JP2007197717A - Polyarylene sulfide-based resin composition and resin composition for sliding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyarylene sulfide (PPS)-based resin composition having more excellent mechanical characteristics and electric characteristics than those of conventional techniques. <P>SOLUTION: The PPS-based resin composition comprises the polyarylene sulfide-based resin (A) and at least one species of fillers (B) comprising fine talc particles and fine fired talc particles and the filler (B) has 0.05-1μm number average particle size, at least 50wt.% of the filler has 0.1-0.9μm particle size. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel polyarylene filled resin composition and a sliding resin composition.

  Polyarylene sulfide based resins, especially polyphenine sulfide based resins (hereinafter also referred to as “PPS resins”) have excellent heat resistance, flame retardancy, rigidity, chemical resistance, electrical insulation, moisture resistance, and the like. However, it has suitable properties as an engineering plastic. For this reason, it is widely used for various electric, electronic parts, mechanical parts, automobile parts, etc. mainly for injection molding.

  However, PPS-based resins have a drawback that arc resistance or tracking resistance is greatly inferior to other engineering plastics such as polyamide resin. For this reason, PPS-based resins can be used in applications where they are exposed to relatively high voltages despite having excellent properties as electrical component materials such as high heat resistance, rigidity, and electrical insulation. Limited.

  Various attempts have been made to improve the tracking resistance of PPS resins. For example, there are JP-A-53-5252 (Patent Document 1), JP-A-54-162752 (Patent Document 2), and JP-A-59-131653 (Patent Document 3). According to these, compositions containing inorganic fillers such as general-purpose talc and clay have been proposed. However, with these compositions, particularly when used for automobile parts, it is impossible to obtain desired performance in both arc resistance and tracking resistance.

Japanese Patent Laid-Open No. 5-21650 (Patent Document 4) proposes a composition containing talc having an oxide content other than SiO ₂ and MgO of 1.2% by weight or less in order to improve tracking resistance. ing. Japanese Patent Application Laid-Open No. 10-298430 (Patent Document 5) discloses a composition containing a PPS resin containing kaolin and, if necessary, talc and / or magnesium hydroxide.

  However, these conventional techniques have not yet obtained a PPS resin that can achieve both desired mechanical properties and electrical characteristics.

  On the other hand, PPS resin is also used for sliding. As the sliding resin composition, for example, JP-A-9-31328 (Patent Document 6), JP-A-2001-123061 (Patent Document 7), and the like describe polytetrafluoro PPS-based resin compositions to which ethylene (fluorine powder resin), graphite or the like is added are described (see claims and the like).

However, these PPS resin compositions still have room for improvement in terms of sliding properties.
JP-A-53-5252 Japanese Patent Laid-Open No. 54-162752 JP 59-131653 A JP-A-5-21650 JP 10-298430 A JP-A-9-313218 Japanese Patent Laid-Open No. 2001-123061

  Accordingly, the main object of the present invention is to provide a PPS resin composition having mechanical and electrical properties superior to those of the prior art.

  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 blending a specific filler with a polyarylene sulfide filled resin, thereby completing the present invention. It came to.

That is, the present invention relates to a polyarylene filled resin composition and a sliding resin composition.
1. A resin composition comprising a polyarylene sulfide filled resin (A) and at least one filler (B) made of fine talc and finely baked talc, wherein the filler (B) 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.
2. Item 2. The polyarylene sulfide filled resin composition according to Item 1, wherein the filler (B) has a number average particle size of 0.05 μm to 1 μm and at least 50% by weight is 0.1 μm to 0.4 μm.
3. Item 3. The polyarylene sulfide filled resin composition according to Item 1 or 2, wherein the polyarylene sulfide filled resin (A) is contained in an amount of 20 to 95 wt% in the resin composition.
4). Item 4. The polyarylene sulfide filled resin composition according to any one of Items 1 to 3, wherein the filler (B) is contained in an amount of 5 to 300 parts by weight per 100 parts by weight of the polyarylene sulfide filled resin (A).
5). Item 5. The polyarylene sulfide filled resin composition according to any one of Items 1 to 4, wherein the polyarylene sulfide filled resin (A) is a polyphenylene sulfide resin.
6). 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 70% relative humidity and a temperature of 25 ° C. for one month and dispersing the talc fine powder A with an ultrasonic wave 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 _{6. The polyarylene sulfide} filled resin composition according to any one of Items 1 to 5, wherein the ratio [D50 _{19.5 kHz} / D50 _{45 kHz} ] is 0.88 or more.
7). Item 7. The polyarylene sulfide filled resin composition according to Item 6, wherein the talc fine powder has an aspect ratio of 15 or more.
8). Item 8. The polyarylene sulfide filled resin composition according to Item 6 or 7, wherein the talc fine powder has a bulk specific gravity of 0.12 or less.
9. The polyarylene sulfide filled resin composition according to claim 1, wherein 100 parts by weight of the polyarylene sulfide filled resin (A) is used.
(1) Filler (B): 5 to 30 parts by weight,
(2) Fluororesin powder: 3-70 parts by weight,
(3) Polyolefin resin: 1 to 40 parts by weight,
(4) An inorganic filler (however, excluding the filler): 2 to 10 parts by weight and (5) a fibrous reinforcing agent: 1 to 10 parts by weight of a sliding resin composition.
10. The coefficient of dynamic friction (JIS K7218) is 0.21 or less, the specific wear amount (JIS K7218) is 0.02 mm ³ / N / km or less, and the specific material wear rate (JIS K7218) is 0.002 mm ³ / N / km or less. Item 10. The sliding resin composition according to Item 9 above.
11. Item 11. The sliding resin composition according to Item 9 or 10, wherein the polyarylene sulfide-based resin (A) is a polyphenylene sulfide-based resin.

  Since the polyarylene sulfide filled resin composition of the present invention contains fine talc particles and / or fine baked talc particles having a specific particle size, the mechanical properties inherent to PPS resins are maintained. However, excellent electrical properties such as arc resistance, tracking resistance and solder heat resistance can be exhibited.

  In addition, the sliding resin composition of the present invention contains fine talc particles and / or fine baked talc particles having a specific particle size in the PPS resin as a slidability improving agent. Can exhibit sliding characteristics. Particularly, since it has a slidability (low dynamic friction coefficient, low specific wear amount, low wear amount of the other material, etc.) that is balanced, it is suitable as a machine part. When the sliding resin composition of the present invention is used as a sliding part, it is possible to meet a maintenance-free request.

1. Polyarylene sulfide-filled resin composition The polyarylene sulfide-filled resin composition of the present invention comprises a polyarylene sulfide-filled resin (A) and a resin comprising at least one filler (B) made of fine talc and finely baked talc. The composition is characterized in that the filler (B) 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.

Polyarylene sulfide-based resin The polyarylene sulfide-based resin (PPS resin) used in the present invention is not limited, and the same resins as those used in conventional PPS resins can be used. . For example, a homopolymer, a random copolymer, a block copolymer, a cross-linked product thereof, or two or more of these containing a repeating unit having a structure in which an aromatic ring which may have a substituent and a sulfur atom are bonded And the like. Among these PPS resins, those having a structure in which the bond between the aromatic ring and the sulfur atom is in the para position with respect to the aromatic ring are preferable in terms of heat resistance and crystallinity.

  Typical examples of the PPS resin include PPS resins such as polyphenine sulfide, polyphenine sulfide ketone, polyphenine sulfide sulfone, and polyphenine sulfide ketone sulfone, and in particular, represented by the following structural formula (1). A PPS resin containing 70 mol% or more of the structural unit is preferable in terms of physical properties and economy.

  As a polymerization method of the PPS resin, for example, 1) a method of polymerizing p-dichlorobenzene and, if necessary, other copolymerization components in the presence of sulfur and sodium carbonate, 2) p-diethylene A method in which chlorobenzene and, if necessary, other copolymerization components are polymerized in a polar solvent in the presence of sodium sulfide or sodium sulfide and sodium hydroxide or in the presence of hydrogen sulfide and sodium hydroxide, 3) p -Method for self-condensing chlorothiophenol with other copolymerization components as required 4) Sodium sulfide in an amide solvent such as N-methylpyrrolidone and dimethylacetamide or a sulfone solvent such as sulfolane Examples thereof include a method of reacting p-dichlorobenzene with other copolymerization components if necessary. Among these, the method 4) is suitable. At this time, an alkali metal salt such as carboxylic acid or sulfonic acid may be added or an alkali hydroxide may be added in order to adjust the degree of polymerization.

  Examples of the copolymer component contained in the PPS resin include a meta bond represented by the following structural formula (2), an ether bond represented by the structural formula (3), and a sulfone bond represented by the structural formula (4). A sulfide ketone bond represented by Structural Formula (5), a biphenyl bond represented by Structural Formula (6), a substituted phenyl sulfide bond represented by General Formula (7), and a trifunctional phenyl sulfide represented by Structural Formula (8) Examples thereof include a bond and a naphthyl bond represented by the structural formula (9).

(In the formula, R represents an alkyl group, a nitro group, a phenyl group or an alkoxy group.)
The content of these copolymer components is usually 50 mol% or less, preferably 30 mol% or less. However, the content when trifunctional or higher functional bonds are contained is usually 5 mol% or less, preferably 3 mol% or less.

The melt viscosity (JIS, K7117) of the PPS resin used in the present invention is not particularly limited as long as it can be dissolved and kneaded, but is about 50 to 20000 P (5 to 2000 Pa · s) in a linear type or semi-linear type (test temperature: 320 ° C. , Shear rate: 10S- ¹ ) is preferable.

  The content of the polyarylene sulfide-based resin (A) in the composition of the present invention is generally 20 to 96% by weight, particularly 20 to 95% by weight. By setting within this range, the inherent properties of the PPS resin can be effectively maintained.

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

  The filler (B) 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. The following. When the number average particle diameter is less than 0.05 μm, it may be difficult to disperse in the resin. Further, when the number average particle diameter exceeds 1 μm, desired electrical characteristics may not be obtained. The number average particle diameter in the present invention indicates a value measured using a laser diffraction particle size distribution analyzer (product name “SALD-2000J” manufactured by Shimadzu Corporation).

  Further, the filler in the present invention has at least 50% by weight (50% diameter) in the particle diameter range of 0.1 μm to 0.9 μm, particularly in the range of 0.1 μm to 0.4 μm. desirable. By setting to the above range, a resin composition having both good mechanical properties and electrical properties 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. 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 alteration 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.

  In addition, when using finely baked talc (steatite particles) as a filler, for example, after calcination of commercially available talc particles at 800 ° C. or higher in advance, particle size adjustment (pulverization), classification, etc. are 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 put into a wet or dry jet mill and / or a bead mill and pulverized, whereby the number average particle diameter is 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. 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) A 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.

  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, various properties of the resin composition of the present invention can be further improved.

  The ratio of the filler (B) to the polyarylene sulfide filled resin is not limited, but generally, the filler (B) is 5 to 300 parts by weight with respect to 100 parts by weight of the polyarylene sulfide filled resin (A). It can set suitably according to the use etc. of this invention composition in the range of 5-200 weight part especially. For example, in applications that require arc resistance, tracking resistance, etc., the filler (B) is 30 to 300 parts by weight, particularly 30 to 200 parts by weight, with respect to 100 parts by weight of the polyarylene sulfide filled resin (A). It is desirable to do. In applications where sliding properties are required, the filler (B) is 5 to 30 parts by weight, particularly 10 to 25 parts by weight, and more preferably 10 to 25 parts by weight with respect to 100 parts by weight of the polyarylene sulfide filled resin (A). It is desirable to set it as 13-20 weight part.

Other Components In the composition of the present invention, components other than the components (A) and (B) can be appropriately blended depending on the use of the final product. For example, when used as a sliding material, add a resin other than PPS resin (fluorine resin, polyolefin resin, etc.), metal salt (metal sulfate salt, etc.), fiber reinforcing agent (glass fiber, carbon fiber, etc.) Can do. In addition, a pigment, a flame retardant, etc. can be mix | blended as needed.
<2. Sliding resin composition>
Among the polyarylene sulfide filled resins of the present invention, those having the following composition can be suitably used as a sliding resin composition.

That is, the present invention is based on 100 parts by weight of the polyarylene sulfide filled resin (A)
(1) Filler (B): 5 to 30 parts by weight,
(2) Fluororesin powder: 3-70 parts by weight,
(3) Polyolefin resin: 1 to 40 parts by weight,
(4) Inorganic filler (excluding the filler): 2 to 10 parts by weight and (5) Fibrous reinforcing agent: 1 to 10 parts by weight A resin composition for sliding is included.

Polyarylene sulfide-based resin The polyarylene sulfide-based resin includes the above-mentioned 1. Those listed in (1) can be used.

  The content of the polyarylene sulfide-based resin (A) in the sliding resin composition is generally 35 to 93% by weight, and particularly preferably 35 to 90% by weight. By setting within this range, the inherent properties of the PPS resin can be effectively maintained.

As the filler , the above-mentioned 1. The same fillers listed in (1) can be used.

  The content of the filler is 5 to 30 parts by weight, preferably 10 to 25 parts by weight, more preferably 13 to 20 parts by weight with respect to 100 parts by weight of the polyarylene sulfide filled resin (A). By setting within this range, balanced sliding characteristics can be effectively exhibited.

The kind of fluororesin powder fluororesin is not limited, and a known or commercially available fluororesin can be used. For example, polytetrafluoroethylene (PTFE), ethylene trifluoride chloride resin, vinyl fluoride resin, vinylidene fluoride resin, or the like can be used.

  The average particle size of the fluororesin powder is not limited, but is usually about 1 to 30 μm, and preferably 1 to 10 μm. Therefore, for example, PTFE can be obtained by subjecting a polymer obtained by suspension polymerization or emulsion polymerization of tetrafluoroethylene to a treatment such as pulverization and classification, and further radiation-crosslinked as necessary. If the average particle size is too large, the specific wear during sliding may increase. On the other hand, if the average particle size is too small, the reinforcing action is lost, it is difficult to contribute to the increase in rigidity, and the dynamic friction coefficient may be lowered.

  The blending amount of the fluororesin powder is preferably about 3 to 70 parts by weight, and more preferably about 5 to 40 parts by weight with respect to 100 parts by weight of the PPS resin. If the blending amount is excessive, the relative fluororesin ratio increases, and the overall specific wear amount may increase. PTFE has a small surface friction coefficient, but is inferior in wear resistance. If the blending amount is too small, it is difficult to achieve blending effects (dynamic friction coefficient reduction, material fluidity improvement).

The kind of polyolefin resin polyolefin resin is not limited, If it is not contained in the said PPS type resin and fluororesin, a well-known or commercially available thing can be used. For example, polyethylene modified with polyethylene (ethylene homopolymer), ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic acid anhydride, and the like are preferable.

  The polyolefin resin is usually blended in the form of a powder. The average particle size in this case is not limited, but is usually 100 μm or less, and preferably 1 to 50 μm. If the average particle size is excessively large, the transfer film at the time of sliding becomes excessive, and the apparent specific wear amount may increase. On the other hand, if the average particle size is too small, it is difficult to form a transfer film, and it may be difficult to obtain the effect (reduction of the dynamic friction coefficient) of the polyolefin.

  The content of the polyolefin resin is preferably about 1 to 40 parts by weight, more preferably about 2 to 20 parts by weight with respect to 100 parts by weight of the PPS resin. If the blending amount is excessive, it becomes difficult to obtain practical heat resistance in the molded product. If the blending amount is too small, it becomes difficult for the sliding component to be transferred to the counterpart material, and it is difficult to achieve the polyolefin blending effect (dynamic friction coefficient reduction, material fluidity improvement).

Inorganic filler (excluding the filler)
Any inorganic filler may be used as long as it enhances sliding properties, and in particular, metal sulfate, graphite, sulfide (such as molybdenum disulfide, tungsten disulfide, bismuth trisulfide), boron nitride, graphite fluoride, etc. Species or two or more species can be suitably used.

  Among these, metal sulfate is preferable in the present invention. More preferably, it is at least one of alkali metal sulfate and alkaline earth metal sulfate. Examples of the alkali metal sulfate include sodium sulfate and potassium sulfate. Examples of the alkaline earth metal sulfate include calcium sulfate and magnesium sulfate.

  The average particle size of the inorganic filler is not particularly limited, but is generally 5 to 200 μm, particularly preferably 10 to 50 μm. By setting to the above range, the sliding characteristics can be more effectively enhanced.

  The content of the inorganic filler is usually about 5 to 30 parts by weight, particularly preferably 10 to 20 parts by weight with respect to 100 parts by weight of the PPS resin. If the content is excessive, the PPS sliding resin composition tends to be brittle. If the blending amount is too small, the sliding component is difficult to transfer to the counterpart material, and it is difficult to achieve the effect of blending metal sulfate (reducing dynamic friction coefficient, improving material fluidity).

Fibrous reinforcing agents Examples of fibrous reinforcing agents include inorganic fiber reinforcing agents such as glass fibers and carbon fibers, aromatic polyamide fibers (aramid), polybenzoxazole fibers, polyphenol fibers, polyester fibers, and polyacrylonitrile fibers. An organic fiber reinforcing agent can be mentioned. These can be used alone or in combination of two or more. In the present invention, it is preferable to use an organic fiber reinforcing agent from the viewpoint that there is little attack on the mating material and a reduction in the wear rate of the mating material can be expected. Of these organic fiber reinforcing agents, heat resistant fibers excellent in heat resistance, reinforcement and the like are desirable. Here, the heat-resistant fiber means one having a thermal decomposition temperature or a melting point of 300 ° C. or higher. These heat-resistant organic fibers can be used in the form of chopped strands or further pulverized milled fibers.

  The fiber diameter of the fibrous reinforcing agent is not particularly limited, but is generally 0.1 μm to 100 μm, and particularly preferably 0.5 μm to 30 μm. Moreover, although the fiber length of a fibrous reinforcing agent is not limited, Usually, it is preferable to set it as 5 micrometers-6 mm, especially 100 micrometers-5 mm.

  The content of the fibrous reinforcing agent is preferably 1 to 10 parts by weight, and more preferably 2 to 5 parts by weight with respect to 100 parts by weight of the PPS resin. If the content is excessive, the aggressiveness to the mating material increases, and the mating material specific wear amount may increase. Moreover, when the content is too small, it is difficult to achieve the effect of blending heat-resistant organic fibers (reducing specific wear).

Other Components In the sliding resin composition of the present invention, other components can be blended as necessary. For example, other resin components, stabilizers, internal lubricants and the like can be mentioned.

  As other resin components, for example, polyamide, polyester, polyphenylene ether (PPE), polyketone, polyimide, epoxy, polycarbonate, amino resin, coumarone indene resin, unsaturated polyester, and the like may be mixed. The blending amount thereof can be appropriately blended within the range of 1 to 100 parts by weight with respect to 100 parts by weight of the PPS resin depending on the properties required for the molded product.

  Various organic sliding powders such as waxes (polyethylene-based / paraffin-based), higher fatty acid amides, and silicon resin powders can also be used as appropriate. Furthermore, calcium carbonate, aluminum hydroxide, magnesium hydroxide and the like can be blended as inorganic powder other than the inorganic filler.

Physical properties of sliding resin composition The sliding resin composition of the present invention preferably has a coefficient of dynamic friction (JIS K7218) of 0.23 or less, particularly 0.21 or less. Further, specific wear rate (JIS K7218) is 0.02mm ³ / N / km or less, and particularly preferably 0.012mm ³ / N / km or less. Mating member ratio wear amount (JIS K7218) is 0.002mm ³ / N / km or less, and particularly preferably 0.0007mm ³ / N / km or less.
<3. Production Method of PPS Resin Composition and Sliding Resin Composition>
The manufacturing method of this invention composition can be implemented according to the manufacturing method of a well-known resin composition. For example, the above components may be kneaded by a conventional method to prepare a molding material in the form of pellets or blocks, and this may be used to mold into a desired shape.

  The molding method may be injection molding or extrusion molding, but for example, transfer molding, compression molding or the like can also be employed. Molding conditions vary depending on the type of PPS resin, the composition of the molding material, and the like. For example, in the case of injection molding, molding is performed by heating and melting at 302 to 357 ° C. The molding cycle may be in the range of 15 to 40 seconds.

The PPS slidable resin composition (sliding molded product) thus produced has a dynamic friction coefficient (JIS.K7218) of about 0.21 or less and a specific wear amount (same) of about 0.003 mm, as shown in the examples described later. ^3. Excellent sliding characteristics of ³ / N / km or less and a counterpart material specific wear amount (same as above) of about 0.0007 mm ³ / N / km or less.

Furthermore, in the case of a PPS slidable resin composition containing fine talc particles alone, the coefficient of dynamic friction (JIS K 7218) is about 0.15 or less, and the specific wear amount (the same) is 0.0015 mm ³ / N / km or less. Further, the wear amount of the counterpart material (same as above) is 0.0001 mm ³ / N / km or less, and further shows excellent sliding characteristics.

  The features of the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to the examples.

<Production Example 1>
Fine talc particles used in the present invention were produced.

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.

<Examples 1-3 and Comparative Examples 1-2>
According to each composition prescription shown in Table 1, each component is mixed with a blender, and the obtained PPS resin mixture is put into a 45 mm twin screw extruder and kneaded and mixed (kneading temperature 280 ° C. to 330 ° C.), then pellets And prepared.

Using this pellet, an in-line screw type injection molding machine was used to mold various electrical property measurement test pieces at a cylinder temperature of 320 ° C., a mold temperature of 150 ° C., an injection pressure of 1000 kgf / cm ² , and an injection speed of medium speed. Evaluated. The results are shown in Table 1.

In addition, each component shown in Table 1 is specifically as follows.
(1) PPS resin: Dainippon Ink & Chemicals, Inc. “Dick T-4G”
(2) Fine talc particles a: fine talc particles having a number average particle diameter of 0.05 μm to 1 μm obtained in Production Example 1, of which 50% by weight has a particle size of 0.1 to 0.9 μm (3 ) Fine talc particles b: fine talc particles obtained in the same manner as in Production Example 1, having a number average particle diameter of 0.05 μm to 1 μm, of which 50% by weight is 0.1 μm to 0.4 μm. Fine talc particles.
(4) Fine calcined talc particles: manufactured by Nippon Talc Co., Ltd. Fine calcined talc particles having a number average particle diameter of 0.05 μm to 1 μm, of which 50% by weight is 0.1 μm to 0.9 μm (5) Microace P-4: Nippon Talc Co., Ltd. D50: 4.5 μm
(6) SG-95: Nippon Talc Co., Ltd. D50: 2.5 μm

<Examples 4-5 and Comparative Examples 3-4>
The raw materials used in Examples 1 to 3 and Comparative Examples 1 and 2 were changed in the type of talc particles. A pellet was prepared under the same conditions as in 2. Molding temperature 340 ° C. Each of the pellets, injection pressure (primary pressure 1200kgf ^/ cm 2 (117.6MPa), holding pressure (secondary ^{pressure) 500kgf / cm 2 (49MPa)} , injected at a rate of 20 seconds between the injection dwell time By molding, a wear test piece (hollow cylinder having an outer diameter of 25.6 mm, an inner diameter of 20 mm, and a height of 15 mm) for use in a plastic sliding wear test method (JIS K 7218) was prepared.

  PPS resin (T-4G) / polyethylene powder / PTFE / aramid fiber / potassium sulfate / various talc = 62/3/10/3/10/12 Wear test specimens were subjected to the frictional wear test specified in the above JIS, The dynamic friction coefficient and specific friction amount for each test piece, and the specific wear amount of the counterpart material (carbon steel, S45C) were determined. For the friction and wear test, the Suzuki type friction and wear test was conducted, and for the friction and wear test, the following conditions were used.

Conditions: Load 20 kgf / cm ² (1.96 MPa), peripheral speed 30 cm / sec, travel distance 10 km These results are shown in Table 2 to Tables 4 to 5 showing balanced sliding characteristics. I understand.

<Example 6>
As fine talc particles, talc fine powder obtained in the following Production Example 1 was used, and a PPS resin composition was prepared in the same manner as in Example 1 and Example 4 to produce pellets. As a result of conducting tests similar to those in Example 1 and Example 4 for each of the obtained pellets, results almost the same as those in Example 1 and Example 4 were obtained.

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 (11)

A resin composition comprising a polyarylene sulfide filled resin (A) and at least one filler (B) made of fine talc and finely baked talc, wherein the filler (B) 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. 2. The polyarylene sulfide filled resin composition according to claim 1, wherein the filler (B) has a number average particle diameter of 0.05 μm to 1 μm and at least 50 wt% is 0.1 μm to 0.4 μm. The polyarylene sulfide filled resin composition (A) according to claim 1 or 2, wherein the polyarylene sulfide filled resin (A) is contained in an amount of 20 to 95% by weight in the resin composition. The polyarylene sulfide filled resin composition according to any one of claims 1 to 3, wherein the filler (B) is contained in an amount of 5 to 300 parts by weight per 100 parts by weight of the polyarylene sulfide filled resin (A). The polyarylene sulfide filled resin composition according to any one of claims 1 to 4, wherein the polyarylene sulfide filled resin (A) is a polyphenylene sulfide resin. 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 70% relative humidity and a temperature of 25 ° C. for one month and dispersing the talc fine powder A with an ultrasonic wave 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 _{polyarylene sulfide} filled resin composition according to any one of claims 1 to 5, _wherein the ratio [D50 _{19.5 kHz} / D50 _{45 kHz} ] is 0.88 or more. The polyarylene sulfide filled resin composition according to claim 6, wherein an aspect ratio of the talc fine powder is 15 or more. The polyarylene sulfide filled resin composition according to claim 6 or 7, wherein the bulk specific gravity of the talc fine powder is 0.12 or less. The polyarylene sulfide filled resin composition according to claim 1, wherein the polyarylene sulfide filled resin (A) is 100 parts by weight.
(1) Filler (B): 5 to 30 parts by weight,
(2) Fluororesin powder: 3-70 parts by weight,
(3) Polyolefin resin: 1 to 40 parts by weight
(4) An inorganic filler (excluding the filler): 2 to 10 parts by weight and (5) Fibrous reinforcing agent: 1 to 10 parts by weight of a sliding resin composition. The coefficient of dynamic friction (JIS K7218) is 0.21 or less, the specific wear (JIS K7218) is 0.02 mm ³ / N / km or less, and the specific wear of the mating material (JIS K7218) is 0.002 mm ³ / N / km or less. The sliding resin composition according to claim 9. The sliding resin composition according to claim 9 or 10, wherein the polyarylene sulfide-based resin (A) is a polyphenylene sulfide-based resin.