply having the following structure, which can solve the above-mentioned problems. 1) In a heat-resistant bond ply in which an adhesive layer having a thermoplastic polyimide is formed on one or both sides of a heat-resistant base film, the alkali etching rate of the adhesive layer is 1/10 to 10/10 of the alkali etching rate of the heat-resistant base film. A heat-resistant bond ply characterized by being 0 times. 2) The thermoplastic polyimide used for the adhesive layer has the general formula (Chemical Formula 26)

[0007]

Embedded image (In the formula, n is an integer of 1 or more. A represents a tetravalent organic group and X represents a divalent organic group.) A polyimide precursor having a chemical structure of amic acid represented by the following formula: The heat-resistant bond ply according to 1), which is a polyimide. 3) A in the above general formula (Chemical formula 26) is the following formula (Chemical formula 27)

[0008]

Embedded image The heat-resistant bond ply according to 2), wherein the heat-resistant bond ply is a tetravalent organic group containing the structure as a main component. 4) R in the above (Chemical formula 27) is represented by the following formulas (Chemical formulas 28 to 30)

[0009]

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[0010]

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[0011]

Embedded image 3. The heat-resistant bond ply according to 3), which is at least one member selected from the group shown in (1). 5) X in the general formula (Chemical formula 26) is the following formula (Chemical formula 31) to (Chemical formula 50)

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[0031]

Embedded image 3. The heat-resistant bond ply according to 3) or 4), which is at least one selected from the group of divalent organic groups shown in (1). 6) A heat-resistant bond ply, wherein the base film of the heat-resistant bonding sheet according to any one of 1) to 4) is a non-thermoplastic polyimide film.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION A heat-resistant bond ply according to the present invention is a heat-resistant bond ply in which a thermoplastic polyimide is formed on one or both sides of a heat-resistant base film, and the alkali etching rate of the thermoplastic polyimide film layer is lower than that of the base film. 1/10 of the alkali etching rate of the layer
１10.0 times. Preferably 1/3 to 3.0
It is in the range of double. In such a thermoplastic polyimide, the precursor polyamic acid has a general formula (Formula 51)

[0033]

Embedded image (Wherein, n is an integer of 1 or more. A is a tetravalent organic group,
X represents a divalent organic group. ). Further, A in the general formula (Formula 51) is represented by the following formula (Formula 52)

[0034]

Embedded image Is a tetravalent organic group having the structure: Further, R of (Chemical Formula 52) is represented by the following formulas (Chemical Formula 53)

[0035]

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[0036]

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[0037]

Embedded image At least one selected from the group represented by Further, X in the general formula (Formula 51) is represented by the following formulas (Formula 56) to (Formula 75)

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[0057]

Embedded image Or at least one selected from the group of divalent organic groups shown in (1). Further, the base film made of the heat-resistant resin is a non-thermoplastic polyimide film. A method for preparing a polyamic acid copolymer solution used as a thermoplastic polyimide layer in the present invention will be described.

The polyamic acid copolymer can be obtained by reacting an acid dianhydride with a diamine in an organic solvent. In the present invention, first, in an atmosphere of an inert gas such as argon or nitrogen, general Formula (Formula 76)

[0059]

Embedded image (In the formula, C represents a tetravalent organic group.) At least one acid dianhydride is dissolved or diffused in an organic solvent. The solution has the general formula

[0060]

Embedded image (In the formula, X represents a divalent organic group.) At least one kind of diamine is added in a solid state or an organic solvent solution state. Furthermore, a mixture of one or more acid dianhydrides represented by the above general formula (Chemical Formula 11) is added in a solid state or an organic solvent solution, and a polyamic acid solution as a polyimide precursor is added. Get. In this reaction, contrary to the above addition procedure, a diamine solution may be prepared first, and a solid acid dianhydride or an organic solvent solution of acid dianhydride may be added to the solution. The reaction temperature at this time is preferably from 10C to 0C. The reaction time is 30 minutes to 3 hours. By this reaction, a polyamic acid solution which is a precursor of the thermoplastic polyimide is prepared.

Examples of the organic solvent used for the polyamic acid synthesis reaction include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N dimethylformamide and N, N diethylformamide, and N, N dimethyl Acetamide solvents such as acetamide and N, N diethylacetamide can be mentioned. These may be used alone or in combination of two or more. Further, a mixed solvent composed of these polar solvents and a non-solvent of polyamic acid can also be used. Examples of the non-solvent for the polyamic acid include acetone, methanol, ethanol, isopropanol, benzene, and methyl cellosolve.

The molecular weight of the polyamic acid copolymer and the polyimide copolymer is not particularly limited, but in order to maintain the strength as a heat-resistant adhesive, the number average molecular weight is 50,000 or more, and 80,000 or more, especially 100,000 or more is preferable. The molecular weight of the polyamic acid copolymer (solution) as an adhesive can be measured by GPC (gel permeation chromatography).

Next, as a method for obtaining a polyimide from these polyamic acids, a method of thermally or chemically dehydrating a ring closure (imidization) may be used. Specifically, the method of thermally dehydrating ring closure (imidization) includes heating and drying under normal pressure or heating and drying a polyamic acid solution under reduced pressure.

In the case of drying by heating under normal pressure, first, the organic solvent is evaporated at a temperature of 150 ° C. or lower for about 5 minutes to 9 hours to evaporate the organic solvent.
It is preferably performed for 0 minutes. Subsequently, this is dried by heating to imidize it. Heating temperature for imidization is 150 ° C
The range of -400 ° C is preferred. Especially the final heat treatment is 30
0 ° C. or higher is preferred. More preferably 300 to 400
C is preferred.

When heating and drying under reduced pressure, solvent removal and imidization are performed simultaneously. The heating temperature is 150 ° C
The range of -200 ° C is preferred. In this method, since heating is performed under reduced pressure, water is easily removed from the system. Therefore, it is characterized in that the hydrolysis of the imide ring and the accompanying decrease in the molecular weight are less likely to occur as compared with the heating under normal pressure. In the method of chemically dehydrating ring closure (imidization), a stoichiometric or more dehydrating agent and a tertiary amine as a catalyst are added to the polyamic acid solution,
When the treatment is performed in the same manner as in the case of thermal dehydration, a desired polyimide film can be obtained in a shorter time than in the case of thermal dehydration.

As the tertiary amine used as a catalyst, pyridine, α-picoline, β-picoline, γ-picoline, trimethylamine, triethylamine, isoquinoline and the like are preferable.

Examples of the organic solvent for dissolving the obtained polyimide resin include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N dimethylformamide and N, N diethylformamide, and N, N dimethylacetamide. Acetamide solvents such as N, N diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone, tetrahydrofuran,
Examples thereof include ether solvents such as 1,4-dioxane and dioxolan. These may be used alone or in combination of two or more.

Next, the base film will be described.
Apical A is already on the market for base film
H, NPI and HP (Kanebuchi Chemical Industry Co., Ltd.) are preferably used.

In addition, polyimides obtained from various combinations of acid dianhydrides and diamines can be used according to required characteristics.

The base film is coated with the above-mentioned thermoplastic polyimide solution or an amic acid generally known to those skilled in the art as a precursor thereof, to obtain a bond ply having a desired structure. A heat resistant flexible thin metal sheet laminate can be formed by selecting a heat and pressure laminating method that can continuously process any kind of thin metal sheet that can be conceived technically easily by those skilled in the art. You can get it.

Although the embodiment of the heat-resistant bond ply according to the present invention has been described above, the present invention is not limited to this, and the present invention is based on the knowledge of those skilled in the art without departing from the scope of the present invention. , Various improvements, changes,
It can be implemented in a modified manner. The present invention will be described more specifically with reference to the above examples, but the present invention is not limited to these examples.

[0072]

Example 1 The whole system was cooled with ice water and purged with nitrogen.
100 g of 2,2 'in a 000 ml three-neck separable flask
Bis [4- (4-aminophenoxy) phenyl] propane (hereinafter, referred to as BAPP) was charged with 708.4 g of dimethylformamide (hereinafter, referred to as DMF) and sufficiently dissolved. After stirring for 15 minutes, 108.2 g of p-phenylenebis (trimellitic acid monoester anhydride) monomer (hereinafter referred to as TMHQ) was charged as a powder. After stirring for 30 minutes, 3.4 g of TMHQ was further slurried with 8.4 g of DMF, and gradually added while paying attention to the viscosity of the solution in the flask.
% Polyamic acid was obtained. Thereafter, 1296 g of DMF was added and stirred for 1 hour to adjust the viscosity to about 5 poise. This polyamic acid solution is applied to a polyimide film (Apical 12.5 HP;
(Kanebuchi Chemical Industry Co., Ltd.) on both sides so that the final one-sided thickness of the thermoplastic polyimide layer is 2 μm,
Heating at 120 ° C. and 350 ° C. for 2 minutes each to remove the solvent,
A bond ply was obtained. After measuring the thickness of the obtained bond ply, an alkali solution (25% by weight of potassium hydroxide, 25% of water
w%, ethanolamine 50 w%), the alkali etching rate of the adhesive layer was measured by measuring the thickness of the bond ply immersed for a predetermined time (taken out before the base film was etched). Further, only the base film was immersed in an alkali solution, and the alkali etching rate was determined in the same manner. Table 1 shows the results.

[0073]

Example 2 100 g of BAPP was sufficiently dissolved in 704.7 g of DMF. After stirring for 15 minutes, 100.5 g of TM
HQ and 7 g of 3,3′4,4′-ethylene glycol dibenzoate tetracarboxylic dianhydride (hereinafter referred to as TMEG) were charged as powder. After stirring for 30 minutes, an additional 3.0 g of TME
A solution in which G was dissolved in 7.0 g of DMF was gradually added while paying attention to the viscosity in the flask, and then left for 1 hour with stirring. Thereafter, 1190 g of DMF was charged and stirred for 1 hour to obtain a polyamic acid solution. This polyamic acid solution was applied to a base film in the same manner as in Example 1;
Drying was performed at 350 ° C. for 2 minutes to obtain a bond ply.
The alkali etching rate was measured in the same manner as in Example 1.
Table 1 shows the results.

[0074]

Example 3 697.0 g of DMF and 7 of TMHQ of Example 2
A polyamic acid solution was obtained in the same manner except that 8.2 g and 27 g of TMEG were used, and the same measurement as in Example 1 was performed. Table 1 shows the results.

[0075]

Example 4 96.8 g of BAPP and 8.7 g of bis (2- (4-
Aminophenoxy) ethoxy) ethane (hereinafter referred to as DA3EG) was sufficiently dissolved in 747.9 g of DMF. After stirring for 15 minutes, 108.0 g of TMHQ and 5.7 g of TMEG were charged as powder. After stirring for 30 minutes, another 5.0 g of TME
A solution in which G was dissolved in 45.0 g of DMF was gradually added while paying attention to the viscosity in the flask, and then left for 1 hour with stirring. Then, this polyamic acid solution was used in Example 1
Adjust the viscosity in the same manner as above, apply to the base film,
Each was dried at 330 ° C. for 2 minutes to obtain a bond ply. The alkali etching rate was measured in the same manner as in Example 1. Table 1 shows the results.

[0076]

Example 5 95.7 g of BAPP was sufficiently dissolved in 731.2 g of DMF. After stirring for 15 minutes, 94.0 g of 2,2-
Bis (4-hydroxyphenyl) propane-3,3 ', 4,4'benzophenonetetracarboxylic dianhydride (hereinafter referred to as ESDA)
And 23.7 g of TMEG were charged as a powder. After stirring for 30 minutes, a solution in which 5.0 g of TMEG was dissolved in 45.0 g of DMF was gradually added while paying attention to the viscosity in the flask, and then left for 1 hour with stirring. Thereafter, the viscosity of this polyamic acid solution was adjusted in the same manner as in Example 1, applied to a base film, and dried at 120 ° C. and 330 ° C. for 2 minutes each to obtain a bond ply. The alkali etching rate was measured in the same manner as in Example 1. Table 1 shows the results.

[0077]

COMPARATIVE EXAMPLE 1 123.1 g of BAPP was dissolved in 607 g of DMF, 33.2 g of benzophenonetetracarboxylic dianhydride (hereinafter referred to as BTDA) and 76.0 g of TMEG were added as powders and stirred for 30 minutes. Thereafter, DMF in which TMEG was dissolved was added while paying attention to the viscosity to obtain a polyamic acid solution. A bond ply was prepared and physical properties were measured in the same manner as in Example 1. Table 1 shows the results.

[0078]

Comparative Example 2 369.6 g of BAPP was converted to 2125.2 g of DMF
And stirred for 15 minutes. Then, 2 g of benzophenonetetracarboxylic dianhydride (hereinafter referred to as BPDA)
Was introduced. After stirring for 30 minutes, an additional 8.0 g of BPD
A was made into a slurry using 18.0 g of DMF, and gradually added while paying attention to the viscosity of the solution in the flask. After that, the mixture was allowed to stand with stirring for 1 hour to obtain a polyamic acid solution of SC23%. The obtained polyamic acid solution was further added to DMF358.
8 g was added for dilution, and the viscosity was adjusted to about 5 poise. Using this polyamic acid solution, a bond ply was prepared in the same manner as in Example 1, and the characteristics were evaluated. Table 1 shows the results.

[0079]

Comparative Example 3 219.6 g of BAPP and 1282.8 g of DMF
Was sufficiently dissolved by stirring with a stirrer. After stirring for 15 minutes, 141.6 g of BPDA and 15.4 g of TMEG were charged as a powder. After stirring for 30 minutes, a solution in which 6 g of TMEG was dissolved in 100 g of DMF was gradually added while paying attention to the viscosity of the solution in the flask.
Then, the mixture was left for 1 hour with stirring. After that, 2166
g of DMF was added and stirred for 1 hour to obtain a polyamic acid solution. Using this polyamic acid solution, a bond ply and a CCL were produced in the same manner as in Example 1, and physical properties were measured in the same manner as in Example 1. Table 1 shows the results.

[0080]

[Table 1]

[0081]

As described above, the heat-resistant bond ply according to the present invention is excellent in alkali etching property, and is expected to be used for FPC, rigid-flex substrate material, HDD wireless suspension COF and LOC package, MCM, etc. It is suitable for high-density packaging materials, and other uses are not particularly limited.

Continued on front page F-term (reference) 4F100 AK01A AK49A AK49B AK49C BA02 BA03 BA06 BA10B BA10C BA13 GB41 JB01B JB01C JB16B JB16C JJ03A JL00 JL11B JL11C YY00B YY00C 4J004 AA11 CA06 EA03 J04A03 SA06 SA43 SA44 SA71 SB01 SB02 TA22 TB01 TB02 UA121 UA122 UA131 UA132 UA141 UA142 UA151 UA152 UB011 UB012 UB021 UB022 UB061 UB121 UB131 UB162 UB301 UB402 VA011 VA012 VA021 VA022 VA031 VA041 VA041 VA061 VA051 VA051 VA041 VA051 VA041 VA051 VA041 VA041 VA041

Claims (6)

[Claims] 1. In a heat-resistant bond ply having an adhesive layer having thermoplastic polyimide formed on one or both sides of a heat-resistant base film, an alkali etching rate of the adhesive layer is 1/10 of an alkali etching rate of the heat-resistant base film. A heat-resistant bond ply, which is up to 10.0 times. 2. The thermoplastic polyimide used for the adhesive layer has a general formula (1). (In the formula, n is an integer of 1 or more. A represents a tetravalent organic group and X represents a divalent organic group.) A polyimide precursor having a chemical structure of amic acid represented by the following formula: The heat-resistant bond ply according to claim 1, which is a polyimide. 3. A in the general formula (Chem. 1) is represented by the following formula (Chem. 2). The heat-resistant bond ply according to claim 2, wherein the bond is a tetravalent organic group containing the structure of (1) as a main component. 4. The compound of the formula (2) wherein R is represented by the following formulas (3) to (5). Embedded image Embedded image The heat-resistant bond ply according to claim 3, wherein the heat-resistant bond ply is at least one member selected from the group consisting of: 5. X in the above general formula (Chem. 1) is represented by the following formula (Chem. 6)
~ (Chemical formula 25) Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image 5. The heat-resistant bond ply according to claim 3, wherein the heat-resistant bond ply is at least one selected from the group consisting of divalent organic groups shown in (b). 6. A heat-resistant bond ply, wherein the base film of the heat-resistant bonding sheet according to any one of claims 1 to 5 is a non-thermoplastic polyimide film.