JPH11199668A - Polytmide composition, and tape for tab and flexible printed circuit board therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of manifesting excellent characteristic such as high modulus and small expansion coefficient by moisture absorption by carrying out a dehydration cyclization of an polyamic acid obtained by using a diamine having a specific ester structure. SOLUTION: This composition has <=1.6 wt.% water absorption and <=15 ppm expansion coefficient by moisture absorption, and is a polyimide composition of formula I [R1 and R2 are each a tetravalent organic group; X is a divalent organic group; R3 is a divalent organic group; (m) and (n) are each an integer, and (m)>=1 and (n)>=0]. The composition is obtained by carrying out dehydration cyclization of a polyamic acid copolymer which is a precursor. The polyamic acid solution is obtained by dissolving or dispersing a diamine of formula II and an aromatic acid dianhydride of formula III in an organic polar solvent, adding a diamine compound of formula IV to the obtained solution or dispersion and further adding the aromatic acid dianhydride of formula V to the organic polar solvent. The polyimide film using the composition is useful for the tape or the like for TAB(Tape Automated Bonding).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel polyimide composition and a method for producing the same. More specifically, the present invention relates to a polyimide composition having appropriate flexibility, low water absorption, and low moisture absorption expansion. Also, TAB (Ta
A tape having a three-layer structure of a protective layer, an adhesive layer, and an organic insulating film (hereinafter, referred to as a TAB tape) used for a pe-automated bonding (hereinafter referred to as TAB tape), and a flexible printed board (hereinafter, the flexible printed board is abbreviated as FPC). ).

[0002]

2. Description of the Related Art Good adhesion that can be suitably used as a semiconductor package, a COL and LOC package, a high-density mounting material such as an MCM (Multi Chip Module), a printed wiring board material such as a multilayer FPC, and an aerospace material. There is a demand for an insulating material having a property.

As an insulating adhesive material generally used for electronic parts and electronic materials, an epoxy resin or an acrylic resin is used because it can be processed at a low temperature (200 ° C. or lower) and is easy to handle. In many cases, these adhesive materials are also used for bonding a lead frame and an element when manufacturing a semiconductor element.

[0004] Although these adhesive materials are easy to handle at low temperatures, they have a problem of poor heat resistance at high temperatures. In addition, since the use form is used in the form of a solution,
There is also a problem that the manufacturing process becomes complicated. Furthermore, since bonding requires a long curing time and a gas is generated during the curing, for example, when used for bonding a lead frame to a semiconductor element, the gas contaminates the element surface and the bonding between the lead frame and the element. In addition, there is also a problem that the properties are deteriorated and the yield of products is deteriorated.

[0005] Therefore, there is a strong demand for an even higher-performance adhesive material especially for high-density packaging materials such as when manufacturing semiconductor elements. For example, it is desired that a base film for a flexible printed board, a carrier tape for TAB (tape automated bonding), or a resin for a laminate have a high elastic modulus and a small coefficient of hygroscopic expansion.

More specifically, the TAB Kyria tape is formed by slitting, punching, laminating copper foil, curing an adhesive, forming an arrangement pattern (resist coating,
It is mounted by the above processing steps of copper etching, resist stripping), plating, inner lead bonding, resin sealing, punching, and outer lead bonding. In order to mount the LSI on the TAB tape, the base film needs to be a film having a high elastic modulus enough to support the LSI.

[0007] Among them, copper foil laminating, adhesive curing, inner lead bonding, resin sealing,
In the process of outer lead bonding,
Since heat is applied, there is an inconvenience if the coefficient of thermal expansion of the base film of the TAB tape is large. For example, in a processing step of inner lead bonding, a displacement of a bonding position with an LSI occurs due to thermal expansion of a base film. Similarly, in the processing step of the outer lead bonding, a displacement of the bonding position between the outer lead and the substrate occurs. In the copper foil laminating processing step, the copper foil is heated together with the copper foil. If the copper foil has a thermal expansion coefficient different from that of the copper foil, the thermal behavior is different, which causes curling.

Accordingly, in the processing step of inner lead bonding, it is necessary that the thermal expansion coefficient of the LSI (silicon wafer) and that of the base film are close (the thermal expansion coefficient of the LSI is 0.4 × 10 ⁻⁵ ° C. ⁻¹ ). In the outer lead bonding processing step, the substrate to be bonded and the base film have close thermal expansion coefficients. In the copper foil laminating processing step, the thermal expansion coefficient of the copper foil and the base film (the thermal expansion coefficient of the copper foil). The expansion coefficient must be close to 1.6 × 10 ⁻⁵ ° C. ⁻¹ ).

From these facts, the base film used for the TAB tape may have a high elastic modulus and a thermal expansion coefficient of about 0.4 to 2.6 × 10 ^-5 ° C.- ^1. Desirably, TA using a base film having these properties
The appearance of the tape for B has been long-awaited.

[0010] In the FPC, a base film, which is a long insulating material, is roll-to-roll coated with an adhesive, dried copper foil laminating, hardening the adhesive, and forming an arrangement pattern (resist coating, copper etching, resist peeling). ). In general, when a pattern is formed, a dimensional change occurs in an etching process. Therefore, when designing a circuit, it is necessary to design the circuit in consideration of changes in subsequent processes in advance.

This dimensional change is caused by: a) a dimensional change due to moisture absorption / dehumidification of a base film, which is an insulating material of the FPC; b) a distortion caused by a difference in thermal expansion between the copper foil and the base film caused during lamination of the copper foil; This is caused by strain caused by tension generated in the process.

Among them, the dimensional change due to b) is as follows.
If the coefficient of thermal expansion of the base film is constant, this dimensional change can be easily incorporated into the design. The dimensional change due to the cause c) can be controlled by controlling the tension in each step, and the amount of the dimensional change can be easily incorporated into the design. However,
In the manufacturing process of the FPC, a process of absorbing and drying moisture is repeated in a washing process and the like, and therefore, it is difficult to control a dimensional change due to moisture absorption and dehumidification of the base film in a). Since the base film has a large hygroscopic expansion coefficient, the dimensional change due to moisture absorption and dehumidification in the FPC manufacturing process was a serious problem.

[0013] Among various organic polymers, polyimide having excellent heat resistance is widely used from the fields of space and aviation to the field of electronic communication. However, not only excellent heat resistance but also various properties are required. Has been desired, and a polyimide which solves the above problem has been long-awaited.

[0014]

In order to obtain a polyimide which solves the above-mentioned problems, it is necessary to make the polyimide main chain as rigid as possible to exhibit low thermal expansion. When a polyimide is synthesized using pyromellitic acid having an existing most rigid structure, high elasticity can be easily expressed, but polarization of an imide group becomes large, and low hygroscopicity cannot be expressed. In order to lower the water absorption, it is conceivable to introduce fluorine, but this is not preferable because the production cost is expected to increase. Therefore, a polyimide which sufficiently satisfies the performance of high elastic modulus and small coefficient of hygroscopic expansion has not been obtained at present.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyimide composition having excellent properties such as low water absorption and low moisture absorption swelling property, and a method for producing the same. Also,
The present inventors have found that the intended purpose of obtaining a TAB tape and a flexible printed circuit board using a polyimide film obtained from the polyimide composition having the above specific structure can be achieved, and have completed the present invention.

A first aspect of the present invention is that the water absorption is 1.6% or less, the coefficient of hygroscopic expansion is 15 ppm or less, and the general formula (1) is used.

[0017]

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(Where R ₁ and R ₂ are tetravalent organic groups,
X represents a divalent organic group, and R ₃ represents a divalent organic group. The integers m and n satisfy m ≧ 1 and n ≧ 0. )).

A second aspect of the present invention is that the water absorption is 1.6% or less, the coefficient of hygroscopic expansion is 15 ppm or less, and the general formula (1) is used.

[0020]

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(Where R ₁ and R ₂ are a tetravalent organic group, X is a divalent organic group, R ₃ is a divalent organic group,
R ₁ is

[0022]

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One or two or more tetravalent organic groups selected from The integers m and n satisfy m ≧ 1 and n ≧ 0. The content is a polyimide composition represented by ()).

The third aspect of the present invention is that the water absorption is 1.6% or less, the coefficient of hygroscopic expansion is 15 ppm or less, and the compound represented by the general formula (1)

[0025]

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(Where X is a divalent organic group, R ₃ is
R ₁ represents a valent organic group;

[0027]

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One or more tetravalent organic groups selected from the group consisting of: R ₂ is

[0029]

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One or more tetravalent organic groups selected from The integers m and n satisfy m ≧ 1 and n ≧ 0. The content is a polyimide composition represented by ()).

A fourth aspect of the present invention is that the water absorption is 1.6% or less, the coefficient of hygroscopic expansion is 15 ppm or less, and

[0032]

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(Where R ₃ represents a divalent organic group,
R ₁ is

[0034]

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One or more tetravalent organic groups selected from R ₂ is

[0036]

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One or more tetravalent organic groups selected from the group consisting of: X is

[0038]

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One or more divalent organics selected from the group consisting of: The integers m and n satisfy m ≧ 1 and n ≧ 0. The content is a polyimide composition represented by ()).

A fifth aspect of the present invention is that the water absorption is 1.6% or less, the coefficient of hygroscopic expansion is 15 ppm or less, and the general formula (1) is used.

[0041]

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(Where R ₁ is

[0043]

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One or two or more tetravalent organic groups selected from R ₂ is

[0045]

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One or more tetravalent organic groups selected from X is

[0047]

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One or more divalent organics selected from the group consisting of: R ₃ is represented by Chemical Formula 31 or Chemical Formula 32

[0049]

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[0050]

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One or more divalent organic groups selected from The integers m and n satisfy m ≧ 1 and n ≧ 0. The content is a polyimide composition represented by ()).

A sixth aspect of the present invention is a polyimide film containing the polyimide composition described in any of the above.

A seventh aspect of the present invention is a TAB tape comprising the polyimide film provided with an adhesive layer and a protective layer.

An eighth aspect of the present invention is the flexible printed circuit board including at least a conductor and an insulating material, wherein the insulating material is the polyimide film.

[0055]

BEST MODE FOR CARRYING OUT THE INVENTION The polyimide composition according to the present invention is a polyimide composition having excellent properties such as low water absorption and low hygroscopic expansion. Specifically, the polyimide composition according to the present invention has the general formula (1)

[0056]

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(Where R ₁ is

[0058]

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R ₂ is a tetravalent organic group selected from
5

[0060]

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X is a tetravalent organic group selected from

[0062]

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R ₃ is a divalent organic group selected from

[0064]

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[0065]

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And a divalent organic group selected from However, it is characterized by being a polyimide composition represented by m ≧ 1, n ≧ 0).

Hereinafter, the novel polyimide composition and the method for producing a polyimide film according to the present invention will be described in detail.

This polyimide composition can be obtained by dehydrating and ring-closing a polyamic acid copolymer as a precursor thereof. This polyamic acid solution uses substantially equimolar amounts of an acid dianhydride and a diamine component. It is obtained by polymerization in an organic polar solvent.

Next, a method for producing the polyimide composition according to the present invention will be described with reference to examples. First, in an inert atmosphere such as argon or nitrogen, general formula (2) H ₂ N—C ₆ H ₄ —OCO—X—COO—C ₆ H ₄ —NH ₂ (2) 39

[0070]

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And a divalent organic group selected from ) And one or more diamines represented by general formula (3)

[0072]

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(Wherein R ₁ is

[0074]

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And a tetravalent organic group selected from (1) dissolving or diffusing one or more acid dianhydrides selected from the aromatic dianhydrides in an organic polar solvent; In this solution, the general formula (4) H ₂ N—R ₃ —NH ₂ (4) (where R ₃ is

[0076]

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[0077]

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And a divalent organic group selected from The diamine compound represented by the formula (1) is dissolved in an organic solvent and added in a state of being dispersed in a slurry or in a solid state. The solution is represented by the general formula (5):

[0079]

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(Wherein R ₂ is

[0081]

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And a tetravalent organic group selected from A) a solution of a polyamic acid polymer, which is a precursor of the polyimide composition according to the present invention, wherein at least one acid dianhydride selected from aromatic acid dianhydrides represented by Get.

The order of addition of each monomer is as follows. The above-mentioned general formulas (2) and (4), which are diamine components, are added to an organic polar solvent first, and then the diamine component, which is a general formula ( 3) may be added, and then the general formula (5) may be added to obtain a solution of a polyamic acid polymer. In addition, the general formula (4) is first added to the organic polar solvent, the general formula (3) which is an acid dianhydride component is added, the general formula (2) is added, and then the general formula (5) ) May be added to form a polyamic acid polymer solution. Further, the above-mentioned general formulas (2) and (4), which are diamine components, are previously added to an organic polar solvent, and then the general formulas (3) and (5), which are acid dianhydride components, are added. It may be added at the same time to form a polyamic acid polymer solution.

The same is true even if the above addition method is reversed so that the acid dianhydride is added first and the diamine component is added later.

The reaction temperature of the above reaction is from -20 ° C to 60
C is desirable. The reaction time is about 30 minutes to 24 hours.

The weight average molecular weight of the polyamic acid obtained as described above is desirably 10,000 to 1,000,000. If the weight average molecular weight is less than 10,000, the resulting film becomes brittle, while
If it exceeds 3, the viscosity of the polyamic acid varnish becomes too high and handling becomes difficult, which is not preferable.

Examples of the organic polar solvent used in the polyamic acid forming reaction include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and formamides such as N, N-dimethylformamide and N, N-diethylformamide. Acetamide solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone,
A pyrrolidone solvent such as N-vinyl-2-pyrrolidone,
Phenols such as phenol, o-, m-, or p-cresol, xylenol, halogenated phenol, catechol, and the like, or hexamethylphosphoramide, γ-butyrolactone, and the like can be used, and these can be used alone or as a mixture. However, it is also possible to use a part of aromatic hydrocarbons such as xylene and toluene.

The diamine component monomer used in the present invention is synthesized by first synthesizing a dinitro compound and reducing the dinitro compound. First, a dinitro compound is a reaction between aromatic diacid chloride and nitrophenol in the presence of pyridine in a solvent such as benzene or toluene, or a catalyst for esterification of nitrophenol and aromatic dicarboxylic acid with p-nitrosulfonic acid or the like. It is synthesized by reacting in the presence of

The reduction of the dinitro compound is performed by various reduction reactions such as reduction with tin / hydrochloric acid, reduction with hydrogen in the presence of activated carbon, and reduction with hydrazine.

The polyamic acid is preferably dissolved in the organic polar solvent in an amount of 5 to 40% by weight, preferably 10 to 30% by weight, from the viewpoint of handling.

In the polyimide composition represented by the general formula (1) obtained by dehydrating and ring-closing a polyamic acid polymer, the number m of repeating block units is an integer of 1 or more, and n is an integer of 0 or more. The range of n / m is 0 ≦ n / m <100
Take. In order to exhibit low water absorption, the diamine component represented by the general formula (2) is preferably used in an amount of 10 mol% or more of all diamine components, in other words, 0 ≦ n / m <9.
/ 1, more preferably 30% or more, in other words, 0 ≦ n / m <7/3.

In order to obtain the polyimide composition represented by the general formula (1) from the polyamic acid copolymer solution obtained above, either a thermal method of thermally dehydrating or a chemical method using a dehydrating agent is used. May be used. According to the chemical method, the resulting polyimide composition tends to have a higher elastic modulus and a lower coefficient of thermal expansion than the thermal method. Polyimide composition having a specific structure according to the present invention is a method of dehydrating a polyamic acid copolymer by a thermal method, or by using a chemical method or both,
It is possible to vary the properties within the scope of the present invention.

An example of a method for preparing a polyimide film (chemical method) will be described below.

A solution obtained by adding a dehydrating agent having a stoichiometric amount or more and a catalytic amount of a tertiary amine to the polyamic acid polymer or a solution thereof is cast or coated on a drum or an endless belt to form a film. The membrane is dried at a temperature below 150 DEG C. for about 5 to 90 minutes to obtain a self-supporting polyamic acid membrane. Next, this is peeled off from the support and the end is fixed. Thereafter, the polyimide film is imidized by gradually heating it to about 20 to 550 ° C., and after cooling it is removed to obtain the polyimide film of the present invention.

Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline and isoquinoline.

In the thermal dehydration and ring closure method, for example, a polyamic acid solution is cast or coated on a support plate, an organic film such as polyimide or PET, or a support such as a drum or an endless belt to form a film. In addition, a polyimide film can be obtained by heating and drying in the same manner as in the case of chemical dehydration.

It is also possible to compound various organic additives, inorganic fillers, or various reinforcing materials with the polyimide film.

The diamine component represented by the general formula (2) used in the present invention:
A benzene derivative having a bond at the p-position,
If a diphenyl having a biphenyl derivative having only a bond at the 1-position, 1,4-naphthalene, or a diamine having a 2,6-naphthalene structure is employed, the elasticity is high, the Tg is 400 ° C. or more, and the water absorption rate and the moisture absorption and expansion properties are combined. A polyimide film useful as a base film for a flexible printed board, a carrier film for a TAB (tape automated bonding), or a base film for a laminated board can be obtained.

In the diamine component of the general formula (2) used in the present invention, the structure of X is benzene having an o- or m-position bond, biphenyl derivative having a bond other than p-position,
If a diamine having a naphthalene structure other than 4 and 2, 6 is adopted, a semiconductor package, a COL and LOC package, and an MCM (Multi Chip Module) having a Tg of 400 ° C. or less and having a low water absorption and a low moisture absorption expansion property And other high-density packaging materials, printed wiring board materials such as multilayer FPCs,
Furthermore, a polyimide film exhibiting good adhesiveness, which can be suitably used as an aerospace material, is obtained.

As described above, the obtained polyimide composition and the polyimide film comprising the same have high elasticity,
Moderate coefficient of linear expansion, moderate flexibility, and 1.6% or less,
Further, it can have a low water absorption of 1.0% or less, further preferably 0.5% or less, and has a low moisture absorption and expansion of 15 ppm or less, further 12 ppm or less, further 5 ppm or less. Therefore, it can be suitably used for electronic parts such as TAB tapes and flexible printed boards, electronic materials, and other aerospace materials.

Next, a method for producing the TAB tape of the present invention will be described.

The thickness of the polyimide film is from about 25 μm to about 180 μm, but it is more preferably from 50 μm to 125 μm in consideration of the balance between convenience in handling, film strength, and demand for thinning for miniaturization.

Examples of the adhesive of the present invention include, but are not limited to, epoxy resins, polyamide resins, phenol resins, acrylic resins, polyimide resins, and rubber resins. These resins may be used alone or mixed with solvents at various ratios, and if necessary, additives such as a curing agent and a curing accelerator may be added.

The protective film serving as a protective layer of the adhesive layer is not particularly limited as long as it has heat resistance to the extent that it does not soften or deteriorate when the adhesive is dried, but it may be a polyester film such as polyethylene terephthalate or the like.
Polyolefin films such as polypropylene are preferred.

In the TAB tape according to the present invention, an adhesive having a predetermined composition is uniformly applied on a protective film so as to have a final film thickness of 10 to 40 μm, preferably 15 to 30 μm. The adhesive solution is dried, and the adhesive layer is in a semi-cured state (B-
Stage). The polyimide film according to the present invention is superimposed on the adhesive layer and pressed at 20 to 180 ° C. under a condition of 0.1 kg / cm ² or more.

As described above, the TAB according to the present invention
Tape is obtained.

Next, a method of manufacturing an FPC according to the present invention will be described. An adhesive having a predetermined composition is used in a final film thickness of 10 to 100.
It is applied uniformly on a base film made of the polyimide film according to the present invention as an insulating material so as to have a thickness of 15 μm, preferably 15 to 30 μm. The adhesive solution is dried, and the adhesive layer is in a semi-cured state (B-
Stage). Laminate copper foil on the adhesive layer, 0.1k at 20-180 ° C
The adhesive is pressed under the condition of g / cm ² or more and cured at a temperature at which the adhesive is cured. A resist is applied, a circuit is drawn on the resist by exposure or the like, development is performed, copper is etched, and the resist is peeled off to form an FPC.

By the above manufacturing method, the TAB tape and the flexible printed board according to the present invention can be obtained. The TAB tape and the flexible printed circuit board obtained in this way have no difference in linear expansion coefficient with respect to metal or glass, and use a polyimide film having a specific high elastic modulus as a base film and an insulating material. In the process, since there is no warp or curl, and the dimensional change during processing and mounting is small, it can be a material suitable for a tape carrier with a multi-pin high-density pattern.

[0109]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, ODA is 4,4'-diaminodiphenyl ether, and BAPT is bis (4-aminophenyl)
Terephthalate and BAPI are bis (4-aminophenyl) isophthalate, and BAPB is 4,4′-bis (4
- aminophenoxy) biphenyl, p-PDA is paraphenylenediamine, PMDA is pyromellitic anhydride, s-BPDA is 3,3 ^{', 4,4'} - biphenyltetracarboxylic acid, ODPA is oxydiphthalic anhydride Stuff,
DMF is N, N-dimethylformamide, NMP is
Represents N-methyl-2-pyrrolidone.

The properties of the obtained polyimide film were measured as follows.

(Coefficient of thermal expansion) Under a nitrogen gas flow, Rigaku Denki T
It is an average value of 100 ° C to 200 ° C measured by MA 8140.

(Tg: glass transition temperature) The temperature at the inflection point of the chart (horizontal axis temperature vs. vertical axis size change) obtained at the time of the above thermal expansion coefficient measurement was defined as Tg.

(Water Absorption) The water absorption was measured according to ASTM D570.
It measured based on. The weight of a film obtained by drying the film at 150 ° C. for 30 minutes is defined as W1, and the weight of a film obtained by immersing the film in distilled water for 24 hours and then wiping off water droplets on the surface is defined as W2.
It is calculated from the following equation. Water absorption (%) = (W2−W1) ÷ W1 × 100

(Hygroscopic Expansion Coefficient) The film was left for 24 hours in an environmental tester at 50 ° C. and 30% Rh, and the film dimensions were measured (L
1) Then, the film was left for 24 hours in an environmental tester at 50 ° C. and 80% Rh, and the film dimensions were measured (L2).
It is calculated from the following equation. Hygroscopic expansion coefficient (ppm) = (L ₂ −L ₁ ) {L ₁ } (8
0-30) × 10 ⁶

(Elastic Modulus) The elastic modulus is based on ASTM D882.

(Dimensional stability) The dimensional stability of the TAB tape and the flexible printed circuit board was evaluated by obtaining the dimensional change rate by the following method.

That is, a base polyimide film, an adhesive, and polyethylene terephthalate for protection (hereinafter referred to as PE
T) A TAB tape composed of a film is laminated with a copper foil (Low-profile electrolytic copper foil VLP-3EC made by Mitsui Kinzoku) except for the PET film, and after heating and curing, two pieces for measuring a dimensional change rate are obtained. marking holes a, b opened by punching MD (machine direction of production) direction, was measured the initial value l ₁ between a-b in this case.
Next, the entire surface of the copper foil was etched, and l ₂ between a and b was measured.

The dimensional change before and after the etching was calculated based on the following formula.

[0119]

Production Example 1 Synthesis of (Diamine Component: Bis (4-aminophenyl) terephthalate; BAPT) 278 g (2 mol) of p-nitrophenol was placed in a 3000 ml three-necked flask equipped with a dropping funnel and a reflux condenser.
400 ml of toluene and 300 ml of pyridine
Stir at 0 ° C. 203 g of terephthalic acid chloride (1.
0 mol) is dissolved in 500 ml of toluene and added dropwise to the above three-necked flask from a dropping funnel.

After the dropwise addition, the mixture was stirred under reflux for about 2 hours.
The precipitate was filtered off to give a white solid. The white solid was washed with 3 liters of water, dried, recrystallized from DMF,
0 g of a white needle-like solid was obtained. 204 g of this white solid
(0.5 mol), 3.5 g of activated palladium on carbon, DMA
c 800 ml in a three-necked flask and heated to 70 ° C.
Hydrogen was introduced and reduced by hydrogen (hydrogen consumption 3
5 liters). After completion of the reaction, the solution was separated by filtration, the filtrate was poured into water, and the white precipitate was separated by filtration and dried to obtain a white solid. This white solid was recrystallized with an alcohol / DMF mixture,
104 g of a white solid were obtained.

[0121]

Production Example 2 Synthesis of (diamine component: bis (4-aminophenyl) isophthalate; abbreviation BAPI) 278 g (2 mol) of p-nitrophenol was placed in a 3000 ml three-necked flask equipped with a dropping funnel and a reflux condenser.
400 ml of toluene and 300 ml of pyridine
Stir at 0 ° C. 203 g of isophthalic acid chloride (1.
0 mol) is dissolved in 500 ml of toluene and added dropwise to the above three-necked flask from a dropping funnel. After the dropwise addition, the mixture was stirred under reflux for about 2 hours. After cooling, the precipitate was separated by filtration to obtain a white solid. This white solid was washed with 3 liters of water and dried,
Recrystallization with a DMF / toluene mixed solution gave 300 g of a white needle-like solid. 204 g (0.5 mol) of this white solid 3.5 g of activated palladium carbon, 800 ml of DMAc
Was placed in a three-necked flask, heated to 70 ° C., hydrogen was introduced, and reduction with hydrogen was performed. (Hydrogen consumption: 35 liters) After completion of the reaction, the solution was separated by filtration, the filtrate was poured into water, and a white precipitate was separated by filtration and dried to obtain a white solid. This white solid was recrystallized from an alcohol / DMF mixture to obtain 100 g of a white solid.

[0122]

Example 1 Two equivalents of NMP and BAPT and one equivalent of p-PDA were placed in a separable flask and stirred well at room temperature.
Next, slowly add 2.85 equivalents of s-BPDA as a powder,
Thereafter, the mixture was stirred for 40 minutes. And s-BPDA 0.15
The equivalent was dissolved in NMP, gradually added, and then cooled and stirred for 1 hour to obtain a polyamic acid NMP solution. NM
The amount of P used was such that the concentration of charged monomers of diamines and aromatic tetracarboxylic dianhydrides was 18% by weight.

Next, the polyamic acid solution was mixed with acetic anhydride and β-picoline, cast and applied on a glass plate, dried at about 100 ° C. for about 5 minutes, and then the polyamic acid coating film was peeled off from the glass plate. The membrane is fixed to a support frame and then at about 100 ° C for about 5
For about 5 minutes at about 200 ° C, for about 5 minutes at about 300 ° C, and for about 5 minutes at about 400 ° C.
A polyimide film of 0 μm was obtained. Table 1 shows the physical properties of the obtained polyimide film.

[0124]

[Table 1]

[0125]

Example 2 Two equivalents of NMP and BAPT and one equivalent of p-PDA were placed in a separable flask and stirred well at room temperature.
2 equivalents of s-BPDA was gradually added as a powder, and then stirred for 40 minutes. Slowly add 0.85 equivalents of ODPA as a powder,
Thereafter, the mixture was stirred for 40 minutes. Then, 0.15 equivalents of ODPA was dissolved in NMP, added gradually, and then cooled and stirred for 1 hour to obtain a polyamic acid NMP solution. The amount of NMP used was such that the concentration of charged monomers of diamines and aromatic tetracarboxylic dianhydrides was 18% by weight. The firing conditions were the same as in Example 1. Table 1 shows the physical properties of the obtained polyimide film.

[0126]

Example 3 One equivalent of NMP and BAPT and one equivalent of ODA were placed in a separable flask and stirred well at room temperature. Next, 1.85 equivalents of s-BPDA was gradually added as a powder, followed by stirring for 40 minutes. Then, 0.15 equivalent of s-BPDA was dissolved in NMP, gradually added, and then cooled and stirred for 1 hour to obtain an NMP solution of polyamic acid. Note that NMP
Was used so that the concentration of charged monomers of diamines and aromatic tetracarboxylic dianhydrides was 18% by weight. The firing conditions were the same as in Example 1. Table 1 shows the physical properties of the obtained polyimide film.

[0127]

Example 4 One equivalent of NMP and BAPI and one equivalent of ODA were placed in a separable flask and stirred well at room temperature. Next, 1.85 equivalents of s-BPDA was gradually added as a powder, followed by stirring for 40 minutes. Then, 0.15 equivalent of s-BPDA was dissolved in NMP, gradually added, and then cooled and stirred for 1 hour to obtain an NMP solution of polyamic acid. Note that NMP
Was used so that the concentration of charged monomers of diamines and aromatic tetracarboxylic dianhydrides was 18% by weight. The firing conditions were the same as in Example 1. Table 1 shows the physical properties of the obtained polyimide film.

[0128]

Example 5 The polyamic acid solution used in Example 1 was cast on a glass plate as it was, dried at about 100 ° C. for about 60 minutes, and the polyamic acid coating was peeled off from the glass plate. Fix to the support frame, then at about 150 ° C for about 30 minutes, about 20 minutes
Heat at 0 ° C for about 30 minutes and about 300 ° C for about 30 minutes,
Heat at 0 ° C for about 30 minutes, dehydrate ring-close and dry,
Was obtained. Table 1 shows the physical properties of the obtained polyimide film.

[0129]

Comparative Example 1 PMD was produced in the same manner as in Example 1 above.
A and ODA were used in equimolar amounts to obtain a polyimide film. Table 1 shows the physical properties of the obtained polyimide film.

[0130]

Example 6 Two equivalents of NMP and BAPT and one equivalent of ODA were placed in a separable flask and stirred well at room temperature. Next, 2.85 equivalents of s-BPDA was gradually added as a powder, followed by stirring for 40 minutes. Then, 0.15 equivalent of s-BPDA was dissolved in NMP, gradually added, and then cooled and stirred for 1 hour to obtain an NMP solution of polyamic acid. Note that NMP
Was used so that the concentration of charged monomers of diamines and aromatic tetracarboxylic dianhydrides was 18% by weight.

Next, the polyamic acid solution was mixed with acetic anhydride and β-picoline, cast and applied on a glass plate, dried at about 100 ° C. for about 5 minutes, and then the polyamic acid coating film was peeled off from the glass plate. The membrane is fixed to a support frame and then at about 100 ° C for about 5
For about 5 minutes at about 200 ° C, for about 5 minutes at about 300 ° C, and for about 5 minutes at about 400 ° C.
A polyimide film of 0 μm was obtained. Table 2 shows the physical properties of the obtained polyimide film.

[0132]

[Table 2]

A bisphenol A type epoxy resin (E1001) was applied to a polyimide film having a surface treated with a release agent.
50 parts of cresol novolak type epoxy resin (180H65 / product of Yuka Shell Epoxy Co., Ltd.), polyamide resin (M12
76 / Elf Atochem Japan K.K.) 40
Part, diaminodiphenyl sulfone 7 parts, dicyandiamide 2 parts, toluene 35 parts, isopropyl alcohol 1
After drying, 5 parts of an adhesive was applied so as to have a thickness of about 20 μm, and dried at 150 ° C. for 10 minutes. The adhesive surface and a copper foil (Low-profile electrolytic copper foil VLP-3EC manufactured by Mitsui Kinzoku Co., Ltd.) were laminated at 120 ° C., and after observing the appearance in this state, the dimensional change after etching was measured according to the above method. did. Table 2 shows the results.

[0134]

Example 7 Two equivalents of NMP and BAPT and one equivalent of ODA were placed in a separable flask and stirred well at room temperature. s-
2 equivalents of BPDA were slowly added as a powder and then stirred for 40 minutes. ODPA, slowly add 0.85 equivalents of powder,
Thereafter, the mixture was stirred for 40 minutes. Then, 0.15 equivalents of ODPA was dissolved in NMP, added gradually, and then cooled and stirred for 1 hour to obtain a polyamic acid NMP solution. The amount of NMP used was such that the concentration of charged monomers of diamines and aromatic tetracarboxylic dianhydrides was 18% by weight. The firing conditions were the same as in Example 1. Table 2 shows the physical properties of the obtained polyimide film.

This polyimide film was laminated with a copper foil in the same manner as in Example 6 to observe the appearance and measure the dimensional change. The results are shown in Table 2.

[0136]

Example 8 One equivalent of NMP and BAPT and one equivalent of ODA were placed in a separable flask and stirred well at room temperature. Next, 1.85 equivalents of s-BPDA was gradually added as a powder, followed by stirring for 40 minutes. Then, 0.15 equivalents of s-BPDA was dissolved in NMP, gradually added, and then cooled and stirred for 1 hour to obtain an NMP solution of polyamic acid. The amount of NMP used was such that the concentration of charged monomers of diamines and aromatic tetracarboxylic dianhydrides was 18% by weight. The firing conditions were the same as in Example 1. Table 2 shows the physical properties of the obtained polyimide film.

An adhesive similar to that used in Example 6 was applied to a PET film having a surface subjected to a release agent treatment so as to have a thickness of about 20 μm after drying, and dried at 150 ° C. for 10 minutes. The PET film with the adhesive was slit to a width of 26 mm, and the polyimide film slit to a width of 35 mm was pressed at 40 ° C. to obtain a TAB tape.

After removing the PET tape from the TAB tape, the adhesive surface and a copper foil (Low-produced by Mitsui Kinzoku) were used.
(File electroplated copper foil VLP-3EC) was laminated at 120 ° C., and after observing the appearance in this state, the dimensional change after etching was measured according to the above method. Table 2 shows the results
Shown in

[0139]

Example 9 Two equivalents of NMP and BAPB and one equivalent of ODA were placed in a separable flask and stirred well at room temperature. Next, 2.85 equivalents of s-BPDA was gradually added as a powder, followed by stirring for 40 minutes. Then, 0.15 equivalent of s-BPDA was dissolved in NMP, gradually added, and then cooled and stirred for 1 hour to obtain an NMP solution of polyamic acid. Note that NMP
Was used so that the concentration of charged monomers of diamines and aromatic tetracarboxylic dianhydrides was 18% by weight. The firing conditions were the same as in Example 1. Table 2 shows the physical properties of the obtained polyimide film.

Using this polyimide film, a tape for TAB was obtained in the same manner as in Example 8, and the tape was laminated with a copper foil to observe the appearance and measure the dimensional change. The results are shown in Table 2.

[0141]

Example 10 The polyamic acid solution used in Example 6 was
It is cast on a glass plate as it is, dried at about 100 ° C for about 60 minutes, the polyamic acid coating film is peeled off from the glass plate, and the coating film is fixed to a support frame, and then at about 150 ° C for about 30 minutes.
Heat at 200 ° C for about 30 minutes and at about 300 ° C for about 30 minutes.
Heat at 400 ° C for about 30 minutes, dehydrate ring-closed and dry, about 50μ
m was obtained. Table 2 shows the physical properties of the obtained polyimide film.

Using this polyimide film, a TAB tape was obtained in the same manner as in Example 8, laminated with a copper foil, and the appearance was observed and the dimensional change was measured. The results are shown in Table 2.

[0143]

Comparative Example 2 PMD was produced in the same manner as in Example 1 above.
A and ODA were used in equimolar amounts to obtain a polyimide film. Table 2 shows the physical properties of the obtained polyimide film.

Using this polyimide film, a TAB tape was obtained in the same manner as in Example 8, laminated with a copper foil, and the appearance was observed and the dimensional change was measured. The results are shown in Table 2.

[0145]

As described above, a polyimide film containing a polyimide obtained from a polyamic acid using a diamine having a specific ester structure has a high elasticity, an appropriate linear expansion coefficient, an appropriate flexibility, and a low hygroscopic expansion property. Thus, a useful polyimide film having low hygroscopicity can be obtained.

Further, it is possible to provide a TAB tape using a polyimide film as a base film which has a linear expansion coefficient which is not extremely different from that of metal or glass and which is obtained as a polyimide film having a specific high elastic modulus. .

Further, a flexible printed circuit board using such a polyimide film as an insulating material has no warp or curl, and has little dimensional change during processing and mounting. Therefore, it is a material suitable for a flexible printed circuit board having a high-density pattern.

Claims (8)

[Claims] A water absorption rate of 1.6% or less, a coefficient of hygroscopic expansion of 15 ppm or less, and a compound represented by the following general formula (1): (Where R ₁ and R ₂ are a tetravalent organic group, X is a divalent organic group, and R ₃ is a divalent organic group. Integers m and n are m
Satisfies ≧ 1, n ≧ 0. A polyimide composition represented by the formula: 2. The water absorption rate is 1.6% or less, and the coefficient of hygroscopic expansion is 15 ppm or less. (Where R ₁ and R ₂ are a tetravalent organic group, X is a divalent organic group, R ₃ is a divalent organic group, and R ₁ is And one or more tetravalent organic groups selected from The integers m and n satisfy m ≧ 1 and n ≧ 0. A polyimide composition represented by the formula: 3. A water absorption rate of 1.6% or less, a coefficient of hygroscopic expansion of 15 ppm or less, and a compound represented by the following general formula (1). (Where X is a divalent organic group, R ₃ is a divalent organic group, and R ₁ is And one or more tetravalent organic groups selected from R ₂ is represented by the following formula: And one or more kinds of tetravalent organic groups selected from The integers m and n satisfy m ≧ 1 and n ≧ 0. A polyimide composition represented by the formula: 4. A water absorption rate of 1.6% or less, a coefficient of hygroscopic expansion of 15 ppm or less, and a compound represented by the following general formula (1). (However, R ₃ represents a divalent organic group, and R ₁ represents And one or more tetravalent organic groups selected from R ₂ is represented by the following chemical formula 9 And one or more kinds of tetravalent organic groups selected from X is And one or more divalent organic groups selected from The integers m and n satisfy m ≧ 1 and n ≧ 0. A polyimide composition represented by the formula: 5. A compound having a water absorption of 1.6% or less, a coefficient of hygroscopic expansion of 15 ppm or less, and a compound represented by the following general formula (1). (However, R ₁ is And one or more tetravalent organic groups selected from R ₂ is And one or more kinds of tetravalent organic groups selected from X is And one or more divalent organic groups selected from R ₃ is a compound represented by the following formulas: Embedded image And one or more divalent organic groups selected from The integers m and n satisfy m ≧ 1 and n ≧ 0. A) a polyimide composition represented by 6. A polyimide film comprising the polyimide composition according to any one of claims 1 to 5. 7. A TAB tape comprising the polyimide film according to claim 6 provided with an adhesive layer and a protective layer. 8. A flexible printed circuit board including at least a conductor and an insulating material, wherein the insulating material is the polyimide film according to claim 6.