JP2007197715A - Heat resistant resin composition and print wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat resistant resin composition able to present a material having a relatively low linear expansion coefficient and expressing excellent mechanical characteristics and the like. <P>SOLUTION: The heat resistant resin composition comprises (1) a polyarylketone-based resin, (2) a polyetherimide-based resin and (3) at least one species of filler selected from fine talc particles and fine fired talc particles having 0.05-1μm number average particle size. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a heat resistant resin composition mainly used for producing printed wiring boards and the like. Furthermore, the present invention relates to a printed wiring board obtained from the composition.

  Various materials are known for printed wiring boards. Currently, copper foil is laminated on one or both sides of an insulating film base material, and the copper foil is etched to form a circuit pattern. So-called copper-clad laminates are used in electrical / electronic equipment, communication equipment, and automotive parts. Etc. are widely used.

  Conventionally, as these insulating film substrates, for example, paper, glass cloth, glass nonwoven fabric, glass mat or the like impregnated with phenol resin, epoxy resin or the like is known. However, these rigid insulated wiring boards have problems such as hygroscopicity and cannot meet the demand for higher performance. In addition, a rigid wiring board obtained by impregnating a glass cloth or a glass nonwoven fabric with an epoxy resin can maintain desired physical properties in a well-balanced manner, but cannot cope with downsizing, high frequency, and the like.

  As a copper-clad laminate other than the above, there is a film for flexible printed wiring boards. This film is obtained by extruding a thermoplastic resin such as polyester, polyimide, polysulfone or the like. The thermoplastic resin is formed into a film by molding a composition formed by blending an appropriate inorganic filler as required.

  Since these thermoplastic resin compositions have good processability, they can be downsized, can be multilayered, and those with a low dielectric constant can also be applied to high frequency countermeasures. Various research and development has been actively conducted.

  However, since a thermoplastic resin has insufficient heat resistance as compared with a thermosetting resin, a film made of a thermoplastic resin composition lacks long-term durability and reliability.

  In order to eliminate such drawbacks, a film formed by molding a resin composition containing a mixed resin of polyetherimide resin and polyetheretherketone resin and an inorganic filler such as talc, silica powder, mica, etc. is proposed. (Patent Document 1). Polyetheretherketone is an engineering plastic generally excellent in heat resistance and has a low coefficient of linear expansion. For this reason, the said film mix | blends a specific amount of inorganic fillers, adjusts the linear expansion coefficient of a film to the same grade as copper foil, and the curl which arises in a film when laminating | stacking copper foil is prevented.

  However, when an inorganic filler is blended and the linear expansion coefficient is adjusted to the same level as that of the copper foil, on the other hand, the physical properties such as the elongation property and the deflection property of the film and the durability are lowered, and it is high over a long period of time. It becomes impossible to provide a reliable printed wiring film.

  Patent Document 2 and Patent Document 3 include a resin containing a polyetherketone resin such as polyetheretherketone and a polyetherimide resin, and an inorganic filler having an average major axis of 1 μm to 50 μm such as boron nitride. A film comprising the composition is described.

However, in this film, it is very difficult to adjust the linear expansion coefficient to the same level as that of the copper foil, and thus the curling cannot be prevented. In addition, polyetheretherketone is slightly inferior in bondability with copper foil compared to other thermoplastic resins, and thus is improved in bondability by using polyetherimide. Even in combination, the adhesive processability is not sufficient, and therefore it cannot sufficiently cope with the miniaturization of the printed wiring board.
Japanese Patent Laid-Open No. 62-149436 (Claims 1 and 2) JP-A-3-20354 (Claim 1) JP 2003-26914 A (Claim 1)

  Accordingly, a main object of the present invention is to provide a heat-resistant resin composition that can provide a material having a relatively low linear expansion coefficient and exhibiting excellent mechanical properties and the like.

  The present invention also provides a printed wiring board having substantially the same linear expansion coefficient as that of the conductive layer, particularly a flexible printed wiring board having substantially the same linear expansion coefficient as that of the conductive layer and in which curling is effectively suppressed. Objective.

  As a result of intensive studies to solve the above problems, the present inventor has found that a resin composition having a specific composition can achieve the above object, and has completed the present invention.

That is, the present invention relates to the following heat-resistant resin composition and printed wiring board.
1. 1) a polyaryl ketone resin, 2) a polyetherimide resin, and 3) a heat-resisting material containing at least one filler selected from fine talc particles having a number average particle diameter of 0.05 μm or more and 1 μm or less and finely fired talc particles. Resin composition.
2. Item 2. The heat-resistant resin composition according to Item 1, wherein the polyaryl ketone-based resin is at least one selected from polyether ketone, polyether ether ketone, polyether ketone ketone, and polyether ether ketone ketone.
3. Item 3. The heat-resistant resin composition according to Item 1 or 2, wherein the filler has a number average particle size of 0.05 μm or more and less than 1 μm, and at least 50% by weight has a particle size of 0.1 μm to 0.9 μm.
4). Item 3. The heat-resistant resin composition according to Item 1 or 2, wherein the filler has a number average particle size of 0.05 μm or more and less than 1 μm, and at least 50% by weight has a particle size of 0.1 μm to 0.4 μm.
5). Item 5. The heat resistant resin composition according to any one of Items 1 to 4, wherein the content of the polyaryl ketone-based resin is 30 to 50% by weight.
6). Item 6. The heat-resistant resin composition according to any one of Items 1 to 5, wherein the content of the polyetherimide resin is 20 to 40% by weight.
7). Item 7. The heat-resistant resin composition according to any one of Items 1 to 6, wherein the polyaryl ketone resin is contained in an amount of 30 to 70% by weight in a total of 100% by weight of the polyaryl ketone resin and the polyetherimide resin.
8). Item 8. The heat-resistant resin composition according to any one of Items 1 to 7, wherein the filler content is 20 to 40% by weight.
9. The filler is talc fine powder having a median diameter D50 of 0.1 to 2 μm by a laser diffraction / scattering method,
The talc fine powder obtained by dispersing the talc fine powder in an atmospheric pressure at a relative humidity of 70% and a temperature of 25 ° C. for one month and then dispersing the talc fine powder A with ultrasonic waves having an oscillation frequency of 45 kHz and a rated output of 100 W for 1 minute. and the median diameter D50 _{45 kHz} of the powder B, a further said talc said median diameter D50 _{19.5 kHz} fine powder B the oscillation frequency 19.5kHz- rated output 300W ultrasound by 3 minutes dispersion obtained was talc fine powder C The heat resistant resin composition according to any one of Items 1 to 8, wherein the ratio [D50 _{19.5 kHz} / D50 _{45 kHz} ] is 0.88 or more.
10. Item 10. The heat-resistant resin composition according to Item 9, wherein the talc fine powder has an aspect ratio of 15 or more.
11. Item 11. The heat-resistant resin composition according to Item 9 or 10, wherein the bulk specific gravity of the talc fine powder is 0.12 or less.
12 The printed wiring board containing the film formed with the heat resistant resin composition in any one of said claim | item 1 -11.
13. Item 13. The printed wiring board according to Item 12, wherein a conductor layer is further formed on the film.
14 Item 14. The printed wiring board according to Item 13, wherein the conductor layer is formed of copper or a copper-based alloy.
15. Item 15. The printed wiring board according to Item 13 or 14, wherein the conductive layer is a layer formed by any one of 1) lamination of metal foil, 2) coating by plating, or 3) an inkjet method.
16. Item 16. The printed wiring board according to any one of Items 12 to 15, wherein the printed wiring board is flexible.
17. Item 17. The printed wiring board according to any one of Items 12 to 16, wherein the linear expansion coefficient at 165 to 175 ° C. is 3 × 10 ⁻⁵ / K or less.

  According to the heat-resistant resin composition of the present invention, the polyaryl ketone resin and the polyetherimide resin contain fine talc and / or baked fine talc having a predetermined number average particle diameter as fillers, so that a relatively low line In addition to achieving an expansion coefficient, it is possible to exhibit, for example, elongation characteristics, deflection characteristics, molding shrinkability, heat resistance, bondability with metal conductors, and the like. Furthermore, the composition of the present invention can also exhibit durability and high reliability over a long period of time.

  Such a composition of the present invention can be used for each application (electronic material, molding material, etc.) requiring the above-described characteristics. In particular, the composition of the present invention can be suitably used as a printed wiring board (in particular, a flexible printed wiring board). A printed wiring board made of the composition of the present invention has excellent elongation characteristics, deflection characteristics, molding shrinkability, and the like, as well as excellent heat resistance and adhesion workability with a metal conductor. Moreover, in the flexible printed wiring board, since the linear expansion coefficient can be set almost the same as that of the conductive layer, curling that occurs during the formation of the conductive layer can be effectively suppressed. That is, a flexible printed wiring board substantially free from curling can also be provided.

  Furthermore, the film for a printed wiring board of the present invention satisfies various characteristics required for the printed wiring board at a high level with a good balance. Specifically, the printed wiring board film of the present invention has, for example, good dimensional accuracy and soldering, is less likely to warp and twist, has a low coefficient of thermal expansion, and has an adhesive strength with copper foil and bending strength. It has high mechanical strength, excellent flexibility, and excellent electrical characteristics such as dielectric breakdown voltage, dielectric constant, dielectric loss tangent, and volume resistance.

  Thus, the printed wiring board of the present invention maintains high durability and reliability over a long period of time, and can be widely used in various fields including various electronic and electric devices.

1. Heat-resistant resin composition The heat-resistant resin composition of the present invention comprises 1) a polyarylketone resin, 2) a polyetherimide resin, and 3) fine talc particles and fine particles having a number average particle diameter of 0.05 μm to 1 μm. It is characterized by containing at least one filler selected from sintered talc particles.

As the polyaryl ketone-based resin, any known polyaryl ketone-based resin can be used, and is not particularly limited. For example, the polyaryl ketone-based resin includes one or more of the basic repeating units shown below. I can give you.

  Moreover, the polyaryl ketone-type resin of this invention may contain the 1 type (s) or 2 or more types of the repeating unit illustrated below.

  Specific examples of the polyaryl ketone resin include at least one of polyether ketone, polyether ether ketone, polyether ketone ketone, polyether ether ketone ketone, and the like.

  In the present invention, known or commercially available polyaryl ketone resins can be used. Commercially available products include, for example, polyether ether ketone and polyether ketone (both trade names: VICTREX) manufactured by Victrex, polyether ketone (trade name: Ultrapek) manufactured by BASF, polyether ketone manufactured by Amoco ( (Trade name: ADEL), polyaryl ketone resin (trade name: OXPEKK) manufactured by Oxford, and the like can be used.

  Among these polyaryl ketone resins, considering the heat resistance of the resulting heat-resistant resin composition, at least one of polyether ether ketone, polyether ketone ketone, and polyether ether ketone ketone is preferable. Ether ketone is particularly preferred.

  The content of the polyaryl ketone-based resin can be appropriately set according to the use of the composition of the present invention, the type of the polyaryl ketone-based resin to be used, etc., but usually 30 to 60% by weight, particularly 30 to 30% by weight in the composition of the present invention. 50% by weight is preferable.

Polyetherimide resin Any known polyetherimide resin can be used. For example, the polyetherimide which has 1 type, or 2 or more types of the repeating unit represented by following formula (1) or (2) can be mentioned.

[Wherein, R ₁ represents a divalent aromatic hydrocarbon residue or aliphatic hydrogen residue having 6 to 30 carbon atoms, and R ₂ represents 1) a divalent carbon number optionally substituted by a halogen atom. 6-20 aromatic hydrocarbon residue, 2) a cycloalkylene group having 3-20 carbon atoms, or 3) a group represented by the following formula (3) (wherein R ₃ is -S-, -O-, -CO -, - SO ₂ - or - indicates a _{(CH 2)} shows the _n wherein n is an integer of 1 to 5)... ]

An example of the organic group represented by R ₁ and R ₂ is as follows.

  Preferable specific examples of the polyetherimide resin include those containing the following repeating units.

  In the present invention, a known or commercially available polyetherimide resin can be used. Examples of commercially available products include polyetherimide (trade name: ULTEM) manufactured by General Electric Co., Ltd.

  The content of the polyetherimide resin can be appropriately set according to the use of the composition of the present invention, the kind of the polyetherimide resin to be used, etc., but usually 20 to 50% by weight, particularly 20 to 40% by weight in the composition of the present invention. % Is preferable.

  Further, the mixing ratio of the polyaryl ketone-based resin and the polyetherimide resin is not particularly limited and can be appropriately selected from a wide range, but these two kinds of resins have fine talc particles and / or fine baked talc having a specific shape. Considering the balance of heat resistance, mechanical properties (particularly linear expansion coefficient), adhesion processability with metal conductors, etc. of the heat-resistant resin composition containing particles, the total amount of these two kinds of resins is usually Thus, the polyether ketone resin may be blended in an amount of 30 to 70% by weight, preferably 35 to 65% by weight, and the balance may be polyether imide.

Filler In the present invention, at least one filler selected from fine talc particles having a number average particle diameter of 0.05 μm to 1 μm and fine fired talc particles is used.

  The number average particle size of the filler is usually 0.05 μm or more and 1 μm or less, preferably 0.05 μm or more and less than 1 μm, more preferably 0.05 μm or more and 0.9 μm or less, and most preferably 0.1 μm or more and 0.9 μm or less. To do. When the number average particle diameter is less than 0.05 μm, dispersion into the resin may be difficult. Further, when the number average particle diameter exceeds 1 μm, a desired linear expansion coefficient may not be obtained. In general, the particle size of commercially available talc exceeds 1 μm. For this reason, even if commercially available talc having such a particle size is contained in a mixed resin of a polyaryl ketone-based resin and a polyetherimide resin, a heat resistant resin composition having desired physical properties cannot be obtained. In addition, the number average particle diameter in this invention shows the value measured using the laser diffraction type particle size distribution measuring apparatus (Product name "SALD-2000J" (made by Shimadzu Corp.)).

  In addition, it is desirable that the filler in the present invention has a particle size of at least 50% by weight (50% diameter) of 0.1 μm to 0.9 μm (particularly 0.1 μm to 0.4 μm). By setting to the above range, desired physical properties can be effectively obtained. The 50% diameter measurement method is the same as the median diameter D50 measurement method by laser diffraction / scattering method described later.

  Furthermore, the filler of the present invention preferably has a Mohs hardness of 1 or more. By using such a filler, for example, it is possible to provide a heat-resistant resin composition or a printed wiring board film having good elongation characteristics and deflection characteristics.

The linear expansion coefficient of the filler of the present invention is preferably 5.0 × 10 ⁻⁵ / K or less. By using such a filler, even if the filler content varies, the linear expansion coefficient of the printed wiring board film can be easily adjusted to the same level as that of the conductor layer.

  The filler of the present invention is preferably chemically inert up to at least 400 ° C. and preferably retains the crystal structure. In the present invention, “chemically inert” means not only that it is difficult to chemically react, but also that the crystal structure is stable during the kneading (pellet granulation) or film extrusion process.

  In general, when a flaky inorganic filler containing a metal oxide as a main component is contained in a resin, the bending deflection characteristic and the tensile elongation characteristic are often lowered. This is presumed that the metal oxide attacks the main chain structure of the resin to cause deterioration. In contrast, when the fine talc particles and fine baked talc particles used in the present invention are used, there is no deterioration due to moisture in the air, and there is no adverse effect on physical properties such as bending deflection and tensile elongation characteristics of the printed wiring board film. .

  The filler in the present invention may be obtained by any method as long as it has the above particle size. For example, it can also be used as the filler by using commercially available talc and adjusting the particle size (pulverization), classification and the like according to known methods.

  When finely baked talc (steatite particles) is used as the filler, for example, after commercially talc particles are baked to 800 ° C. or higher in advance, the particle size is adjusted (pulverized), classified, etc., and used as the filler. You can also.

  The pulverization method applied in these methods is not limited. For example, the pulverization method can be suitably manufactured according to the “method for producing fine talc particles” (Japanese Patent Application No. 2005-301995) already filed by the present inventors. That is, it can also be prepared according to the following method.

1) The white powder talc particles represented by the chemical formula Mg ₃ Si ₄ O ₁₀ (OH) ₂ are charged into a wet or dry jet mill and / or a bead mill and pulverized to obtain a number average particle diameter of 0.05 μm to 1 μm. And a method of producing fine talc particles in which at least 50% by weight of the particles have a particle size in the range of 0.1 to 0.9 μm.

  2) The method according to item 1, wherein at least 50% by weight of the particles have a particle size in the range of 0.1 μm to 0.4 μm.

3) A dry-type jet mill entrains white powder talc particles represented by the chemical formula Mg ₃ Si ₄ O ₁₀ (OH) ₂ in concentric vortices formed by a high-speed air stream ejected from a nozzle, and is caused by the impact between talc particles in the previous period. Item 2. The method according to Item 1, wherein the method is a dry jet mill that is pulverized by impact force and frictional force.

4) The wet jet mill applies pressure to the liquid in which the white powder talc particles represented by the chemical formula Mg ₃ Si ₄ O ₁₀ (OH) ₂ are dispersed, and introduces it into the opposing collision chamber, ball collision chamber or single nozzle chamber and pulverizes it. Item 2. The method according to Item 1, wherein the method is a wet jet mill.

5) A white milled talc particle represented by the chemical formula Mg ₃ Si ₄ O ₁₀ (OH) ₂ and 1) microbeads or 2) microbeads and liquid in a gap formed between the rotating rotor and the stationary stator. Item 2. The method according to Item 1, wherein the method is a bead mill in which the mixture is introduced and pulverized.

6) white powder talc particles represented by the chemical formula _{Mg 3 Si 4 O 10 (OH} ) 2 is in a range of particle sizes 2Myuemu～6myuemu, production method according to the claim 1.

  These production methods can be appropriately carried out using a known pulverizer (jet mill, bead mill, etc.).

In the present invention, the following fine talc powder can also be suitably used as the filler. That is, a talc fine powder having a median diameter D50 of 0.1 to 2 μm by a laser diffraction / scattering method,
The talc fine powder obtained by dispersing the talc fine powder in an atmospheric pressure at a relative humidity of 70% and a temperature of 25 ° C. for one month and then dispersing the talc fine powder A with ultrasonic waves having an oscillation frequency of 45 kHz and a rated output of 100 W for 1 minute. and the median diameter D50 _{45 kHz} of the powder B, a further said talc said median diameter D50 _{19.5 kHz} fine powder B the oscillation frequency 19.5kHz- rated output 300W ultrasound by 3 minutes dispersion obtained was talc fine powder C A fine talc powder characterized in that the ratio [D50 _{19.5 kHz} / D50 _{45 kHz} ] is 0.88 or more can also be used.

<Median diameter D50>
The fine talc powder has a median diameter D50 by laser diffraction / scattering method of usually 0.1 to 2 μm, preferably 0.1 to 1.0 μm, more preferably 0.1 to 0.9 μm. The present invention exhibits excellent dispersion stability despite being composed of such fine particles. In particular, in the present invention, even nano-scale fine particles (nano fine particles) can effectively suppress aggregation and exhibit high dispersibility over a long period of time.

  The median diameter D50 indicates a value measured using a laser diffraction particle size distribution measuring apparatus (product name “SALD-2000J” manufactured by Shimadzu Corporation) (hereinafter the same).

<Ratio [D50 _{19.5 kHz} / D50 _{45 kHz} ]>
The greatest feature of the talc fine powder is that the ratio is 0.88 or more, preferably 0.90 or more, more preferably 0.92 or more. The ratio has a maximum value of 1, and the closer to 1, the higher the dispersion stability. That is, the higher the ratio value, the higher the dispersibility can be maintained over a long period.

Even if the conventional talc fine powder is refined by pulverization (even if it is just after pulverization), aggregation proceeds with the passage of time, and relatively large secondary particles are formed. In particular, almost all talc fine powders aggregate after being allowed to stand for 1 month at 70% relative humidity and 25 ° C. in atmospheric pressure. Such agglomerated particles are subjected to relatively weak ultrasonic treatment (first treatment). Next, the talc fine powder obtained by the first treatment is subjected to relatively strong ultrasonic treatment. In this case, in the particle group in which the aggregation has progressed, the aggregation is not sufficiently solved by the first treatment, and is further solved by the second treatment. For this reason, the particle size is reduced in the second treatment, and thus the ratio [D50 _{19.5 kHz} / D50 _{45 kHz} ] is reduced. That is, the ratio is less than 0.88. On the other hand, in the talc fine powder of the present invention, since the progress of aggregation is suppressed or prevented even after being left for 1 month at a relative humidity of 70% and a temperature of 25 ° C. in the atmospheric pressure, the first treatment is almost impossible. Therefore, even if the second treatment is performed, no significant decrease in particle size is observed. That is, the ratio is 0.88 or more.

In the measurement method of the above ratio, first, a fine powder (measurement powder) to be measured is left to stand for one month at a relative humidity of 70% and a temperature of 25 ° C. in an atmospheric pressure. The median diameter D50 of _{45 kHz} of talc fine powder B obtained by carrying out continuous dispersion for 1 minute with ultrasonic waves having an oscillation frequency of 45 kHz and a rated output of 100 W is measured for talc fine powder A immediately after being left for 1 month. Next, the talc fine powder B obtained by dispersing the talc fine powder B with ultrasonic waves having an oscillation frequency of 19.5 kHz and a rated output of 300 W for 3 minutes (repetition of 3-second oscillation and 2-second pause, irradiation for a total of 108 seconds) was obtained. The median diameter D50 _{19.5 kHz} is measured.

  The dispersion method may be performed under the conditions defined in the measurement method under the conditions of the first process and the second process. For example, a 100 ml glass beaker can be used as a container, 1% by weight of an anionic surfactant can be added to 50 ml of distilled water, and 0.1 g of talc fine powder can be added thereto, followed by ultrasonic dispersion.

  As the ultrasonic disperser, a known device may be used, and for example, a commercially available ultrasonic cleaner may be used. The ultrasonic conditions may be as described above. In particular, it is preferable in terms of reproducibility to intermittently perform ultrasonic dispersion such that the first treatment is changed to the second treatment.

<Aspect ratio>
The aspect ratio of the talc fine powder is preferably 15 or more, particularly preferably 17 or more. As can be seen from the aspect ratio, the talc fine powder has high flatness even if it is fine, and is a thin particle compared to the conventional talc fine powder. In general, talc powder is reduced in aspect ratio as it is miniaturized and becomes a shape close to a granular shape rather than a scale, but the talc fine powder is 15 or more even if the median diameter is as fine as 2 μm or less, for example. It has a high aspect ratio.

  The method for measuring the aspect ratio is to observe fine particles of talc with an ultra-high resolution field emission scanning electron microscope (product name “S-4800” manufactured by Hitachi, Ltd.) at a magnification of 30,000 to 100,000, and to observe the cross section. Ten possible particles were selected arbitrarily, the thickness and length of each cross section were measured, each aspect ratio (length / thickness) was calculated, and the arithmetic average value was calculated.

<Bulk specific gravity>
The bulk specific gravity of the talc fine powder is usually 0.12 or less, preferably 0.11 or less, and more preferably 0.07 or less. For this reason, the said talc fine powder is bulky rather than the conventional talc fine powder. The lower limit of bulk specific gravity is generally about 0.05.

  The measuring method of bulk specific gravity is implemented based on the method prescribed | regulated to the bulk specific gravity and stationary method of JISK5101.

  The talc fine powder is obtained by accelerating particles of a talc powder having a median diameter D50 of 2 μm or more by a laser diffraction / scattering method with a jet stream to collide with each other or a collision plate, thereby obtaining a median diameter D50 by a laser diffraction / scattering method. Can be suitably produced by a method for producing a fine talc powder having a thickness of 0.1 to 2 μm.

  As the talc powder used as a starting material, a talc powder having a median diameter D50 by laser diffraction / scattering method exceeding 2 μm is used. In particular, in the present invention, it is preferable to use talc powder having a median diameter D50 of more than 2 μm and not more than 10 μm, and further having a median diameter D50 of not less than 3 μm and not more than 10 μm. By using a talc powder in the above range as a starting material, a fine talc powder excellent in dispersion stability can be obtained more efficiently. As such talc powder, a known or commercially available product can be used.

  The pulverization is performed by accelerating the talc powder on a jet stream and causing the talc powder to collide with each other or the collision plate. As the collision plate, a collision plate made of a material such as alumina ceramic can be preferably used.

  The gas used as the jet stream is not particularly limited as long as desired acceleration performance can be obtained. For example, in addition to air, an inert gas such as nitrogen gas or helium gas can be used alone or in combination. In particular, in the present invention, it is desirable to use helium gas in that higher acceleration performance can be obtained.

  The pressure condition (pulverization pressure) can be appropriately set according to the desired particle size of the talc fine powder to be obtained, the type of gas used, etc., but is usually 0.4 to 1.5 MPa, particularly 0.6. It is desirable to adjust so that it may be -1.4MPa.

  The number of times of pulverization (number of passes) is not particularly limited, and can be one or more times. If the target particle size is small, the number of passes may be increased.

  The pulverization is not limited as long as dry jet pulverization can be performed, and a known or commercially available jet pulverization apparatus (system) can be used. For example, a dry jet mill can be used. By using these devices and performing pulverization under the above-mentioned pulverization conditions, talc fine powder having excellent dispersion stability can be suitably produced.

  The filler used in the present invention may be subjected to a surface treatment as necessary. Generally, the surface treatment may be the same as the surface treatment of the inorganic filler. For example, the surface treatment can be performed using a coupling agent such as a silane coupling agent or a titanate treatment agent. By performing the surface treatment, the characteristics (for example, tensile elongation characteristics) of the film for printed wiring board of the present invention can be further improved.

  The filler content is appropriately selected from a wide range according to various conditions such as the blending ratio of the polyaryl ketone-based resin and the polyetherimide resin, the thickness of the obtained printed wiring board film, and the usage form as the printed wiring board. Just do it. In particular, in consideration of satisfying the linear expansion coefficient, tensile elongation characteristics, molding shrinkage ratio, and other characteristics of the printed wiring board film at a high level in a well-balanced manner, the composition of the present invention is 15 to 50% by weight, preferably 20 to 20% by weight. It may be 40% by weight.

In addition, in the composition of the present invention, known additives and the like can be appropriately blended depending on the use and the like. For example, when the heat-resistant resin composition of the present invention is used as a film for printed wiring boards, a polyketone resin, a polyarylate resin, a polysulfone resin, a polyethersulfone resin, a polyphenylene sulfide resin, and the like within a range not impairing desired properties, A thermoplastic resin such as a polyphenylene oxide resin can be blended. Moreover, 1 type, or 2 or more types of well-known resin additives, such as a stabilizer, a lubricant, a mold release agent, a pigment, dye, a ultraviolet absorber, a lubricant, a filler, a reinforcing agent, can be mix | blended suitably.

2. Manufacturing method of heat resistant resin composition The manufacturing method of the heat resistant resin composition of this invention should just be able to mix said each component uniformly, and can also be implemented according to a well-known mixing method, a kneading method, etc. For example, each component in the form of powder, beads, flakes or pellets is mixed or kneaded using a known extruder, kneader, or the like to obtain a heat resistant resin composition in the form of pellets or the like. be able to.

  Examples of the extruder include a single-screw extruder and a multi-screw extruder having two or more axes. Examples of the kneader include a kneader, a Banbury mixer, a pressure kneader, and two rolls.

3. Printed wiring board This invention includes the printed wiring board formed with the said heat resistant resin composition. The printed wiring board may be either a rigid type or a flexible type. In particular, in the case of a flexible printed wiring board, the film for a printed wiring board of the present invention can be produced by forming into a film according to a normal resin molding method.

  Any known method can be adopted for processing into a film. For example, a) a heat-resistant resin composition is melt-kneaded, extruded from a T-die into a film, cast on a roll surface and cooled by casting (T-die method), b) a heat-resistant resin composition An unstretched film can be obtained by a tubular method or the like of air-cooling or water-cooling what is melt-kneaded and extruded into a tube shape from a ring-shaped die.

  In the present invention, if necessary, an unstretched film obtained by the above casting method, tubular method or the like is uniaxially or biaxially stretched at a temperature of 50 to 180 ° C., and if necessary, at a temperature lower than the melting point. It can be set as a stretched film by heat-setting.

  Although there is no restriction | limiting in particular in the thickness of the film for printed wiring boards of this invention, When the use is considered, it is about 5 micrometers-about 200 micrometers normally, Preferably it is good to set it as about 20 micrometers-125 micrometers.

  A predetermined printed wiring board can be obtained by laminating a conductor layer on the printed wiring board film. More specifically, for example, a conductor layer can be laminated on one or both sides of a printed wiring board film, or a multilayer structure of four or more layers can be formed.

  The conductor layer is a good electrical conductor layer, and a conductor layer formed of copper or a copper-based alloy is generally used. The thickness of the conductor layer is not particularly limited, but considering its use, it is usually about 5 to 50 μm, preferably about 10 to 40 μm per conductor layer.

  The method for laminating the conductor layer on the printed wiring board film is not particularly limited, and any known method can be employed. For example, a) a method of pressure-bonding a copper foil at a temperature of 200 ° C. or higher, preferably 210 to 250 ° C. (under heating), b) a method of forming a copper layer on the film surface by vapor deposition or electroless plating, c) adhesion The method etc. which laminate | stack a film and copper foil through an agent layer can be mentioned. Among these, the method of thermocompression bonding a copper foil is the most common among these.

  In the present invention, the film formation and the pressure bonding of the film to the copper foil may be performed simultaneously. This can also be carried out according to known methods.

  The production method of fine talc particles as a reference example will be described below with reference to examples and comparative examples, and the features of the present invention will be described more specifically. However, the scope of the present invention is not limited to the examples.

<Reference example>
Production of Fine Talc Particles A commercially available jet mill (product name “Nano Grinding Mill”, manufactured by Aisin Nano Technologies Inc.) was used. The pulverization conditions were a pulverization pressure of 1.4 Mpa and a raw material supply amount of 16 kg / hr. Fine grinding was carried out with 4 passes of grinding. As a starting material, white powder talc particles (product name “Microace P-4”, manufactured by Nippon Talc Co., Ltd., D ₅₀ : 4.5 μm) were used. Thereby, fine talc particles were obtained.

The particle size of the fine talc particles obtained was measured with a particle size distribution analyzer (“SALD-2000J” manufactured by Shimadzu Corporation). As a result, the number average particle size was 0.05 μm to 1 μm, and 50% by weight of these fine talc particles were finely pulverized to a particle size of 550 nm.
<Example 1 and Comparative Examples 1-2>
[resin]
Polyetheretherketone: trade name 450G, manufactured by Victrex, hereinafter referred to as “PEEK” Polyetherimide: trade name Ultem 1000-1000, manufactured by Nippon GE Plastics Co., Ltd., hereinafter referred to as “PEI”.

[Talc particles]
Fine talc particles: The number average particle size produced in the above reference example is 0.05 μm to 1 μm, and 50% by weight of these fine talc particles have a particle size of 550 nm.

Commercial talc particles: Commercial talc particles manufactured by Nippon Talc Co., Ltd. Product name “Microace P-4” D ₅₀ : 4.5 μm
Product name “SG-95” D ₅₀ : 2.5 μm
The resin and various talc particles are supplied to a twin-screw extruder (trade name: KTX46, manufactured by Kobe Steel, Ltd.) at a blending ratio (parts by weight) shown in Table 1, and pellets of the heat-resistant resin composition of the present invention. And the resin composition for a comparison was manufactured.

  The obtained pellets were injection molded to produce a molded product. The obtained molded product was measured for tensile elongation, bending strength and bending deflection, which are indicators of mechanical strength, and molding shrinkage, which is an indicator of anisotropy.

  Tensile elongation (%): Measured according to JIS K7161.

  Bending strength (MPa) and bending deflection (%): Measured according to JIS K7171.

  Molding shrinkage (%): A molded product was produced with a film gate on a metal mold having a size of 90.01 × 49.99 × 3.20 mm, and calculated according to the following formula.

Mold shrinkage (%) = [(mold size−molded product dimension) / mold size] × 100
The results are shown in Table 1.

<Example 3>
A heat resistant resin composition was obtained in the same manner as in Example 1 using 38.5 parts by weight of PEEK, 38.5 parts by weight of PEI, and 40 parts by weight of fine talc particles obtained in Reference Example. The pellets were extruded by a coat hanger die extruder to form a film having a thickness of 75 μm. The obtained film was evaluated by the following method. The results are shown in Table 2.

  Film extrudability: “○” indicates that the molten resin composition pulled down from the T-die is wound, and film processing is possible. Evaluated as “x”.

  Toughness (flexibility): The film was bent 180 degrees to examine whether the film was brittlely broken. Those that were broken like glass and those in which the bent part was partially or wholly broken were evaluated as “X”, and those that did not break or break were evaluated as “◯”.

Cu laminar curl property: 35 μm of electrolytic Cu foil and a film were press-pressed under a pressure of 30 Kg / cm ² at 210 ° C. for 30 minutes, and the curl property of the obtained Cu laminate film was measured. The curvature radius of 200 mm or more was evaluated as “◯”, 100 mm to 200 mm as “Δ”, and 100 mm or less as “x”.

  Tensile strength: Based on JIS K 7311, a tensile test was performed at a speed of 300 mm / min, and the tensile strength was measured.

  Linear expansion coefficient: A linear expansion coefficient of 165 to 175 ° C. was measured using an SSC5200H discation manufactured by Seiko Instruments Inc. and a TMA120 thermomechanical analyzer. The film drawing direction was MD, and the perpendicular direction was TD.

  TMA Elongation: Using a TMA120 thermomechanical analyzer, elongation (%) was measured on a 5 × 25 mm strip test piece under a tensile load of 50 g at 20 to 250 ° C. and a heating rate of 5 ° C./min.

  Solder heat resistance: The film was immersed in a 260 ° C. solder bath for 10 seconds to examine the deformation of the film. The case where the deformation was large was evaluated as “×”, the case where there was a slight deformation was evaluated as “Δ”, and the case where there was little deformation was evaluated as “◯”.

<Comparative Example 3>
A commercially available talc particle (trade name: “Microace P-4” manufactured by Nippon Talc Co., Ltd., D ₅₀ : 4.5 μm) was used in place of the fine talc particles, and a film was produced in the same manner as in Example 3. The resulting film was evaluated. The results are shown in Table 2.

<Comparative example 4>
A film was obtained in the same manner as in Example 3 except that commercially available talc particles (trade name: “SG-95”, Nippon Talc Co., Ltd. D ₅₀ : 2.5 μm) were used instead of the fine talc particles. Was evaluated. The results are shown in Table 2.

From the above results, the film for printed wiring board of the present invention has a linear expansion coefficient (3 × 10 ⁻⁵ / K or less, particularly 2.5 × 10 ⁻⁵ / K or less) comparable to that of copper foil. It does not cause curling even when laminated with copper foil, and has excellent elongation characteristics, deflection characteristics, molding shrinkability, etc., and has excellent heat resistance and workability for bonding with metal conductors. .

<Example 4>
As fine talc particles, talc fine powder obtained in the following Production Example 1 was used, and pellets and molded articles of a heat resistant resin composition were produced in the same manner as in Example 1 and Example 3. As a result of performing the same tests as those of Example 1 and Example 3 for these, results almost the same as those of Example 1 and Example 3 were obtained, respectively.

Production Example 1
Talc powder as a starting material (product name “Microace P-3” manufactured by Nippon Talc Co., Ltd., D50: 5.1 μm, BET specific surface area: 8.5 m ² / g) was pulverized by dry jet pulverization, and talc fine A powder (D50: 0.5 μm) was obtained.

As the pulverizer, a helium circulation type pulverization system (product name “PJM-80SP” manufactured by Nippon Pneumatic Industry Co., Ltd.) was used. The pulverization conditions were a pulverization pressure of 0.6 MPa and a raw material supply amount of 0.5 kg / hr. The number of pulverizations was 2 passes. The atmosphere of the entire line was a helium gas atmosphere. About the obtained talc fine powder, (1) ratio D50 _19.5kHz / D50 _45kHz (SALD ratio), (2) bulk specific gravity, and (3) aspect ratio were investigated, respectively. The results are shown in Table 3.

Each physical property was measured as follows.
(1) Ratio D _19.5kHz / D _45kHz
0.1 g of talc fine powder immediately after being left in a thermostatic chamber set at 70% relative humidity and a temperature of 25 ° C. in atmospheric pressure for 1 month is taken into a 100 ml glass beaker as a container. To the container is added 50 ml of distilled water to which 1% by weight of an anionic surfactant has been added and adjusted. The container is placed in an ultrasonic cleaner, and the median diameter D50 of _{45 kHz} of talc powder B obtained by continuous dispersion for 1 minute with ultrasonic waves having an oscillation frequency of 45 kHz and a rated output of 100 W is measured. The median diameter D50 of _{19.5 kHz} of talc fine powder C obtained by dispersing for 3 minutes (repetition of oscillation for 3 seconds and pause for 2 seconds, irradiation for a total of 108 seconds) with ultrasonic waves having an oscillation frequency of 19.5 kHz and a rated output of 300 W, The ratio [D50 _{19.5 kHz} / D50 _{45 kHz} ] was determined.
(2) Bulk specific gravity It implemented based on the method prescribed | regulated to JISK5101, bulk specific gravity stationary method.
(3) Aspect ratio The particles of talc fine powder can be observed with an ultra-high resolution field emission scanning electron microscope (product name “S-4800” manufactured by Hitachi, Ltd.) at a magnification of 30,000 to 100,000, and the cross section can be observed. Ten particles were selected arbitrarily, the thickness and length of each cross section were measured, each aspect ratio (length / thickness) was calculated, and the arithmetic average value was calculated. More specifically, as shown in FIG. 1, a particle whose cross section can be observed is selected, the cross section thickness (t) and the cross section length (D) are measured, and the ratio [D / t] is determined. Asked.

It is a figure (image image) which shows the result of having observed the particle | grains of the talc fine powder obtained by manufacture example 1 with the ultrahigh resolution field emission scanning electron microscope.

Claims (17)

1) a polyaryl ketone resin, 2) a polyetherimide resin, and 3) a heat-resisting material containing at least one filler selected from fine talc particles having a number average particle diameter of 0.05 μm or more and 1 μm or less and finely fired talc particles. Resin composition. The heat resistant resin composition according to claim 1, wherein the polyaryl ketone-based resin is at least one selected from polyether ketone, polyether ether ketone, polyether ketone ketone, and polyether ether ketone ketone. The heat resistant resin composition according to claim 1 or 2, wherein the filler has a number average particle size of 0.05 µm or more and less than 1 µm, and at least 50 wt% has a particle size of 0.1 µm to 0.9 µm. The heat resistant resin composition according to claim 1 or 2, wherein the filler has a number average particle size of 0.05 µm or more and less than 1 µm, and at least 50 wt% has a particle size of 0.1 µm to 0.4 µm. The heat resistant resin composition according to any one of claims 1 to 4, wherein the content of the polyaryl ketone resin is 30 to 50% by weight. The heat resistant resin composition according to any one of claims 1 to 5, wherein the content of the polyetherimide resin is 20 to 40% by weight. The heat resistant resin composition according to any one of claims 1 to 6, wherein the polyaryl ketone resin is contained in an amount of 30 to 70% by weight in a total of 100% by weight of the polyaryl ketone resin and the polyetherimide resin. The heat-resistant resin composition according to any one of claims 1 to 7, wherein the filler content is 20 to 40% by weight. The filler is talc fine powder having a median diameter D50 of 0.1 to 2 μm by a laser diffraction / scattering method,
The talc fine powder obtained by dispersing the talc fine powder in an atmospheric pressure at a relative humidity of 70% and a temperature of 25 ° C. for one month and then dispersing the talc fine powder A with ultrasonic waves having an oscillation frequency of 45 kHz and a rated output of 100 W for 1 minute. and the median diameter D50 _{45 kHz} of the powder B, a further said talc said median diameter D50 _{19.5 kHz} fine powder B the oscillation frequency 19.5kHz- rated output 300W ultrasound by 3 minutes dispersion obtained was talc fine powder C The heat resistant resin composition according to claim 1, _wherein the ratio [D50 _{19.5 kHz} / D50 _{45 kHz} ] is 0.88 or more. The heat resistant resin composition according to claim 9, wherein the talc fine powder has an aspect ratio of 15 or more. The heat resistant resin composition according to claim 9 or 10, wherein the bulk specific gravity of the talc fine powder is 0.12 or less. The printed wiring board containing the film formed with the heat resistant resin composition in any one of Claims 1-11. The printed wiring board according to claim 12, wherein a conductor layer is further formed on the film. The printed wiring board according to claim 13, wherein the conductor layer is formed of copper or a copper-based alloy. The printed wiring board according to claim 13 or 14, wherein the conductive layer is a layer formed by any one of 1) lamination of metal foil, 2) coating by plating, or 3) an inkjet method. The printed wiring board according to any one of claims 12 to 15, wherein the printed wiring board is flexible. The printed wiring board in any one of Claims 12-16 whose linear expansion coefficient in 165-175 degreeC is 3 * 10 < ^-5 > / K or less.