JP2009096192A - Laminated body for thermally-conductive flexible boards, and thermally-conductive polyimide film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated body for a thermally-conductive flexible substrate and a thermally-conductive polyimide film excellent in heat radiation characteristic, thermal resistance, and size stability and having excellent tear resistance even in a thin film. <P>SOLUTION: The laminated body and the thermally-conductive polyimide film contain a polyimide resin of 30 mol.% or more of a structural unit represented by a general formula (1) in the thermally-conductive polyimide film in which a thermally-conductive filler is dispersed in the polyimide resin, wherein the content of the thermally-conductive filler is in a range from 25 wt.% to 55 wt.% with flexibility, alternatively, in the formula, Ar1 is an organic group of tetravalent having one or more aromatic rings, and R is lower alkyl group, lower alkoxy group, phenyl group, phenoxy group or halogen with 1-6C. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a heat conductive flexible substrate laminate and a heat conductive polyimide film used for a heat dissipation substrate and a flexible circuit substrate.

  In recent years, there has been an increasing demand for downsizing and weight reduction of electronic devices typified by mobile phones, and flexible circuit boards that are advantageous for downsizing and weight reduction of devices have come to be widely used in the field of electronic technology. It is coming. Among them, a flexible circuit board using a polyimide resin as an insulating layer has been widely used since its heat resistance and chemical resistance are good. Recently, with the miniaturization of electronic devices, the degree of circuit integration has increased, and in conjunction with the speeding up of information processing, heat dissipation means for heat generated in the device has attracted attention.

  In order to provide a flexible circuit board excellent in heat dissipation, heat dissipation from the polyimide resin layer constituting the insulating layer, that is, improvement in heat conductivity, is required in addition to heat dissipation from a metal circuit having high heat conductivity. In order to improve the thermal conductivity of the polyimide layer, in the case of a certain composition, the method of adjusting the heat treatment conditions to increase the degree of orientation of the polyimide layer, the method of changing to a highly oriented composition, and the high thermal conductivity of the resin A method of highly filling a porous inorganic filler is mentioned.

Until now, examination which improves the heat conductivity of the thickness direction by the heat processing conditions at the time of polyimide film preparation is made | formed (refer patent document 1). This is because the polyamic acid is partially imidized on the support to form a gel film, and then in the process of peeling from the support and performing the heat treatment, the solvent residual rate of the gel film and the conditions for gripping both ends by the fixture after peeling are determined. It has been found that the thermal conductivity in the thickness direction is increased by controlling the orientation in the plane direction by controlling. However, the film forming conditions are complicated, and a long time is required for the heat treatment, so that the production is not easy. Further, although there is a description that the polyimide resin may contain a filler in a range of less than 30% by weight, there is a limit in improving the thermal conductivity while maintaining the flexibility and good characteristics of the polyimide. .

  On the other hand, regarding a heat conductive polyimide film containing a heat conductive filler, Patent Document 2 discloses a polyimide film composite material in which a heat conductive filler is dispersed in a polyimide derived from an aromatic diamine having a benzoxazole structure. Yes. In the technique shown here, the polyimide resin used has good dispersibility with the thermally conductive filler, and has a linear expansion coefficient of −1 to 8 ppm / ° C. close to the linear expansion coefficient of the filler of 2 to 5 ppm / ° C. On the other hand, there is an advantage that stress concentration at the interface between the filler and the resin is less likely to occur. On the other hand, since the diamine terminal has a bent structure in the molecule compared to the rigid diamine used in the past, a film having a thickness of 50 μm or less is formed. When produced, the strength of the polyimide film, such as tear resistance, may be inferior.

  Generally, heat dissipation depends on the shape of the material in addition to the thermal conductivity. In particular, in a low heat conductive material such as a polyimide resin, a thin film is easier to transfer heat than a block molded body. However, when a thermally conductive filler is filled in the resin for improving the thermal conductivity, the interface between the resin and the filler increases, and the resin becomes brittle. Further, when the thickness of the material is reduced and the filler is highly filled in order to obtain a highly heat conductive flexible material, the polyimide layer becomes more brittle due to a decrease in mechanical strength accompanying the filler filling. Therefore, it has been desired to develop a laminate for a heat conductive flexible substrate or a heat conductive polyimide film having a polyimide layer having a large strength such as sufficient tear resistance even in a thin film.

JP 2006-274040 A JP 2005-162878 A

As mentioned above, it has heat conduction characteristics above a certain level, is excellent in heat resistance and the dimensional stability indicated by the thermal expansion coefficient of polyimide resin, and is used in flexible circuit boards that are used repeatedly Therefore, development of a material that is difficult to break has been desired.
Therefore, the present invention is effectively used for a base film such as a flexible circuit board or a heat radiating board, which has excellent heat radiation characteristics, heat resistance, dimensional stability, and has a high tear propagation resistance, and thus has a high strength even when used as an insulating layer. An object of the present invention is to provide a flexible heat conductive polyimide film. Another object of the present invention is to provide a laminate for a heat conductive flexible substrate that has an insulating layer having such characteristics and is suitable for similar applications.

  As a result of repeated studies to solve the above problems, the present inventors have used a polyimide having a specific structure as a polyimide constituting a polyimide layer in which a thermally conductive filler is dispersed. The present inventors have found that the above-mentioned problems can be solved by containing them in a specific range, and have completed the present invention.

（式中、Ａｒ_１は芳香環を１個以上有する４価の有機基であり、Ｒは炭素数１〜６の低級アルキル基、低級アルコキシ基、フェニル基、フェノキシ基又はハロゲンである。） That is, the present invention provides a laminate for a flexible substrate having a metal layer on one or both sides of an insulating layer having at least one filler-containing polyimide resin layer in which a thermally conductive filler is dispersed in a polyimide resin. The resin layer has a heat conductive filler content of 25 to 55 wt%, and the polyimide resin in the filler-containing polyimide resin layer contains 30 mol% or more of a structural unit represented by the following general formula (1). This is a flexible substrate laminate.

(In the formula, Ar ₁ is a tetravalent organic group having one or more aromatic rings, and R is a lower alkyl group having 1 to 6 carbon atoms, a lower alkoxy group, a phenyl group, a phenoxy group, or a halogen.)

  Moreover, the present invention provides a polyimide film having at least one filler-containing polyimide resin layer in which a thermally conductive filler is dispersed in a polyimide resin, wherein the polyimide resin has 30 structural units represented by the general formula (1). It is a heat conductive polyimide film characterized by containing at least mol%, having a heat conductive filler content of 25 to 55 wt% and having flexibility.

  The laminate for a flexible substrate and the heat conductive polyimide film of the present invention have excellent heat conduction characteristics, excellent dimensional stability and heat resistance, and have high resistance to tear propagation even when highly filled with a heat conductive filler. Since it has good tear resistance and flexibility, it is also flexible, so it can be used for insulation layers of flexible circuit boards used in bent parts of mobile phones, etc. Suitable for substrate insulation layer.

The present invention is described in detail below.
The laminated body for flexible substrates of this invention consists of a metal layer which has an insulating layer and its one or both surfaces. The insulating layer is composed of a polyimide resin, and at least one layer is a filler-containing polyimide resin layer in which a thermally conductive filler is dispersed in the polyimide resin. An insulating layer may consist only of a filler containing polyimide resin layer, and may have a polyimide resin layer which does not contain a filler. When it has a polyimide resin layer which does not contain a filler, the thickness is in the range of 1/100 to 1/2 of the filler-containing polyimide resin layer, preferably in the range of 1/20 to 1/3. In the case of having a polyimide resin layer containing no filler, if the polyimide resin layer is in contact with the metal layer, the adhesion between the metal layer and the insulating layer is improved.

The polyimide resin of the filler-containing polyimide resin layer in the laminate for a flexible substrate and the thermally conductive polyimide film (hereinafter also simply referred to as a polyimide film) of the present invention contains 30 mol% or more of the structural unit represented by the general formula (1). The polyimide resin contained is a constituent element, and the polyimide resin mainly serves as a matrix for dispersing the heat conductive filler described later. Ar ₁ represented by the general formula (1) is a tetravalent organic group having one or more aromatic rings, and can be said to be a residue generated from an aromatic tetracarboxylic dianhydride. Therefore, Ar ₁ is understood by describing the aromatic tetracarboxylic dianhydride used. The aromatic tetracarboxylic dianhydride used is preferably pyromellitic dianhydride, but other aromatic tetracarboxylic dianhydrides such as 3,3′4,4′-biphenyltetracarboxylic acid in a proportion of 30 mol% or less. Things can be included. R is a lower alkyl group having 1 to 6 carbon atoms, a lower alkoxy group, a phenyl group, a phenoxy group, or a halogen. Preferably, they are a methyl group, an ethyl group, a methoxy group or an ethoxy group.

  As a polyimide resin of the filler-containing polyimide resin layer of the present invention, any one of the structural units represented by the following general formulas (3) and (4) that contains a structural unit represented by the following general formula (2): One or both are preferably contained within a certain range.

In the general formula (2), R has the same meaning as R in the general formula (1). In the general formula (3), Ar ₂ represents at least one divalent aromatic group selected from the following formulas (a) and (b), and Ar ₄ is selected from the following formulas (c) and (d) And at least one kind of divalent aromatic group to be produced. In the general formula (4), Ar ₃ represents a divalent residue obtained by removing an amino group from at least one diamine selected from 3,4′-diaminodiphenyl ether and 4,4′-diaminodiphenyl ether.

  In the general formulas (2), (3), and (4), l, m, and n represent the molar ratio, and when the polyimide is composed of the structural units represented by the general formulas (2) and (3), l is preferably a number in the range of 0.3 to 0.9 and m is in the range of 0.1 to 0.7, in particular, l is 0.6 to 0.9, and m is 0.4 to 0.7. When the polyimide is composed of structural units represented by the general formulas (2), (3) and (4), l is 0.3 to 0.9, m Is preferably a number in the range of 0.09 to 0.5, n is in the range of 0.01 to 0.2, particularly l is 0.6 to 0.9, m is 0.09 to 0.3, n is preferably a number in the range of 0.01 to 0.2. Furthermore, when the polyimide is composed of structural units represented by the general formulas (2) and (4), l is a number in the range of 0.3 to 0.9 and n is in the range of 0.1 to 0.7. It is good.

  The structural unit of the above general formula (2) mainly improves the properties such as low thermal expansion and high heat resistance, and the structural unit of the general formula (3) mainly improves the properties such as toughness and adhesiveness. However, it is not exact because of synergistic effects and molecular weight effects. However, in order to increase toughness and the like, it is usually effective to increase the structural unit of the general formula (3). The structural unit of the general formula (4) is effective for adjusting the balance between low thermal expansion and toughness.

Preferable examples of the structural unit represented by the general formula (2) include a structural unit represented by the following formula (5).

In General Formula (3), Ar ₂ represents a divalent aromatic group represented by Formula (a) or (b), and Ar ₄ represents a divalent group represented by (c) or (d). Indicates an aromatic group. Preferred examples of Ar ₂ include divalent aromatic groups represented by the following formulas (e), (f) and (g).

In the general formula (4), Ar ₃ represents a residue of 3,4′-diaminodiphenyl ether or 4,4′-diaminodiphenyl ether (group remaining after removing the amino group: 3,4′-diyl-diphenyl ether or 4, 4'-diyl-diphenyl ether).

  The polyimide resin of the filler-containing polyimide resin layer is preferably obtained by imidizing polyamic acid which is a polyimide precursor having a weight average molecular weight in the range of 100,000 to 800,000, more preferably 150,000 to 800,000. If the value of the weight average molecular weight is less than 100,000, the tear propagation resistance of the film tends to be weak, and if it exceeds 800,000, it may be difficult to produce a uniform film. The weight average molecular weight can be determined in terms of polystyrene by the GPC method. In addition, since the weight average molecular weight of the polyimide resin obtained by imidizing the polyamic acid is substantially equal to that measured in the polyamic acid state, the weight average molecular weight of the polyamic acid can be regarded as the weight average molecular weight of the polyimide resin. it can.

  The filler-containing polyimide resin layer contains a thermally conductive filler at a constant rate. The thermally conductive filler is preferably a highly thermally conductive filler, and specifically includes aluminum, copper, nickel, silica, diamond, alumina, magnesia, beryllia, boron nitride, aluminum nitride, silicon nitride, and silicon carbide. The filler shape is not particularly limited, such as a spherical or plate-like material, or a needle shape. Among these, at least one spherical filler selected from silica, alumina, aluminum nitride, boron nitride, silicon nitride and magnesia, or at least one plate filler of boron nitride and aluminum oxide is preferable.

When a spherical filler is used as the thermally conductive filler in the polyimide resin layer, the average particle diameter is preferably in the range of 0.3 to 15 μm, and more preferably in the range of 1 to 8 μm. If the average particle diameter of the heat conductive filler is less than 0.3 μm, the heat conduction inside each filler is reduced, and as a result, the heat conductivity of the polyimide resin layer is not improved. In addition, the particles tend to agglomerate, making it difficult to uniformly disperse the particles. On the other hand, if it exceeds 15 μm, the possible filling rate of the polyimide resin layer is lowered, and the polyimide film tends to be brittle due to the influence of the interface between the filler and the resin. In the case of using a plate-like filler in the thermally conductive filler has an average long diameter _{D L} is preferably in the range of 0.1-15, more preferably in the range of 0.5 to 10 [mu] m. Optimum flake-like filler has an average long diameter _{D L} is boron nitride 1 to 9 m. When the average long diameter D _L is less than 0.1 [mu] m, low thermal conductivity, thermal expansion coefficient becomes large, plate-like effect is reduced. If the thickness exceeds 15 μm, it is difficult to orient at the time of film formation. Here, the average long diameter D _L means the average value of the longitudinal diameter of the plate-like filler. In the present invention, when referred to as a plate-like filler, the filler is a plate-like or flake-like filler, and the average thickness is sufficiently smaller than the average major axis or minor axis of the surface portion (preferably 1/2 or less). Say. The average diameter means the median diameter, and the mode diameter is preferably one in the above range, and this is the same for the spherical filler.

  The content rate of the heat conductive filler in a filler containing polyimide resin layer is the range of 25-55 wt%. A range of 27 to 50 wt% is preferable, and a range of 30 to 40 wt% is particularly preferable. If the content ratio of the heat conductive filler is less than 25 wt%, the heat dissipation characteristics when the heat dissipation board or the flexible circuit board is used are not sufficient, and if it exceeds 55 wt%, the bendability is significantly reduced. Further, the strength of the polyimide resin layer also decreases.

In the insulating layer and the heat conductive polyimide film of the laminate for a flexible substrate of the present invention, the preferred thickness range of the polyimide film is 5 to 50 μm, more preferably 5 to 35 μm, and particularly preferably 10 to 10 μm. 30 μm. In the present invention, when the thickness of the insulating layer (polyimide film) is in the range of 5 to 50 μm, the tear propagation resistance value (mN) is Y, and the thickness (μm) of the polyimide film is X, the formula (I )
Z = Y / X ^1.5 (I)
Flexible with excellent bendability and tear resistance, which makes it difficult to break and deform, by using a polyimide film with a Z value of 0.5 or more, preferably 0.7 to 2.5 calculated in It can be set as the laminated body for substrates, or a polyimide film.
In the formula (I), Y is the tear propagation resistance value (mN), and X is the thickness (μm) of the insulating layer (polyimide film). The tear propagation resistance is measured by the method described in the examples.

In the present invention, the thermal expansion coefficient of the insulating layer (polyimide film) is preferably 30 × 10 ⁻⁶ / K or less, and more preferably 25 × 10 ⁻⁶ / K or less, so that the flexible wiring When applied to a substrate or the like, deformation such as curling can be suppressed.

  Furthermore, by setting the glass transition temperature of the insulating layer (polyimide film) to 310 ° C. or higher, preferably 310 to 500 ° C., an insulating layer for a flexible circuit board having excellent heat resistance and heat dissipation can be obtained. it can.

  The method for producing the laminate for a flexible substrate or the heat conductive polyimide film of the present invention is not particularly limited, and a known method can be adopted. If the typical example of the laminated body for flexible substrates is shown, metal foil, such as copper foil which is a metal layer, will be used for the resin solution of the polyamic acid which is a polyimide precursor resin containing the heat conductive filler which is a raw material of an insulating layer. The film is directly casted on the surface, and the solvent is removed to some extent at a temperature of 150 ° C. or less, and then further heat treatment is performed at 100 to 450 ° C., preferably 300 to 450 ° C. for 5 to 40 minutes for imidization. Is generally used to form an insulating layer made of a polyimide resin containing a thermally conductive filler on the metal layer. As will be described later, when the insulating layer is composed of two or more polyimide layers, after applying and drying the first polyamic acid resin solution, applying and drying the second polyamic acid resin solution, and so on. Then, after applying and drying the resin solution of the third or lower polyamic acid sequentially, it is preferable to perform imidization by collectively performing a heat treatment at a temperature range of 300 to 450 ° C. for about 5 to 40 minutes. If the temperature of the heat treatment is lower than 100 ° C, the dehydration ring-closing reaction of polyimide does not proceed sufficiently. Conversely, if it exceeds 450 ° C, the polyimide resin layer and the copper foil may be deteriorated due to oxidation or the like.

  Moreover, as a manufacturing example of a heat conductive polyimide film, after manufacturing the laminated body of metal foil, such as copper foil, and a polyimide resin like the said laminated body for flexible substrates, metal foil is removed by peeling or an etching. , A method of forming a polyimide film, and a resin solution of a polyamic acid containing a heat conductive filler as a raw material for an insulating layer is cast on an arbitrary support substrate, cast into a film, and dried on a support by heating A method of forming a gel film having a self-supporting property by peeling off from the support and further heat-treating at a high temperature to form an imidized film is exemplified. In order to make a laminate for a flexible substrate using this polyimide film as an insulating layer, a method of heat-pressing a metal foil directly or via an arbitrary adhesive on a polyimide film, or a method of forming a metal layer by metal vapor deposition or the like Is common.

  The polyamic acid resin solution containing the heat conductive filler used in the formation of the insulating layer may be blended directly with the polyamic acid resin solution. However, considering the filler dispersibility, the raw material ( A heat conductive filler may be added in advance to the reaction solvent in which one of the acid dianhydride component or the diamine component) is added, and the polymerization may be allowed to proceed with stirring.

  The insulating layer and the polyimide film of the laminate for a flexible substrate may be composed of a single layer or a plurality of layers. However, the dimensional stability and the copper foil when a flexible copper-clad laminate is used. In order to improve the adhesive strength between the insulating layer and the insulating layer, a plurality of layers can be used. Here, when making an insulating layer into multiple layers, it is good to make all the layers contain a heat conductive filler and to make it a filler containing polyimide resin layer. In addition, although this invention does not exclude using the adhesive agent for adhere | attaching a filler containing polyimide resin layer and metal foil, it is an adhesive layer in the laminated body for double-sided flexible substrates which has a metal layer on both surfaces of an insulating layer. Is preferably in the range of less than 30% of the thickness of the entire insulating layer, more preferably less than 20%. In a laminate for a single-sided flexible substrate having a metal layer only on one side of the insulating layer, the total insulating layer The range of less than 15% of the thickness is preferable, and less than 10% is more preferable. And since an adhesive bond layer comprises a part of insulating layer, it is preferable that it is a polyimide resin layer.

  A polyamic acid containing a filler is prepared by previously introducing a thermally conductive filler into a solvent such as N, N-dimethylacetamide (DMAc) used for the reaction of the polyimide, and in a state where the thermally conductive filler is dispersed under stirring. It can be obtained by sequentially adding a diamine and an acid anhydride as a polyimide raw material and advancing the synthesis of the polyimide. Here, the stirring is preferably performed simultaneously with ultrasonic irradiation. Moreover, the addition order of a diamine and an acid anhydride can be suitably selected suitably. In addition, as needed, it is good to remove the aggregated filler and the coarse particle-shaped foreign material which were produced using the strainer or the filtration apparatus after the preparation process or preparation of the polyamic acid containing the filler. By these operations, a heat conductive polyimide film in which the heat conductive filler is uniformly dispersed in the polyimide resin can be obtained.

  The polyamic acid used for the thermally conductive polyimide layer should be produced by a known method of polymerizing in an organic polar solvent using substantially equimolar amounts of aromatic diamine and aromatic tetracarboxylic dianhydride. Can do. In the production example of the polyamic acid containing the filler, an example in which the thermally conductive filler is dispersed in advance before the polymerization of the polyimide is shown. However, in the present invention, the production method is not limited, and the resin of the polyamic acid is used. You may employ | adopt the method of adding a heat conductive filler to a solution. A polyamic acid is obtained by dissolving an aromatic diamine in an organic polar solvent such as DMAc under a nitrogen stream, and then adding an aromatic tetracarboxylic dianhydride and reacting at room temperature for about 3 to 5 hours. The aromatic diamine and aromatic tetracarboxylic acid used as raw materials are understood from the explanation of the general formulas (2), (3) and (4), but specific examples include 2,2′-dimethyl as the diamine. There are benzidine (m-TB), 1,3-bis (4-aminophenoxy) benzene (TPE-R), 3,4'-diaminodiphenyl ether (3,4'-DAPE), etc. Examples of the anhydride include pyromellitic dianhydride (PMDA) and 3,3′4,4′-biphenyltetracarboxylic acid (BPDA).

  The application of the polyamic acid resin solution on the metal foil or the supporting substrate can be performed by a known method, for example, appropriately selected from a barcode method, a gravure coating method, a roll coating method, a die coating method, and the like. Can be adopted.

  The polyamic acid applied on the substrate is heat-treated for drying and imidization. Preferable drying conditions are that heat treatment is performed at a temperature of 150 ° C. or lower for 2 to 60 minutes to remove the solvent in the film, and preferable imidization conditions are usually about 130 to 360 ° C. for 2 to 120 minutes. It is preferable to heat treat to a certain extent.

EXAMPLES Hereinafter, the content of the present invention will be specifically described based on examples, but the present invention is not limited to these examples.
The abbreviations used in the examples represent the following compounds.
m-TB: 2,2′-dimethyl-4,4′-diaminobiphenyl (2,2′-dimethylbenzidine)
PDA: p-phenylenediamine TPE-R: 1,3-bis (4-aminophenoxy) benzene 3,4′-DAPE: 3,4′-diaminodiphenyl ether 4,4′-DAPE: 4,4′-diaminodiphenyl ether PMDA: pyromellitic dianhydride BPDA: 3,3′4,4′-biphenyltetracarboxylic acid DMAc: N, N-dimethylacetamide

The measuring methods of various physical properties in the examples are shown below. In addition, what was expressed as a polyimide film below refers to the polyimide film obtained by carrying out the etching removal of the copper foil of the laminated body which used copper foil as a support base.
[Measurement of tear propagation resistance]
A 63.5 mm × 50 mm test piece was prepared from the polyimide film, a 12.7 mm length cut was made in the test piece, and measurement was performed in accordance with ASTM D1922 using a light load tear tester manufactured by Toyo Seiki.

[Measurement of coefficient of thermal expansion (CTE)]
The polyimide film (3 mm × 15 mm) was subjected to a tensile test in a temperature range of 30 ° C. to 260 ° C. at a constant temperature increase rate while applying a 5.0 g load with a thermomechanical analysis (TMA) apparatus. The thermal expansion coefficient was measured from the amount of elongation of the polyimide film with respect to temperature.

[Glass transition temperature (Tg)]
When a polyimide film (10 mm × 22.6 mm) was heated from 20 ° C. to 500 ° C. at 5 ° C./min by dynamic viscoelasticity measurement (DMA), the dynamic viscoelasticity was measured, and the glass transition temperature Tg ( tan δ maximum value) was determined.

[Heat conductivity in plane direction (λxy)]
The polyimide resin film to be measured was cut into a size of 30 mm × 5 mm, and the thermal diffusivity in the direction of the thin film surface by the optical alternating current method, the specific heat by differential scanning calorimetry (DSC), and the density by the underwater substitution method were measured. Based on the above, the thermal conductivity in the plane direction was calculated.

[Thermal conductivity in the thickness direction (λz)]
A polyimide resin film to be measured is cut into a size of 30 mm × 30 mm, the thermal diffusivity in the thickness direction by the periodic heating method, the specific heat by the DSC, and the density by the underwater substitution method are measured, and based on these results. The thermal conductivity in the thickness direction was calculated.

[Folding resistance]
A polyimide film cut into a rectangle with a width of 5 mm and a length of 30 mm is made to have a shape with a radius of curvature of 3 mm by combining both ends in the length direction, and then the operation of returning to the original rectangle is repeated 100 times, It was investigated whether or not a tear occurred. The case where no change was observed in the appearance after 100 repetitive operations was marked with ◯, and the case where a tear occurred during the 100 repetitive operations was marked with x.

[Solder heat resistance]
Circuit processing is performed on the flexible substrate laminate in a predetermined shape, and the laminate is immersed in a 350 ° C. solder bath for 30 seconds. Those that did not bulge were marked as ◯, and those that did not bulge were marked as x.

[Copper foil peel strength (peel strength)]
The copper foil layer of the laminate was pattern-etched into a long rectangle having a width of 1.0 mm and a length of 180 mm, and a test piece was cut out to a width of 20 mm and a length of 200 mm so that the pattern was in the center, and IPC-TM-650. A 180 ° peel test was conducted according to 2.4.19.

Synthesis example 1
A separable flask equipped with a stirrer is immersed in a water bath of an ultrasonic device, and a spherical alumina filler (manufactured by Micron) having an average particle size of 3 μm and DMAc are added to the flask, and ultrasonic waves with an oscillation frequency of 28 kHz are applied in a nitrogen atmosphere. The mixture was stirred for 2 hours with irradiation at a stirring speed of 150 rpm. Next, as shown in Table 1, m-TB and TPE-R (molar ratio: 90/10) were added and dissolved as diamine components, and then the acid anhydride component was maintained while maintaining ultrasonic irradiation and stirring. PMDA and BPDA (molar ratio: 80/20) are added and a polymerization reaction is performed in a nitrogen atmosphere at room temperature for 3.5 hours, and the filler content is 40 wt% with respect to the total amount of polyamic acid and filler as resin components. An opaque white viscous polyamic acid solution A (viscosity: 26,100 cP) was obtained. The viscosity was measured at 25 ° C. with a cone plate viscometer (manufactured by Tokimec Co., Ltd.) equipped with a constant temperature water bath. The unit of the amount used in diamine, tetracarboxylic dianhydride, filler and DMAc in Table 1 is g. (Solvents are excluded in calculating the filler content. The same applies hereinafter.)

Synthesis example 2
The same procedure as in Synthesis Example 1 was performed except that m-TB, TPE-R, 3,4′-DAPE (molar ratio: 70/20/10) was used as the diamine component, and PMDA was used as the acid anhydride component.
The amount of each component used is shown in Table 1.

Synthesis example 3
The same procedure as in Synthesis Example 1 was performed except that 4,4′-DAPE was used as the diamine component and PMDA was used as the acid anhydride component. The amount of each component used is shown in Table 1.

Synthesis example 4
A polyamic acid D (viscosity 16,600 cP) was obtained by reacting a diamine having the same composition as in Synthesis Example 1 in Table 1 and an acid anhydride except that no alumina filler was added and no ultrasonic apparatus was used. That is, after adding DMAc and the diamine shown in Synthesis Example 1 in Table 1 to a separable flask equipped with a stirrer, the mixture was stirred and polymerized at room temperature for 3.5 hours in a nitrogen atmosphere.

Synthesis Examples 5 and 6
Polymerization was performed in the same manner as in Synthesis Example 1 in Table 1 except that the alumina filler content was changed to 20 wt% and 60 wt%, respectively, with respect to the total amount of polyamic acid and alumina filler, and polyamic acid E (viscosity: 30, 700 cP) and F (viscosity: 35,000 cP).

Examples 1 and 2
The obtained filler-containing polyamic acid solutions A and B were separately applied onto a copper foil having a thickness of 18 μm and an average surface roughness Rz of 0.7 μm so that the thickness after curing was about 25 μm, and 140 ° C. Less than 30 minutes, the solvent was removed, and heating was performed stepwise in a temperature range of 150 to 360 ° C. over 60 minutes to obtain a laminate for a flexible substrate. Next, after removing the copper foil layer of the laminate for flexible substrate by etching and leaving it for half a day at room temperature and a humidity of 30% or less, as shown in Table 2, tear propagation resistance, thermal expansion coefficient, glass transition temperature, plane direction and thickness The direction thermal conductivity and folding resistance were evaluated. The results are shown in Table 2.
In addition, the polyimide films A and B mean that they were obtained from the corresponding polyamic acids A and B.

Comparative Examples 1-4
Except having used C-F as a polyamic acid, it carried out similarly to Example 1, created polyimide film C-F, and measured the physical property. Table 2 shows the characteristics of the polyimide films C to F.

Synthesis example 7
Under a nitrogen stream, m-TB and 4,4′-DAPE, which are diamine components, were dissolved in 170 g of solvent DMAc with stirring in a 300 ml separable flask at the mixing ratio shown in Table 3, and then acid PMDA was added as an anhydride component. Thereafter, the solution was stirred at room temperature for 3 hours to carry out a polymerization reaction to obtain a brown-brown viscous polyamic acid solution (P1) having a solid content concentration of 15 wt%.

Synthesis Examples 8 to 11
Similarly to the synthesis example 7, it superposed | polymerized by the compounding ratio of Table 1, and the brown-colored viscous polyamic-acid solution (P2-P5) was obtained.

Example 3
200 parts by weight of a polyamic acid solution (P1) having a solid content concentration of 15 wt% synthesized in Synthesis Example 7 and boron nitride obtained by removing particles of 30 μm or more with a classifier (trade name: HGPE, manufactured by Electrochemical Co., Ltd.) A varnish G containing a heat conductive filler was obtained by mixing 30 parts by weight of a scale shape and an average major axis of 5 μm) with a centrifugal stirrer until uniform. This varnish was applied so that the thickness after curing was 20 μm, and dried by heating at 130 ° C. to remove the solvent. Then, in a temperature range of 130 to 360 ° C., the temperature is increased and heated stepwise over 30 minutes to form an insulating layer in which a thermally conductive filler is dispersed in a polyimide resin on a 12 μm thick electrolytic copper foil, A laminate for a flexible substrate was produced. The weight fraction of boron nitride in this insulating layer is 30 wt%.

  In order to evaluate the characteristics of the insulating layer in the obtained laminate for flexible substrate, the copper foil was removed by etching to produce an insulating film (G), and the tear propagation resistance, CTE, glass transition temperature, and surface direction thermal conductivity were measured. Each was evaluated. The results are shown in Table 4.

Examples 4 and 5
A flexible substrate laminate and an insulating film were obtained in the same manner as in Example 3 except that boron nitride was changed to 40 wt% and 50 wt%, respectively. Table 4 shows the evaluation results of the insulating film H and the insulating film I obtained from the flexible substrate laminate produced in Example 4.

Example 6
Except having used polyamic acid P2, it carried out similarly to Example 3, and obtained the laminated body and insulating film for flexible substrates. Table 4 shows the evaluation results of the insulating film J obtained from the flexible substrate laminate produced in Example 6.

Example 7
A flexible substrate laminate and an insulating film were obtained in the same manner as in Example 6 except that the boron nitride content was 25 wt%. Table 7 shows the evaluation results of the insulating film Q obtained from the laminate for a flexible substrate prepared in Example 7.

Comparative Example 5
Except not containing a filler, it carried out similarly to Example 3, and obtained the laminated body and insulating film for flexible substrates. Table 4 shows the evaluation results of the insulating film K obtained from the flexible substrate laminate produced in Comparative Example 5.

Comparative Examples 6 and 7
A flexible substrate laminate and an insulating film were obtained in the same manner as in Example 3 except that the boron nitride content was 15 wt% in Comparative Example 6 and 60 wt% in Comparative Example 7. Table 4 shows the evaluation results of the insulating film L obtained from the flexible substrate laminate produced in Comparative Example 6 and the insulating film M obtained from the flexible substrate laminate produced in Comparative Example 7. In addition, the insulating film M created in Comparative Example 7 was so brittle that the film characteristics could not be evaluated.

Comparative Example 8
Except having used polyamic acid P3, it carried out similarly to Example 3, and obtained the laminated body and insulating film for flexible substrates. Table 4 shows the evaluation results of the insulating film N obtained from the flexible substrate laminate produced in Comparative Example 8.

Example 8
200 parts by weight of polyamic acid P4 was used, and the filler was 40 parts by weight of alumina (manufactured by Sumitomo Chemical Co., Ltd., trade name: AA-3 (average particle size 3 μm), 20 parts by weight, AA-03 (average particle size 0. Varnish O was obtained in the same manner as in Example 3 except that 3 μm) and 20 parts by weight) were used. A film was formed in the same manner as in Example 3 to obtain a 26 μm film O. When the film properties were evaluated, the tear propagation resistance was 3.0 kN / m, the Z value was 0.59, the CTE was 29 ppm / K, the Tg was 381 ° C., the thermal conductivity in the plane direction was 1.14 W / mK, and the heat in the thickness direction. The conductivity was 0.45 W / mK.

Example 9
A polyamic acid (P5) containing no filler was applied onto the copper foil so that the thickness after curing was 2 μm, and dried by heating at 130 ° C. to remove the solvent. Next, varnish H containing a thermally conductive filler was applied thereon so that the thickness after curing would be 21 μm, and dried by heating at 130 ° C. to remove the solvent. Further, a polyamic acid solution (P5) containing no filler is applied thereon so that the thickness after curing is 2 μm, and dried by heating at 130 ° C. to remove the solvent, and then at a temperature of 130 to 360 ° C. Within the range, the temperature was raised and heated stepwise over 30 minutes to produce a laminate for a flexible substrate having an insulating layer composed of three polyimide layers on a copper foil. The characteristics of the laminate for a flexible substrate were evaluated. As shown in Table 5, the solder heat resistance was 400 ° C. and the peel strength was 1.0 kN / m.

Example 10
The same procedure as in Example 9 was performed except that varnish J was used instead of varnish H. The results are shown in Table 5.

Example 11
The same procedure as in Example 9 was performed except that varnish O was used instead of varnish H. The results are shown in Table 5.

  The laminate for a flexible substrate and the highly thermal conductive polyimide film of the present invention have flexibility by containing a specific polyimide resin in the insulating layer and setting the content of the thermal conductive filler in the range of 25 to 55 wt%. In addition, it has excellent heat dissipation characteristics, heat resistance and dimensional stability, and has excellent industrial applicability with excellent tear resistance even in a thin film. Therefore, it is useful as a heat-dissipating sheet, heat-dissipating substrate, adhesive film, etc. for various equipment. For example, OA equipment such as printing / copying devices, small communication equipment for portable / mobile devices, TV, video, DVD, refrigerator, lighting, etc. In addition to being ideal for home appliance parts, automotive parts and optical devices that require heat dissipation, heat exchangers, and hard disk drive parts as information recording materials (hard disk hubs, hard disk substrates, magnetic heads, suspensions, actuators, etc.) In addition, the present invention can be applied to semiconductor devices such as LSI packages, sensors, LED lamps, light emitting diode substrates, connectors, coil bobbins, capacitors, speakers, electromagnetic wave shielding materials, and the like.

Claims (12)

In a laminate for a flexible substrate having a metal layer on one or both sides of an insulating layer having at least one filler-containing polyimide resin layer in which a thermally conductive filler is dispersed in a polyimide resin, the thermal conductivity of the filler-containing polyimide resin layer The filler content is in the range of 25 to 55 wt%, and the polyimide resin in the filler-containing polyimide resin layer contains 30 mol% or more of a structural unit represented by the following general formula (1). Laminate for substrate.

(In the formula, Ar ₁ is a tetravalent organic group having one or more aromatic rings, and R is a lower alkyl group having 1 to 6 carbon atoms, a lower alkoxy group, a phenyl group, a phenoxy group, or a halogen.) When the insulating layer has a thickness in the range of 5 to 50 μm, the tear propagation resistance value (mN) is Y, and the polyimide film thickness (μm) is X,
Formula (I)
Z = Y / X ^1.5 (I)
The laminate for a flexible substrate according to claim 1, wherein the value of Z calculated by (1) is 0.5 or more.   The laminate for a flexible substrate according to claim 1 or 2, wherein the thermal expansion coefficient of the insulating layer is 30 ppm / K or less.   The heat conductive filler is at least one spherical filler selected from silica, alumina, aluminum nitride, boron nitride, silicon nitride, and magnesia, and has an average particle diameter in the range of 0.3 to 15 µm. The laminated body for flexible substrates as described in any one of the above. Thermally conductive filler is boron nitride, a plate-like filler is at least one or more of aluminum oxide, the average major axis D _L is as defined in any one of claims 1 to 3 in the range of 0.1~15μm Laminated body for flexible substrates.   The thermal conductivity in the surface direction in the insulating layer is 1 W / mK or more, and the thermal conductivity in the thickness direction in the insulating layer is 0.4 W / mK or more. The laminated body for flexible substrates of description. In a polyimide film having at least one filler-containing polyimide resin layer in which a thermally conductive filler is dispersed in a polyimide resin, the polyimide resin contains 30 mol% or more of a structural unit represented by the following general formula (1). A thermally conductive polyimide film, wherein the content of the thermally conductive filler is in the range of 25 to 55 wt% and has flexibility.

(In the formula, Ar ₁ is a tetravalent organic group having one or more aromatic rings, and R is a lower alkyl group having 1 to 6 carbon atoms, a lower alkoxy group, a phenyl group, a phenoxy group, or a halogen.) When the thickness of the polyimide film is in the range of 5 to 50 μm, the tear propagation resistance value (mN) is Y, and the thickness (μm) of the polyimide film is X,
Formula (I)
Z = Y / X ^1.5 (I)
The thermally conductive polyimide film according to claim 7, wherein the value of Z calculated by the formula is 0.5 or more.   The thermally conductive polyimide film according to claim 7 or 8, wherein the thermal expansion coefficient of the polyimide film is 30 ppm / K or less.   The thermally conductive filler is at least one spherical filler selected from silica, alumina, aluminum nitride, boron nitride, silicon nitride, and magnesia, and has an average particle diameter in the range of 0.3 to 15 µm. The heat conductive polyimide film as described in any one of the above. Thermally conductive filler is boron nitride, a plate-like filler is at least one or more of aluminum oxide, the average major axis D _L is as defined in any one of claims 7-9 is in the range of 0.1~15μm Thermally conductive polyimide film.   The thermal conductivity in the surface direction in the polyimide film is 1 W / mK or more, and the thermal conductivity in the thickness direction in the polyimide film is 0.4 W / mK or more. The heat conductive polyimide film as described.