KR20060050123A - Flexible laminating board and its manufacture method - Google Patents

Abstract

Provided are flexible laminates that correspond to installation conditions of high temperature and high pressure while maintaining the characteristics of the flexible laminates.

In the flexible laminated board which has metal foil on the single side | surface or both surfaces of an insulated resin layer, the high elastic resin layer of the storage elastic modulus in 350 degreeC of at least 1 layer of polyimide resin which an insulated resin layer contacts with metal foil is 1 * 10 <^8> Pa or more; At least one layer of polyimide resin having a low thermal expansion resin layer of 20 × 10 ⁻⁶ / K or less, and further comprising a thickness ratio of the high elastic resin layer in the insulating resin layer. The range is -45%.

Description

Flexible laminated board and manufacturing method thereof {FLEXIBLE LAMINATING BOARD AND ITS MANUFACTURE METHOD}

TECHNICAL FIELD This invention relates to the field of electronic materials, especially the flexible laminated board which consists of metal foil and polyimide insulating resin layer used in order to form a circuit.

Polyimide films are excellent in thermal properties, insulation properties, solvent resistance, and the like, and are widely used as materials for electric and electronic parts such as mobile phones. In recent years, as ultra-thin and high functionalization of mobile telephones etc. advances, the board | substrate mounted in the device component material is moving from a rigid board to a flexible printed board. Flexible laminated boards are widely used for such flexible printed boards. In some flexible laminated boards, adhesive resins such as epoxy resins are used for insulating resin layers in contact with the metal foil, and polyimide resins are used for insulating resin layers in the base portion. By the way, with recent lead-free hander response and shortening time and high efficiency of semiconductor element installation, the temperature and pressure at the time of installation are expected to increase, and in that case, in a flexible laminate using epoxy resin, thermal resistance such as heat resistance of epoxy resin The problem that the correspondence to high temperature installation is difficult from the low characteristic is pointed out.

Then, as known from patent document 1, although the flexible laminated board which used the polyimide resin with high heat resistance is developed for the insulated resin layer which contact | connects metal foil, even in the two-layer flexible laminated board which consists of this metal foil and a polyimide resin layer, it has insulation until now. Since it is necessary to laminate metal foil on a resin layer, thermoplastic polyimide resin is widely used for the polyimide resin layer which contact | connects metal foil. However, even a flexible laminate using a thermoplastic polyimide resin known so far is excellent in thermal properties that can withstand the installation of semiconductor devices under high temperature and high pressure conditions, and does not maintain all the characteristics of the flexible laminate. It was a situation.

[Patent Document 1] WO02 / 085616 Publication

[Patent Document 2] Japanese Patent Laid-Open No. 2003338525, publication

[Patent Document 3] Japanese Patent Publication No. 2003-264374

On the other hand, in accordance with the demand for miniaturization of electronic devices, a technique for providing a semiconductor element on a wiring board on which a circuit is formed has been developed. For example, Patent Document 2 relates to a semiconductor device and a manufacturing method thereof, but includes the technology described herein, and in a technique similar to the same method, when a semiconductor element is provided on a wiring board through a resin, the resin component interposed is cured. In order to or soften, the semiconductor element is heated to a high temperature together with the sealing jig. According to this heating temperature, although patent document 2 has the meaning of heating to 280-300 degreeC or more, although this temperature depends also on the resin characteristic to interpose, it heats normally at 250 degreeC or more. Moreover, although there exists a method of forming a process with metal which contact | connects without interposing resin, in this case, it will heat at higher temperature. As shown in Patent Literature 2, the installation of the semiconductor element on the substrate is provided by pressing the vamp of the semiconductor element to the conductor layer of the wiring board under heating, and in this case, a protrusion such as a vamp of the semiconductor element in contact with the conductor circuit of the laminated board. Since pressure is pressed against and bonded to the substrate in a high temperature state, if the heat resistance of the resin layer in contact with the wiring board is low or of a soft material, pressure is concentrated with the temperature at the connection portion, and the circuit on the resin layer of the wiring board is A problem arises in that a part of the semiconductor element is immersed in the insulating resin layer of the substrate, so that stable installation cannot be performed.

This problem may be solved if the wiring board is filled with an inorganic material. However, in this case, the flexibility of the wiring board cannot be maintained, and only in a field different from that in which an industrially flexible laminate is used. It becomes inapplicable. Patent Literature 3 describes a heat-resistant resin composition which focuses on an elastic modulus at a high temperature (30 ° C.) of a heat-resistant resin and a multilayer wiring board using the same. However, Patent Document 3 discloses that the resin composition described therein can be used for the surface protection film of a semiconductor chip, the interlayer insulating film of a semiconductor package, the interlayer insulating film of a substrate for semiconductor element installation, and the like, but in a state of maintaining the flexible characteristics in practice. In the case of applying to a semiconductor installation use, the examination is insufficient, and also the conventional flexible laminated board was not designed in consideration of the application to the installation use.

The present invention can withstand high temperature installation conditions by improving the glass transition temperature (Tg) of the polyimide resin and the storage elastic modulus in the high temperature region (350 ° C.) of the polyimide resin in contact with the metal foil without impairing the adhesion to the metal foil. It is to provide a flexible laminate with excellent heat resistance.

As a result of examining in order to solve the said subject, the present inventors discovered what can be set as the flexible laminated board which improved the heat resistance characteristic by designing the structure of the insulating resin layer of a flexible laminated board, and completed this invention.

That is, this invention is a flexible laminated board which has metal foil in the single side | surface or both surfaces of an insulated resin layer, Comprising: The insulated resin layer consists of multiple layers of polyimide resin, and the polyimide resin of at least 1 layer which contact | connects metal foil is 350 degreeC. the storage modulus is ^{1 × 10 8 ~2 × 10 9} pa, and the glass transition temperature is formed by a highly elastic resin layer of 300~400 ℃, also a resin other than the high elastic resin layer, the coefficient of linear expansion of at least one layer It is a flexible laminated board which has a low thermally expansible resin layer of 20x10 <^-6> / K or less, and the thickness ratio of the high elastic resin layer in an insulated resin layer exists in 3 to 45% of range.

Here, 1) both sides of the low thermally expandable resin layer are high elastic resin layers, and 2) polyimide resin constituting the high elastic resin layer in contact with the metal foil is made of pyromellitic dianhydride and diamine, and is used as a diamine as 2,2-bis. [4- (4-aminophenoxy) phenyl] propane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, and 4,4'-bis ( Using at least one diamine selected from 4-aminophenoxy) biphenyl containing 5 to 80 mol%, or 3) the surface roughness (Rz) of the surface of the metal foil in contact with the polyimide resin layer is 0.6 to Either of those in the range of 1.0 µm, which satisfies at least one requirement gives a better flexible laminate.

In addition, in the present invention, the storage modulus at 350 ° C. is 1 × 10 ⁸ to 2 × 10 ⁹ Pa, and the glass transition temperature is on the surface of the metal foil having the surface roughness Rz of 0.6 to 1.0 μm. Process of apply | coating the polyimide precursor resin which consists of a high elastic resin layer of 300-400 degreeC, 2) The polyimide precursor which consists of a low thermally expansible resin layer with a linear expansion coefficient of 20x10 <^-6> / K or less on the said polyimide precursor resin layer. A step of applying a resin, and 3) a step of thermosetting in a state where a plurality of layers of polyimide precursor resin layers are formed on the metal foil, with at least one layer of metal foil and at least two layers of polyimide resin. It is a manufacturing method of the flexible laminated board which consists of.

Hereinafter, the flexible laminated board of this invention is explained in full detail.

The flexible laminated board of this invention is comprised from the insulated resin layer and metal foil, and has metal foil on one side or both surfaces of an insulated resin layer. Here, the insulated resin layer is comprised from the polyimide resin of several layers, The storage elastic modulus in 350 degreeC of the at least 1 layer of polyimide resin layer which contact | connects metal foil has 1x10 <^8> -2 * 10 <^9> Pa, glass The transition temperature is formed of the high elastic resin layer in the range of 300-400 degreeC. And the thickness ratio of this high elastic resin layer in an insulated resin layer needs to exist in 3 to 45% of range. Moreover, it is preferable that the high elastic resin layer is formed adjacent to both sides of the low thermal expansion resin layer.

The polyimide resin used by this invention selects a well-known diamino compound, tetracarboxylic acid, or its anhydride suitably, and combines these so that it may be suited to the characteristic suitable for each layer which comprises an insulating resin layer, The organic solvent It can obtain by making it react. In the present invention, the polyimide resin includes a polyimide resin or a polyamideimide resin having an imide bond in a molecule as a main component, and does not necessarily need to be a single polyimide resin. It may be a mixture. In the case of a mixture with other resin, other resin is 30% or less, Preferably it is 20% or less. In addition, although a small amount may mix | blend an inorganic filler, since these formulations may impair the cut resistance and circuit workability which the flexible laminated board of this invention has, it is preferable to stop in small amounts. It is advantageous to make the insulated resin layer substantially consisting of a polyimide resin layer.

High elastic resin layer in the range of 1 * 10 <^8> -2 * 10 <^9> Pa, and glass transition temperature of 300-400 degreeC in storage elastic modulus at 350 degreeC in this invention (henceforth only a high elastic resin layer.) The polyimide resin (hereinafter also referred to simply as a high elastic polyimide resin) constituting the above is not limited as long as its properties are satisfied, but is preferably a polyimide resin having a structural unit represented by the following general formula (1). .

[Tue 1]

In general formula (I), Ar <_1> , Ar <_3> is a C12 or more divalent aromatic residue, Ar <_2> is a C6 or more tetravalent aromatic residue, and k and 1 are each structural unit in the case where k + 1 = 100. The mol ratio of is represented, k is 20-95, 1 is a number of 80-5.

Here, as Ar ₁ , the bivalent group represented by Formula (a) is mentioned as a preferable thing.

[Tue 2]

Moreover, as Ar <_2> , the tetravalent group represented by Formula (b) is mentioned as what made it preferable.

[Tue 3]

As Ar ₃ , one or more of the divalent groups represented by formulas (c) to (g) may be mentioned as preferable ones, but more preferably any of (e), (f) and (g) Is 1 or more.

[Tue 4]

It is necessary for the high elastic polyimide resin to have a storage modulus at 350 ° C in the range of 1 × 10 ⁸ to 2 × 10 ⁹ pa, and preferably in the range of 1 × 10 ^{8 to} 1 × 10 ⁹ . If this value is not filled to 1 × 10 ⁸ Pa, for example, when the semiconductor element is installed at a high temperature, the insulating resin layer in contact with the metal foil becomes fluid at the installation temperature, and the metal wiring easily sinks. Lose. On the other hand, the storage modulus of the high elastic resin exceeding 2 × 10 ⁹ Pa is preferable from the viewpoint of thermal characteristics at high temperature for the purpose of the present invention, but there is a possibility that the flexibility for expressing the bending characteristics of the flexible laminate is lowered. . In addition, it is necessary for the high elastic resin layer to have a glass transition temperature (Tg) in the range of 300 to 400 ° C, preferably 325 to 380 ° C, particularly preferably 350 ° C or more and 380 ° C or less. It is advantageous. If the glass transition temperature does not reach 300 ° C, sinking of the metal wiring is likely to occur as described above, and the heat resistance of the hand of the flexible laminate is also deteriorated. Moreover, when glass transition temperature exceeds 400 degreeC, favorable adhesiveness between a polyimide layer and metal foil cannot be obtained.

The insulating resin layer of the flexible laminate of the present invention is composed of a plurality of layers, and in addition to the high elastic resin layer described above, the coefficient of linear expansion is 20 × 10 ⁻⁶ / K or less, preferably 1 × 10 ⁻⁷ / K to 20 × 10 ^{− It has a 6} / K low thermal expansion resin layer. The polyimide resin (hereinafter also referred to as low thermally expandable polyimide resin) constituting the low thermally expandable resin layer is not limited as long as its properties are satisfied, but preferably a polyimide having a structural unit represented by the following general formula (H) It is a mid resin.

[Tue 5]

Here, R <_1> , R <_2> may mutually be same or different and represents a lower alkyl group, q and r are the numbers of 0-4, respectively. As Ar <_4> , the 1 or more tetravalent group represented by following formula (h) and (i) is mentioned preferably. In formula (i), X represents S0 ₂ , C0, 0 or a direct bond.

[Tue 6]

Among the unit structures represented by the general formula (II), particularly, the structural unit represented by the following formula (III) is represented as being preferable.

[Tue 7]

It is preferable that the structural unit represented by general formula (II) or (III) is 50 mol% or more of all the polyimide structural units of low thermal expansion polyimide resin.

Examples of the metal foil used in the present invention include copper foil, stainless foil, and alloy foil. Here, alloy foil refers to a metal foil which contains copper foil as an essential, and contains at least 1 type or more of elements, such as chromium, nickel, zinc, and silicon, and means metal foil with a copper content of 90% or more. When using metal foil, you may surface-treat with zinc plating, nickel plating, a silane capping agent, etc.

Thin metal foil is favorably used due to the fine pitch of metal wiring. From such a viewpoint, preferable metal foil thickness is 5-35 micrometers, More preferably, it is the range of 8-18 micrometers. Moreover, it is preferable that the metal foil to be used has the surface roughness Rz of the surface which contact | connects a polyimide resin in the range of 0.6-1.0 micrometer. When surface roughness Rz is less than 0.6 micrometer, the adhesiveness of a metal foil and a polyimide resin layer is not supported, and when it is 1.0 micrometer or more, transparency of a polyimide film falls and it hinders installation of a semiconductor element. Moreover, by making the surface roughness Rz of metal foil into the said range, the residual of the metal component in the polyimide resin layer which arises at the time of a circuit process can also be reduced. In the above, metal foil whose surface roughness Rz is the said range becomes suitable for fine pitch formation of metal wiring.

The flexible laminated board of this invention is comprised by the polyimide resin of multiple layers, and becomes a multilayered structure, by making at least 1 layer of polyimide resin layer which contact | connects metal foil the said high elastic resin layer of a specific thickness range, It can be made into a flexible laminate that can withstand high pressure installation conditions. Here, it can be said that it is suitable especially for a high density installation use by making thickness and the surface roughness Rz of a metal foil into the said range.

In the flexible laminate of the present invention, the insulated resin layer is composed of a plurality of polyimide resins to form a multilayer structure. As a preferable layer structure, a layer structure as shown in the following 1) to 5) is exemplified. Here, M represents metal foil, H represents a high elastic polyimide resin, L represents a low thermally expandable polyimide resin, and P represents a polyimide resin other than satisfying the storage modulus or linear expansion coefficient of H or L.

1) M / H / L, 2) M / H / L / H / M, 3) M / H / L / H, 4) M / H / L / P / M, 5) M / H / L / P,

And the thickness ratio which H occupies in an insulated resin layer is 3 to 45%, Preferably it is the range of 5 to 20%. As other polyimide resin (P), in order to control the warpage after metal foil etching, etc., it is preferable that H and a physical characteristic are approximate, and especially, the difference of H and a linear expansion coefficient is less than 10x10 <^-6> / K. It is good. In order to obtain a flexible laminate having metal foil on both sides of the insulated resin layer, it is advantageous to use a method of heat-compressing the metal foil later. In that case, the polyimide resin (P) laminated in contact with L has a linear expansion coefficient of 30. It is preferable that it is thermoplastic polyimide resin of * 10 <^-6> / K or more.

Next, although the manufacturing method of the flexible laminated board of this invention is mentioned, about the content similar to what was already demonstrated by a flexible laminated board, it is only a brief description.

After apply | coating and drying polyimide precursor resin on metal foil, the flexible laminated board of this invention can be made into the laminated board by which the polyimide resin layer was laminated | stacked on the single side | surface of metal foil by thermosetting treatment. It is preferable that the polyimide precursor resin apply | coated on metal foil is a solution state, and is usually apply | coated in the state dissolved in a suitable solvent. It is preferable that the surface roughness Rz of the metal foil surface to which polyimide precursor resin is apply | coated exists in the range of 0.6-1.0 micrometer. In the manufacturing method of the flexible laminated board of this invention, as for the polyimide precursor resin apply | coated directly on metal foil, the storage modulus in 350 degreeC after hardening is 1 * 10 <^8> -2 * 10 <^9> Pa, and glass transition temperature is 300-. It becomes a highly elastic resin layer of 400 degreeC. By apply | coating the precursor resin used as this highly elastic resin layer directly on metal foil, the stable adhesive strength of metal-polyimide resin can be obtained. The means to apply | coat is not specifically limited, For example, a well-known method, such as a barcode system, a Granby coat system, a roll coat system, a die coat system, can be suitably selected and employ | adopted.

When the polyimide precursor resin layer applied to the metal foil contains a solvent, it is dried to an appropriate range. It is preferable to perform drying temperature at this temperature at the grade which the imidation of a polyimide precursor resin layer does not advance, It is preferable that it is 150 degrees C or less specifically, and the range of 110-140 degreeC is preferable. Moreover, it is preferable to make the amount of solvent contained in a polyimide precursor resin layer in this drying process into 50 weight part or less with respect to 100 weight part of polyimide precursor resin.

The flexible laminated board of this invention has the polyimide resin layer of the low thermal expansion resin layer whose linear expansion coefficient is 20x10 <^-6> / K or less in addition to the polyimide resin layer of the high elastic resin layer mentioned above. It is preferable to apply | coat and form the low thermal expansion resin layer in the precursor state on the polyimide precursor resin layer used as the high elastic resin layer formed as mentioned above. It is preferable to apply | coat the precursor resin of this low thermal expansion resin also in a solution state, and when it is apply | coated in the state containing a solvent, it is good to dry on the above conditions.

When apply | coating and drying the precursor resin layer which becomes a high elastic resin layer and a low thermally expansible resin layer gradually on a metal foil, respectively, it is preferable to provide one layer of polyimide precursor resin layer in order to control the curvature etc. after metal foil etching. Here, it is preferable that the layer laminated | stacked is the same as the above-mentioned high elastic resin layer, or the physical property is approximate, and it is especially preferable that the difference of a high elastic resin layer and a linear expansion coefficient is 10x10 <^-6> / K or less. In order to obtain a flexible laminate having metal foils on both sides of the insulated resin layer, it is advantageous to use a method of hot pressing the metal foil afterwards. In that case, the polyimide layer laminated on the low thermal expansion resin layer has a linear expansion coefficient of 30 × 10. It is preferable that it is thermoplastic polyimide resin of ^-6 / K or more. The polyimide resin layer arbitrarily provided in the flexible laminated board of this invention can also be apply | coated and dried like the formation method of the two polyimide layers mentioned above.

As mentioned above, when 2 or 3 or more polyimide precursor resin layers are apply | coated and dried on metal foil, the polyimide precursor resin layer of the multiple layers on metal foil will be heat-processed and thermoset. The heat treatment is preferably performed by passing through a plurality of curing chambers. In this case, the temperature is increased in steps and steps from around 150 ° C, and is finally heated until it reaches 250 ° C or more, preferably 300 ° C or more. Imidized. If the maximum heating temperature for imidization is too high, the resin may be decomposed. Therefore, it is preferable not to heat above 20 ° C lower than the decomposition start temperature. Moreover, this heat processing does not interfere at all even if it uses the same apparatus following the said drying process. In this process, the polyimide precursor resin is substantially imidized.

On the resin layer which completed imidation, metal foil is laminated | stacked as needed. The lamination | stacking method is a simple method of heating and pressing a predetermined metal foil between presses and rolls. It is preferable that heating temperature here is more than glass transition temperature of the polyimide resin layer which contact | connects the metal foil laminated | stacked. In addition, although the metal foil laminated | stacked here may be the same as the metal foil mentioned above, when lamination | stacking by heat-pressurizing process, it is advantageous that Rz is larger than 1.0 micrometer because of adhesive force maintenance with a polyimide.

Hereinafter, an embodiment of the present invention will be described. In addition, each film physical property value is measured by the following method.

1) The storage modulus of the glass transition temperature (Tg) and the high temperature region (350 ° C.) is a polyimide film obtained by the polyimide precursor resin of each synthesis example. The dynamic viscoelasticity at the time of heating up at ° C / min was measured, and Tg (maximum value of tan-delta) and storage elastic modulus of 350 degreeC were calculated | required.

2) The thermal expansion coefficient was calculated | required from the dimension change from 100 degreeC to 240 degreeC at the temperature increase rate of 20 degree-C / min, and the temperature-fall of 5 degree-C / min using the TMA100 type | mold thermomechanical analyzer of Seiko Instruments.

3) The adhesive force with copper foil was measured and calculated | required by pulling copper foil in the direction of 180 degrees with the load cell 2 kg and a crosshead speed of 50 mm / min using room temperature Straw Graph R-1.

Evaluation criteria were determined as follows according to the adhesive force.

○: more than 0.8 kN / m adhesive force

(Triangle | delta): 0.5 kN / m or more and less than 0.8 kN / m adhesive

×: less than 0.5kN / m adhesive force

4) The surface roughness (Rz) of the metal foil was measured under a condition of a measuring speed of 0.02 mm / sec and a radius of curvature of 2 μm using a highly sensitive surface profiler (P-15 manufactured by KLA Tencol Co., Ltd.) in accordance with JIS B 0651. .

5) The hander heat resistance of the flexible laminated sheet was immersed in a solder bath at a predetermined temperature for 10 seconds, and the maximum temperature among the temperatures without peeling of the metal foil or swelling of the resin was regarded as the hander heat resistance temperature.

The ellipsis in an Example is demonstrated.

DMA _C : N, N'-dimethylacetamide

PMDA: pyromellitic dianhydride

BPDA: 3,3'4,4'-biphenyltetracarboxylic dianhydride

DSDA: diphenylsulfone-3,4,3 ', 4'-tetracarboxylic dianhydride

BTDA: Benzophenone-3,4,3 ', 4'-tetracarboxylic dianhydride

BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane

BAPB: 4,4'-bis (4-aminophenoxy) biphenyl

TPE-Q: 1,4-bis (4-aminophenoxy) benzene

TPE-R: 1,3-bis (4-aminophenoxy) benzene

m-TB: 2,2'-dimethyl-4,4'-diaminobiphenyl

Synthesis Examples 1-3

BAPP and BAPB were supplied and dissolved in DMA _C , PMDA was supplied continuously, and it stirred at room temperature for about 3 hours, and prepared the polyimide precursor resin solution which consists of the component of the composition shown in Table 1.

In addition, in all the synthesis examples, the ratio of the tetracarboxylic dianhydride component and the diamine component was made into about 100 mol% stoichiometry. In addition, the numerical value of the water support fee composition column of Table 1 shows a ratio.

The obtained polyimide precursor resin solution was applied onto a copper foil and dried until the surface of the precursor resin layer became a tack free state at a temperature of 140 ° C. or lower, and then heated in several steps in a temperature range of 150 to 360 ° C. It imidated and it was set as the polyimide film of thickness 25micrometer. Next to this polyimide film, the storage elastic modulus, glass transition temperature (Tg), and linear expansion coefficient in 350 degreeC were measured. The results are shown in Table 1.

Synthesis Example 4, 5

BAPP and TPE-Q were supplied and dissolved in DMA _C , PMDA was supplied continuously, it stirred at room temperature for about 3 hours, and the polyimide precursor resin solution which consists of the component of the composition shown in Table 1 was prepared. This polyimide precursor resin solution was processed by the method similar to the synthesis example 1, the polyimide film was formed and the physical property was evaluated. The results are shown in Table 1.

Synthesis Example 6, 7

BAPP and TPE-R were supplied and dissolved in DMA _C , PMDA was supplied continuously, it stirred at room temperature for about 3 hours, and the polyimide precursor resin solution which consists of a component of the composition shown in Table 1 was prepared. This polyimide precursor resin solution was processed by the method similar to the synthesis example 1, the polyimide film was formed, and the physical property was evaluated. The results are shown in Table 1.

Synthesis Example 8

BAPP was supplied and dissolved in DMA _C , and PMDA and DSDA were supplied sequentially, and it stirred at room temperature for about 3 hours, and prepared the polyimide precursor resin solution which consists of the component of the composition shown in Table 1. This polyimide precursor resin solution was processed by the method similar to the synthesis example 1, the polyimide film was formed, and the physical property was evaluated. The results are shown in Table 1.

Synthesis Example 9

It supplied and dissolved in BAPPfmf DMA _C , Then, PMDA and BTDA were supplied sequentially, it stirred at room temperature for about 3 hours, and the polyimide precursor resin solution which consists of the component of the composition shown in Table 1 was prepared. This polyimide precursor resin solution was processed by the method similar to the synthesis example 1, the polyimide film was formed, and the physical property was evaluated. The results are shown in Table 1.

Synthesis Example 10

BAPP was supplied and dissolved in DMA _C , PMDA was supplied continuously, it stirred at room temperature for about 3 hours, and the polyimide precursor resin solution which consists of a component of the composition shown in Table 1 was prepared. This polyimide precursor resin solution was processed by the method similar to the synthesis example 1, the polyimide film was formed, and the physical property was evaluated. The results are shown in Table 1.

Synthesis Example 11

BAPB was supplied and dissolved in DMA _C , PMDA was supplied continuously, it stirred at room temperature for about 3 hours, and the polyimide precursor resin solution which consists of the component of the composition shown in Table 1 was prepared. This polyimide precursor resin solution was processed by the method similar to the synthesis example 1, the polyimide film was formed and the physical property was evaluated. The results are shown in Table 1.

Synthesis example Fee support  Storage modulus (Pa)  Tg (℃)  Thermal expansion coefficient (ppm)  Diamine component  Acid Anhydride Ingredients One BAPP80 + BAPB20 PMDA 1.8 × 10 ⁸ 326.4 55.7 2 BAPP70 + BAPB30 PMDA 2.7 × 10 ⁸ 342.8 51.8 3 BAPP30 + BAPB70 PMDA 8.6 × 10 ⁸ 369.8 49.5 4 BAPP80 + TPE-Q20 PMDA 1.2 × 10 ⁸ 319.1 50.8 5 BAPP30 + TPE-Q70 PMDA 7.5 × 10 ⁸ 365.2 52.4 6 BAPP80 + TPE-R20 PMDA 5.2 × 10 ⁸ 363.7 57.5 7 BAPP30 + TPE-R70 PMDA 9.2 × 10 ⁸ 374.3 61.3 8 BAPP PMDA40 + DSDA60 2.0 × 10 ⁶ 280.3 62.6 9 BAPP PMDA40 + BTDA60 4.4 × 10 ⁶ 263.7 67.8 10 BAPP PMDA 7.1 × 10 ⁷ 321.3 52.3 11 BAPB PMDA 1.5 × 10 ⁹ 405.8 52.0

Synthesis Example 12

m-TB was supplied and dissolved in DMA _C , PMDA was supplied continuously, and it stirred at room temperature for about 3 hours, and prepared the polyimide precursor resin solution. It was 2.5 ppm when this polyimide precursor resin solution was processed by the method similar to the synthesis example 1, the polyimide film was formed, and the linear expansion coefficient was measured.

Example 1

On the steel foil of thickness 12 micrometers and surface roughness (Rz) 0.7 micrometer, the polyimide precursor resin solution prepared in the synthesis example 1 was apply | coated so that thickness after hardening might be 6 micrometers, and it dried at 140 degreeC for 5 minutes. Moreover, the polyimide precursor resin solution prepared in the synthesis example 12 is apply | coated so that the thickness after hardening may be set to 29 micrometers, and it is dried for 15 minutes at less than 140 degreeC. Moreover, on these two-layer polyimide precursor resin layers, the polyimide precursor resin solution adjusted by the synthesis example 1 was apply | coated so that the thickness after hardening may be 6 micrometers, it dried at 140 degreeC for 5 minutes, and was 150-360 degreeC It divided into several steps in the temperature range of, and heated up stepwise over 15 minutes, and obtained the flexible laminated board which has copper foil on the single side | surface of the insulated resin layer.

The copper foil of the obtained flexible laminated board was processed into the predetermined circuit by etching. About this flexible laminated board, evaluation of adhesiveness with copper foil and evaluation of hander heat resistance were performed, and the adhesiveness with copper foil was 0.8 kN / m or more, and the heat resistance of the hander was 400 degreeC or more, and showed the favorable result. The evaluation results are shown in Table 2.

Examples 2-7

In Example 1, the flexible laminated board was produced by changing the kind of polyimide precursor resin layer formed as the high elastic resin layer of a 1st layer and a 3rd layer into the thing of the synthesis examples 2-7. About the high elastic resin layer surface of this flexible laminated board, adhesiveness with steel foil and hander heat resistance were evaluated. The evaluation results are shown in Table 2.

Comparative Examples 1 to 4

In Example 1, the flexible laminated board was produced by changing the kind of polyimide precursor resin layer formed as a resin layer of a 1st layer and a 3rd layer to the thing of the synthesis examples 8-11. About this flexible laminated board, the adhesiveness with copper foil and the hander heat resistance were evaluated using resin of a 1st layer as an evaluation surface. The evaluation results are shown in Table 2.

Types of polyimide precursor resin layers of the first layer and the third layer Adhesiveness with copper foil Hander heat resistance temperature (℃) Example 1 Synthesis Example 1 ○ ≥400 Example 2 Synthesis Example 2 ○ ≥400 Example 3 Synthesis Example 3 ○ ≥400 Example 4 Synthesis Example 4 ○ ≥400 Example 5 Synthesis Example 5 ○ ≥400 Example 6 Synthesis Example 6 ○ ≥400 Example 7 Synthesis Example 7 ○ ≥400 Comparative Example 1 Synthesis Example 8 ○ 370 Comparative Example 2 Synthesis Example 9 △ 360 Comparative Example 3 Synthesis Example 10 ○ 390 Comparative Example 4 Synthesis Example 11 × ≥400

The polyimide resin in contact with the metal layer of the present invention maintains high adhesion with metal foil while having a high Tg and a high storage elastic modulus at 350 ° C., which are not present in the adhesive polyimide resin. Therefore, since the flexible laminated board of this invention is excellent in the heat resistance characteristic of an insulated resin layer, it can be used suitably as a flexible laminated board for COF (chip-on-film) used suitably for high temperature installation of a semiconductor element. Moreover, the flexible laminated board of this invention is not only high in the thermal characteristic of the polyimide resin which is an insulating resin layer comprised by the multiple layer, and this insulating resin layer, but also has the high flexibility required for bending parts, such as a mobile telephone. Therefore, the invention can be used in small electronic devices such as mobile phones, and is an industrially valuable invention.

Claims (4)

A flexible laminated plate having metal foil on one or both sides of an insulated resin layer, wherein the insulated resin layer is made of a plurality of layers of polyimide resins, and the storage modulus at 350 ° C. of one or more layers of polyimide resins contacting the metal foil is 1 × 10. ^It is formed by the high elastic resin layer of 8-2 * 10 <^9> Pa and glass transition temperature of 300-400 degreeC, and as resin layers other than a high elastic resin layer, one or more linear expansion coefficients are 20x10 <^-6> / K or less It has a low thermally expansible resin layer, and the thickness ratio of the high elastic resin layer in an insulated resin layer exists in 3 to 45% of range, The flexible laminated board characterized by the above-mentioned. The polyimide resin constituting the highly elastic resin layer in contact with the metal foil is made of pyromellitic dianhydride and diamine, and as a diamine, 2,2-bis [4- (4-aminophenoxy) phenyl]. Propane and 1 selected from 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene and 4,4'-bis (4-aminophenoxy) biphenyl The flexible laminated board characterized by using 5-80 mol% or more of diamine or more types. The surface roughness Rz of the surface of the metal foil which contacts a polyimide resin layer exists in the range of 0.6-1.0 micrometer, The flexible laminated board of Claim 1 or 2 characterized by the above-mentioned. The following process, 1) A highly elastic resin layer having a storage modulus at 350 ° C. of 1 × 10 ⁸ to 2 × 10 ⁹ Pa and a glass transition temperature of 300 to 400 ° C. on a metal foil surface having a surface roughness Rz of 0.6 to 1.0 μm. Applying a polyimide precursor resin to be; 2) applying the polyimide precursor resin which becomes a low thermally expandable resin layer whose linear expansion coefficient is 20x10 <^-6> / K or less on the said polyimide precursor resin layer; And  3) The manufacturing of the flexible laminated board which consists of one or more layers of metal foil and two or more layers of polyimide resin characterized by having the process of thermosetting in the state in which the polyimide precursor resin layer of multiple layers was formed on the metal foil. Way.