JP2007197714A - Liquid crystalline resin alloy composition and film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystalline alloy resin composition having little molding shrinkage of molded product, little deflection in bending and relatively large tensile elongation and a film having no anisotropy in a linear expansion coefficient in plane direction and a small linear expansion coefficient in thickness direction. <P>SOLUTION: The resin composition comprises a liquid crystalline resin (A), a thermoplastic resin (B) and at least one species of fillers (C) comprising fine talc particles and fine fired talc particles. In the liquid crystalline resin alloy composition, (1) the thermoplastic resin (B) is at least one species selected from polyether sulfone resins, polyether imide resins, polyamideimide resins, polyarylketone resins, polyarylate resins and polyphenylene sulfide resins, (2) the filler (C) has 0.05-1μm number average particle size and 0.1-0.9μm in at least 50wt.% of the filler. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a liquid crystalline resin alloy composition and a film obtained from the composition.

  The liquid crystalline resin is generally referred to as LCP and is a resin exhibiting liquid crystallinity in a molten state or a solution state. In particular, a thermotropic liquid crystalline resin exhibiting a molten state has excellent properties such as high strength, high heat resistance, high insulation, low water absorption, and high gas barrier properties, and has already been put into practical use as an injection molded part or fiber. In addition, a film using the liquid crystalline resin is expected to be used as an electronic material, a flexible printed circuit (FPC), a packaging material, or the like.

  However, when extruded in the molten state, the liquid crystalline resin is remarkably oriented in the shear direction, and there are problems in appearance such as cracks and wrinkles in the film, the orientation direction of the film (the longitudinal direction of the film). ) (MD), film orientation direction and perpendicular direction (film width direction) (TD) have problems such as large anisotropy.

  Thus, several methods have been proposed as techniques for reducing this anisotropy. For example, using inflation [Japanese Patent Publication No. 01-34134 (Patent Document 1), Japanese Patent Laid-Open No. 03-152131 (Patent Document 2), Japanese Patent Laid-Open No. 05-43664 (Patent Document 3)], using a rotating die Due to inflation [Japanese Patent Laid-Open No. 63-199622 (Patent Document 4), Japanese Patent Laid-Open No. 01-130930 (Patent Document 5), Japanese Patent Laid-Open No. 02-89616 (Patent Document 6), Japanese Patent Laid-Open No. 04-506679 Gazette (Patent Document 7)], a method of crossing the orientation of each layer of a multilayer flat die [JP 02-89617 A (Patent Document 8), JP 63-264323 A (Patent Document 9)], flat Method of applying a magnetic field in the transverse direction at the land portion of the die [Japanese Patent Laid-Open No. 02-89617 (Patent Document 10)], and non-liquid crystalline resins such as polyester and liquid crystalline resins Coextruded [JP-A 63-31729 (Patent Document 11), JP-A 02-178016 (Patent Document 12)], a method of stretching a laminate of a liquid crystalline resin and a synthetic resin film [ JP-A-07-323506 (Patent Document 13), JP-A-09-131789 (Patent Document 14)] and the like have been proposed.

  Some proposals have also been made regarding a method of blending a liquid crystalline resin with another thermoplastic resin. For example, a blend with a thermoplastic resin (B) having an overlapping molding temperature [Japanese Patent Laid-Open No. 56-115357 (Patent Document 15)], a blend with PEI (polyetherimide) [Japanese Patent Laid-Open No. 63-215769] (Patent Document 16), JP-A 64-1758 (Patent Document 17), JP-A-01-301799 (Patent Document 18)], blends with polysulfone [JP 57-40555 (Patent Document 17) Patent Document 19), Japanese Patent Application Laid-Open No. 01-252657 (Patent Document 20)] and the like.

  However, these are all for the purpose of improving mechanical characteristics or electrical characteristics, improving workability, and the like, and although there is a description of the film in use, there is no film in the examples.

  Japanese Patent Application Laid-Open No. 06-506498 (Patent Document 21) discloses a film made of a blend of a liquid crystalline resin and another thermoplastic resin. However, it is a film manufacturing method using a counter-rotating die and is basically a multilayer film, so that there is a high possibility of delamination. In addition, when blending resins with low heat resistance such as PP (polypropylene), PC (polycarbonate), PS (polystyrene), etc., the heat resistance of the film itself is lowered and the thermal stability of the polymer blend during melt processing is reduced. It is not easy to make a film of sufficient quality because of the decrease.

  In addition, Japanese Patent Application Laid-Open No. 08-337710 (Patent Document 22) discloses a film made of a blend of a liquid crystalline resin and another thermoplastic resin. However, in this case, as the thermoplastic resin, an ethylene copolymer having a glycidyl group is described in detail, and only examples of the ethylene copolymer having a glycidyl group are described. Since such a resin is based on ethylene copolymer, its heat resistance is low, and it is difficult to produce a film with satisfactory productivity and quality. This document also describes improving the specific viscosity behavior when the liquid crystalline resin is melted to improve the workability.

  As described above, various methods for producing a liquid crystalline resin film with relaxed anisotropy have been proposed so far, but each film has the following problems.

  In general, a low linear expansion coefficient can be cited as a characteristic of the liquid crystalline resin, but this is a characteristic in the direction in which the resin is oriented, and in the non-oriented direction, rather, the linear expansion coefficient. Is often big. In addition, the liquid crystalline resin does not have a clear glass transition point (that is, a temperature at which the elastic modulus suddenly decreases) as compared with other thermoplastic resins, and has a drawback that the elastic modulus gradually decreases as the temperature rises.

  Recently, in order to improve these drawbacks, 25 to 55% by weight of a liquid crystalline resin and a heat-resistant thermoplastic resin (B) such as polyethersulfone, polyetherimide, polyetheretherketone, polyarylate and polyphenylene sulfide are used. A blended film has been proposed. According to this proposal, the linear expansion coefficient in both the MD and TD directions of the film is reduced to 5 to 25 ppm, and the linear expansion coefficient in the thickness direction of the film exceeds 270 ppm. No film was found.

However, the linear expansion coefficient in the MD and TD directions is 25 ppm at the maximum, which is larger than that of the metal conductor, and the maximum linear expansion coefficient in the thickness direction is 270 ppm, which still has practical problems.
Japanese Patent Publication No. 01-34134 (Claim 1) Japanese Patent Laid-Open No. 03-152131 (Claim 1) JP 05-43664 A (Claim 1) JP 63-199622 A (Claim 1) Japanese Patent Laid-Open No. 01-130930 (Claim 1) JP 02-89616 A (Claim 1) Japanese National Patent Publication No. 04-506679 (Claim 1) Japanese Patent Laid-Open No. 02-89617 (Claim 1) JP 63-264323 A (Claim 1) Japanese Patent Laid-Open No. 02-89617 (Claim 1) JP 63-31729 A (Claim 1) Japanese Patent Laid-Open No. 02-178016 (Claim 1) Japanese Patent Laid-Open No. 07-323506 (Claim 1) JP 09-131789 A (Claim 1) JP-A-56-115357 (Claim 1) JP 63-215769 A (Claim 1) JP-A 64-1758 (Claim 1) Japanese Patent Laid-Open No. 01-301749 (Claim 1) JP-A-57-40555 (Claim 1) JP-A-01-252657 (Claim 1) JP-T 06-506498 (Claim 1) JP 08-337710 A (Claim 1) JP 2004-175959 A (Claim 1) JP 2002-69309 A (paragraphs 0028-0030)

  The present invention provides a liquid crystalline resin alloy composition having a small molding shrinkage rate, a small deflection, a relatively large tensile elongation, and a film having no linear anisotropy in the plane direction linear expansion coefficient and a small linear expansion coefficient in the thickness direction. The issue is to provide.

  As a result of intensive studies in view of the problems of the prior art, the present inventors have found that the above object can be achieved by preparing a specific liquid crystalline resin alloy composition, and have completed the present invention. .

That is, the present invention relates to the following novel liquid crystalline resin alloy composition and the film.
1. A resin composition comprising a liquid crystalline resin (A), a thermoplastic resin (B), and at least one filler (C) comprising fine talc particles and fine baked talc particles,
(1) The thermoplastic resin (B) is a polyether sulfone resin, a polyetherimide resin, a polyamideimide resin, a polyaryl ketone resin, a polyarylate resin, and a polyphenylene sulfide resin,
(2) The filler (C) has a number average particle diameter of 0.05 μm to 1 μm, and at least 50% by weight is 0.1 μm to 0.9 μm.
A liquid crystalline resin alloy composition characterized by that.
2. Item 2. The liquid crystalline resin alloy composition according to item 1, wherein the liquid crystalline resin (A) is a thermotropic liquid crystalline resin having a melting point of 250 ° C or higher.
3. Item 3. The liquid crystalline resin alloy composition according to item 1 or 2, wherein the content of the liquid crystalline resin (A) is 50 to 60% by weight in the resin composition.
4). Item 4. The liquid crystalline resin alloy composition according to any one of Items 1 to 3, wherein the content of the thermoplastic resin (B) is 30 to 50% by weight in a total of 100% by weight of (A) + (B). .
5). Item 5. The liquid crystalline resin alloy composition according to any one of Items 1 to 4, wherein the content of the filler (C) is 10 to 50 parts by weight with respect to 100 parts by weight as a total of (A) + (B).
6). Item 6. The liquid crystalline resin alloy composition according to Items 1 to 5, wherein the filler (C) has a number average particle size of 0.05 μm to 1 μm and at least 50% by weight is a particle size of 0.1 μm to 0.4 μm. .
7). A film obtained by molding the liquid crystalline resin alloy composition according to any one of Items 1 to 6.
8). Item 8. The film according to Item 7, wherein the molding shrinkage is 0.30% or less, the bending deflection is 3.6% or less, and the tensile elongation is 4.0% or more.
9. Item 7. The difference between the linear expansion coefficients of the film MD (film longitudinal direction) and TD (film width direction) in both directions is 10 ppm or less, and the film thickness direction linear expansion coefficient is 200 ppm or less. Or the film of 8.
10. The filler is a talc fine powder having a median diameter D50 of 0.1 to 0.9 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 5. The liquid crystalline resin alloy composition according to any one of Items 1 to 4, wherein the ratio [D50 _{19.5 kHz} / D50 _{45 kHz} ] is 0.88 or more.
11. Item 6. The liquid crystalline resin alloy composition according to Item 5, wherein the talc fine powder has an aspect ratio of 15 or more.
12 Item 7. The liquid crystalline resin alloy composition according to Item 5 or 6, wherein the talc fine powder has a bulk specific gravity of 0.12 or less.

  In particular, since the present invention employs a composition containing a specific filler in a liquid crystalline resin, it is possible to provide a material that exhibits excellent mechanical characteristics, electrical characteristics, and the like. In particular, a film (for example, a film formed by extrusion molding) obtained from the composition of the present invention can relieve stress by reducing the linear expansion coefficient in the MD, TD, and thickness directions of the film. . This film is effective in applications in which the films are laminated, for example, in multilayer wiring boards.

The liquid crystalline resin alloy composition of the present invention is a resin composition containing a liquid crystalline resin (A), a thermoplastic resin (B), and at least one filler (C) composed of fine talc particles and fine baked talc particles. And
(1) The thermoplastic resin (B) is a polyether sulfone resin, a polyetherimide resin, a polyamideimide resin, a polyaryl ketone resin, a polyarylate resin, and a polyphenylene sulfide resin,
(2) The filler (C) has a number average particle diameter of 0.05 μm to 1 μm, and at least 50% by weight is 0.1 μm to 0.9 μm.
It is characterized by that.

Liquid crystalline resin (A)
The liquid crystalline resin (LCP) is preferably a thermotropic liquid crystalline resin having a melting point of 250 ° C. or higher. Various known resins can be used as such a resin. Among these, a liquid crystalline resin having a melting point of 280 ° C. to 380 ° C. is preferable. Examples of the liquid crystalline resin include aromatic polyesters that are synthesized from monomers such as aromatic diols, aromatic carboxylic acids, and hydroxycarboxylic acids and that exhibit liquid crystallinity when melted. Typical examples thereof include a first type consisting of parahydroxybenzoic acid (PHB), terephthalic acid and biphenyl (the following formula 1), and a second type consisting of PHB and 2,6-hydroxynaphthoic acid ( Examples are the following formula 2), the third type consisting of PHB, terephthalic acid and ethylene glycol (following formula 3).

  Although content of liquid crystalline resin (A) can be suitably set according to the kind etc. of liquid crystalline resin to be used, it is usually desirable to set it as 50 to 75 weight% in the said resin composition, especially 50 to 60 weight%. .

Thermoplastic resin (B)
The thermoplastic resin (B) is not limited as long as it is a thermoplastic resin other than the liquid crystalline resin. For example, at least one selected from PES (polyethersulfone), PEI (polyetherimide), PAI (polyamideimide), PEEK (polyetheretherketone), PAR (polyarylate), and PPS (polyphenylene sulfide) A thermoplastic resin (B) can be used suitably.

  In the thermoplastic resin (B) used in the present invention, the melting temperature or the melt molding temperature thereof is preferably set so as to overlap the melt molding temperature of the liquid crystalline resin (A) used. That is, if the melting temperatures of (A) and (B) are different, the melt mixing property is lowered, so it is desirable to match the melting temperatures. Accordingly, the thermoplastic resin (B) used in the present invention can be appropriately selected in relation to the liquid crystalline resin (A) used. Specific examples of the thermoplastic resin (B) preferably used in the present invention include, for example, a product name “PES” of Sumitomo Chemical Co., Ltd. as PES, and a product name of “GE Plastics” “ "Ultem" is shown.

  The content of the thermoplastic resin (B) is generally 25 to 55% by weight, preferably 30 to 50% by weight, based on the total weight of the liquid crystalline resin (A) and the thermoplastic resin (B). When the ratio of the thermoplastic resin (B) is too small, the effect of improving physical properties such as the linear expansion coefficient in the thickness direction in the obtained film becomes poor. On the other hand, if the amount is too large, the mechanical properties of the resulting film may be lowered, and it may be difficult to control the linear expansion coefficient in that direction.

Filler (C)
In the present invention, at least one filler selected from fine talc particles and fine fired talc particles is used as the filler (C).

  The filler (C) has a number average particle size of 0.05 μm to 1 μm, and at least 50% by weight is 0.1 μm to 0.9 μm.

  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. It is as follows. When the number average particle diameter is less than 0.05 μm, sufficient dispersibility may not be obtained. Further, when the number average particle diameter exceeds 1 μm, desired physical characteristics may not be obtained. The number average particle diameter of the present invention indicates a value measured using a laser diffraction particle size distribution analyzer (product name “SALD-2000J” manufactured by Shimadzu Corporation).

  The filler in the present invention has at least 50% by weight (50% diameter) in the range of 0.1 μm to 0.9 μm, and particularly preferably in the range of 0.1 μm to 0.4 μm. By setting the content in the above range, the object of the present invention, that is, a resin alloy composition having a small molding shrinkage ratio and elongation deflection and a relatively large tensile elongation can be efficiently obtained. Further, when the film is formed, a film having a smaller linear expansion coefficient in the surface direction and the thickness direction can be obtained. The 50% diameter measurement method is the same as the median diameter D50 measurement method by laser diffraction / scattering method described later.

White powdery talc particles represented by the chemical formula Mg ₃ Si ₄ O ₁₀ (OH) ₂ are also called talc. This compound can be represented by the composition formula 3MgO, 4SiO ₂ , H ₂ O, and is a plate-like white substance that is crystallographically classified as a triclinic system. Further, the calcined talc particles obtained by calcining the white powder talc particles at a temperature of, for example, 800 ° C. or higher are a mixture of 3MgSiO ₃ and SiO ₂ , also called enstatite, and in the literature, SiO ₂ is referred to as cristobalite. On the X-ray diffraction, no SiO ₂ crystal peak is observed, and the silica is amorphous silica.

Furthermore, the filler of the present invention preferably has a Mohs hardness of 1 or more. 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, a resin alloy composition having a relatively large tensile elongation can be obtained by reducing the molding shrinkage rate and elongation deflection. Moreover, when it makes into a film, the linear expansion coefficient of a surface direction and a thickness direction can be restrained effectively low.

  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. On the other hand, when the fine talc particles and fine baked talc particles used in the present invention are used, it is possible to suppress or prevent alteration due to moisture in the air, and as a result, good bending deflection characteristics, tensile elongation characteristics, etc. can be obtained. .

  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.

  In addition, when using finely baked talc particles (steatite particles) as a filler, for example, after calcination of commercially available talc particles to 800 ° C. or higher in advance, particle size adjustment (pulverization), classification, and the like can be performed as the filler. It can also be used.

  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 0.9 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 talc fine powder has a median diameter D50 by laser diffraction / scattering method of usually 0.1 to 0.9 μm, preferably 0.1 to 0.7 μm, more preferably 0.1 to 0.6 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.

  In the present invention, the median diameter D50 indicates a value measured using a laser diffraction particle size distribution analyzer (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 (C) 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, various properties of the resin composition of the present invention can be further improved.

  Although content of a filler (C) is not limited, Usually, it is desirable to set it as 10-50 weight part with respect to a total of 100 weight part of said (A) + (B), especially 15-45 weight part. If the filler (C) is too smaller than the above range, the warpage of the molded product may be increased. Moreover, when there is too much more than the said range, moldability may be inhibited.

Other components In the present invention, auxiliary components such as a compatibilizing agent, a plasticizer, a flame retardant, and a filler (inorganic powder, fiber, etc.) are added as necessary within the range not impeding the effects of the present invention. Can do. What is necessary is just to set suitably the addition ratio of these auxiliary components according to the kind etc. of the specific auxiliary component.

The manufacturing method of this invention composition is not restrict | limited as long as these components can be mixed uniformly. For example, the liquid crystalline resin alloy composition can be prepared by melt-kneading the liquid crystalline resin (A) and the thermoplastic resin (B) and side-feeding the filler (C) therein. As the melt kneader, a single or twin screw extruder, various kneaders, and the like can be used. Moreover, when supplying to these melt-kneading apparatuses, the liquid crystalline resin (A) and the thermoplastic resin (B) can be dry blended in advance using a mixing apparatus such as a tumbler or a Henschel mixer.

  When the composition of the present invention is molded, a known molding method or the like can be used depending on the desired molded body. For example, a molded body can be suitably manufactured by injection molding. For example, when manufacturing a film, it can manufacture by making a liquid crystalline resin alloy composition into a film using a well-known film forming apparatus, and extending | stretching this film to a uniaxial direction or a biaxial direction. As the film forming apparatus, a known apparatus such as a single or twin screw extruder and a rolling apparatus can be used.

  In the film, the thickness before stretching is desirably set to 15 to 1000 μm (preferably 25 μm to 500 μm). This film is desirably stretched in the machine direction and / or the transverse direction in the stretching process. The thickness of the stretched film is generally about 10 μm to 300 μm, particularly preferably 25 μm to 125 μm.

  The stretching technique for forming these liquid crystalline resin alloy compositions into a film can be performed by a known method. In this case, a laminate film is generally used. This laminating film is preferably a fluororesin porous film. The extending | stretching method of these liquid crystalline resin alloy compositions contains a laminated body film formation process (laminated body which consists of a liquid crystalline resin alloy composition and a laminated film), an extending process, a cooling process, and a peeling process. Each process is described in detail in Japanese Patent Application Laid-Open No. 2004-175995 (Patent Document 23), and can be used as it is in the present invention.

  The liquid crystalline resin alloy composition that is the main material of the film, which is the main purpose, is preferably such that a molded product obtained by injection molding or the like has a bending deflection rate of 3.6% or less. Moreover, it is preferable that a tensile elongation rate is 4.0% or more. Further, the molding shrinkage is preferably 0.30% or less. Thus, it is proposed in Japanese Patent Application Laid-Open No. 2002-69308 (Patent Document 24) that can be applied in each application field and can solve cracking and brittleness. The optimum filler for achieving this object is the fine talc particles and / or fine baked talc particles of the present invention. This is because the talc itself has a Mohs hardness of 1, the softest talc particles or the calcined talc particles themselves have the smallest linear expansion coefficient, and fine talc particles and / or fine calcinated talc particles are added in the same amount. Even so, since the number of particles is greatly added, the effect of preventing the thermal expansion of the thermoplastic resin (B) is great.

  Further, in the film obtained from the liquid crystalline resin alloy composition of the present invention, the linear expansion coefficients in both directions of MD (the longitudinal direction of the film) and TD (the width direction of the film) are both 5 to 25 ppm, particularly 10 It is preferable to set it as -20 ppm. The difference in linear expansion coefficient between MD and TD is preferably 10 or less. By providing such physical properties, substantially isotropic properties can be obtained. In the film of the present invention, the linear expansion coefficient in the thickness direction is preferably 250 ppm or less, particularly preferably 200 ppm or less.

  The film of the present invention can be used as an FPC (for flexible printed circuit) film by forming a metal conductor layer on the surface thereof.

  As a method for forming a metal layer on the surface of the film, for example, 1) a method in which a metal foil is laminated on a film and both layers are fused, 2) a physical method in which sputtering or vapor deposition is performed, and 3) electroless plating Alternatively, a chemical method such as electrolytic plating after electroless plating, 4) a metal paste coating method, and the like can be given.

  Although the thickness of these metal conductor layers is not limited, it is generally about 500 μm to 200 μm, and this metal laminate film can be used as a multilayer power distribution board, but also used for other applications such as a high heat dissipation board and an antenna board. Can do. The multilayer wiring board is optimal as an electronic circuit board, but can also be used for an opto-electronic hybrid board, an IC package, and the like.

  Hereinafter, the present invention will be described with reference to examples and comparative examples. However, the scope of the present invention is not limited to the examples.

<Examples 1-7 and Comparative Examples 1-5>
The liquid crystalline resin (A), thermoplastic resin (B), fine talc particles and / or fine baked talc particles (C) shown in Table 1 were dry blended in the proportions shown in Table 1. This dry blend was supplied into a twin screw extruder (screw diameter: 15 mm), melted and kneaded to prepare a liquid crystalline resin alloy composition. Subsequently, the film was extruded from a T-die (lip length: 10 cm, lip clearance: 2.5 mm) at the tip of the extruder and cooled to obtain a film made of a liquid crystalline resin alloy composition having a thickness of 300 μm. The appearance of the film is uniform and uniform.

  Next, after laminating a fluororesin porous film on both sides of the film thus obtained and thermocompression bonding with a pair of rolls (temperature 340 ° C., roll peripheral speed 2 m / min), a pair of cooling rolls (temperature 150 (C, roll peripheral speed 2 m / min).

  This laminate film was stretched by a biaxial stretching machine at a stretching speed of 20% / second. The draw ratio was appropriately adjusted according to each film. However, the draw ratio is such that the product x × y of the draw ratio x in the MD direction and the draw ratio y in the TD direction is about 6, and the thickness of the film obtained from the liquid crystalline resin alloy composition is about 50 μm. Was set to be. Finally, the laminate film was peeled from both sides of the film of the present invention to obtain the film of the present invention.

With respect to the stretched film thus obtained, the linear expansion coefficient (ppm), elastic modulus (GPa), and tensile strength in the MD, TD, and thickness directions were measured, and the results are shown in Table 1 and the liquid crystal of the present invention. Table 2 shows some of the basic physical properties of the conductive resin alloy composition. The specific contents of the symbols shown in Table 1 are as follows.
・ Liquid crystal resin (A)
E4000 (Sumika Super E4000: manufactured by Sumitomo Chemical Co., Ltd .; melting point 380 ° C.)
E6000 (Sumika Super E6000: manufactured by Sumitomo Chemical Co., Ltd .; melting point 355 ° C., processing temperature 350 ° C.)
C950 (manufactured by Polyplastics Co., Ltd .; melting point 335 ° C, processing temperature 330 ° C)
A950 (manufactured by Polyplastics Co., Ltd .; melting point 285 ° C, processing temperature 300 ° C)
・ Thermoplastic resin (B)
PEI (Polyetherimide: manufactured by GE Plastics; Ultem 1000, processing temperature 340 to 380 ° C.)
PES (polyethersulfone: manufactured by Sumitomo Chemical Co., Ltd .; processing temperature: 320 ° C to 360 ° C
PPS (polyphenylene sulfide: manufactured by Dainippon Ink & Chemicals, Inc .; melting point: 280 ° C., processing temperature: 300 to 340 ° C.)
-Fine talc particles and / or fine baked talc particles Production Example 1 (Production of fine talc particles)
A commercially available jet mill (product name “Nano Grinding Mill” manufactured by Aisin Nano Technologies) 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. In this way, 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 diameter was 0.05 to 1 μm, and 50% by weight of these fine talc particles were finely pulverized to a particle diameter of 0.1 to 0.9 μm. Fine talc obtained by this method and having the following characteristics was used.

Fine talc particles (a) (manufactured by Nippon Talc Co., Ltd .; having a number average particle size of 0.05 μm to 1 μm, of which 50% by weight has a particle size of 0.1 μm to 0.9 μm)
Fine talc particles (b) (manufactured by Nippon Talc Co., Ltd .; having a number average particle size of 0.05 μm to 1 μm, of which 50% by weight has a particle size of 0.1 μm to 0.4 μm)
Fine calcined talc particles (c) (manufactured by Nippon Talc Co., Ltd .; having a number average particle size of 0.05 μm to 1 μm, of which 50% by weight has 0.1 μm to 0.9 μm)
Moreover, the evaluation method of the film physical property shown in Table 1 is as follows.
<Linear expansion coefficient>
After the temperature was raised to 150 ° C. at a rate of temperature rise of 10 ° C./min, the linear expansion coefficient of the film that was lowered to 50 ° C. at a temperature drop temperature of 5 ° C./min was determined. The linear expansion coefficients of MD and TD of the film were measured in the tensile mode, and the linear expansion coefficient in the thickness direction of the film was laminated to a thickness of 1 mm and measured in the push mode. The tensile mode load was 10 g, the push mode load was 100 g, and the measurement was performed by automatic strain control.
<Elastic modulus>
The measurement was performed under the conditions of a heating rate of 10 ° C./min, a strain of 0.3%, and a frequency of 1 Hz.
<Tensile strength>
A test piece was formed according to JIS K 7127 and measured according to JIS K 7127.

  As can be seen from the results shown in Table 1, the tensile strength of the film is slightly reduced because the thermoplastic resin (B) is alloyed with the liquid crystalline resin (A), but practically as a film for multilayer wiring boards. Has sufficient strength. Further, although heat resistance is slightly decreased, it has practically sufficient heat resistance (solder heat resistance, etc.).

<Comparative Examples 6-8>
Pellets were produced in the same manner as in Example 1 except that the following d or e was used as the talc particles and the compositions shown in Table 3 were used. The results are shown in Tables 3 and 4.

d: Trade name “Microace P-4” manufactured by Nippon Talc Co., Ltd., D50: 4.5 μm
e: Trade name “SG-95” manufactured by Nippon Talc Co., Ltd., D50: 2.5 μm

Example 8
As fine talc particles, the talc fine powder obtained in the following Production Example 2 was used, a liquid crystalline resin alloy composition was prepared in the same manner as in Example 1, and a film was further produced. As a result of conducting the test similar to Example 1 about the obtained film, the result almost equivalent to Example 1 was obtained.

Production Example 2
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 5.

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 2 with the ultrahigh resolution field emission scanning electron microscope.

Claims (12)

A resin composition comprising a liquid crystalline resin (A), a thermoplastic resin (B), and at least one filler (C) comprising fine talc particles and fine baked talc particles,
(1) The thermoplastic resin (B) is a polyether sulfone resin, a polyetherimide resin, a polyamideimide resin, a polyaryl ketone resin, a polyarylate resin, and a polyphenylene sulfide resin,
(2) The filler (C) has a number average particle diameter of 0.05 μm to 1 μm, and at least 50% by weight is 0.1 μm to 0.9 μm.
A liquid crystalline resin alloy composition characterized by that. The liquid crystalline resin alloy composition according to claim 1, wherein the liquid crystalline resin (A) is a thermotropic liquid crystalline resin having a melting point of 250 ° C. or higher. The liquid crystalline resin alloy composition according to claim 1 or 2, wherein the content of the liquid crystalline resin (A) is 50 to 60% by weight in the resin composition. The liquid crystalline resin alloy composition according to any one of claims 1 to 3, wherein the content of the thermoplastic resin (B) is 30 to 50% by weight in a total of 100% by weight of (A) + (B). . The liquid crystalline resin alloy composition according to any one of claims 1 to 4, wherein the content of the filler (C) is 10 to 50 parts by weight with respect to a total of 100 parts by weight of (A) + (B). The liquid crystalline resin alloy composition according to claim 1, wherein the filler (C) has a number average particle diameter of 0.05 μm to 1 μm, and at least 50 wt% is a particle diameter of 0.1 μm to 0.4 μm. . The film obtained by shape | molding the liquid crystalline resin alloy composition in any one of Claims 1-6. The film according to claim 7, wherein the molding shrinkage is 0.30% or less, the bending deflection is 3.6% or less, and the tensile elongation is 4.0% or more. The difference between the linear expansion coefficients of the film MD (film longitudinal direction) and TD (film width direction) in both directions is 10 ppm or less, and the linear expansion coefficient in the film thickness direction is 200 ppm or less. Or the film of 8. The filler is a talc fine powder having a median diameter D50 of 0.1 to 0.9 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 _5. The liquid crystalline resin alloy composition according to claim 1, _wherein the ratio [D50 _{19.5 kHz} / D50 _{45 kHz} ] is 0.88 or more. The liquid crystalline resin alloy composition according to claim 5, wherein an aspect ratio of the talc fine powder is 15 or more. The liquid crystalline resin alloy composition according to claim 5 or 6, wherein the bulk specific gravity of the talc fine powder is 0.12 or less.