JP2003292799A - Filler master batch and thermoplastic elastomer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a filler master batch which highly improves the dispersion of a filler on the production of a thermoplastic elastomer composition, and to obtain the thermoplastic elastomer composition containing the same. <P>SOLUTION: The filler master batch is obtained by mixing (a) 100 pts.wt. of a filler, especially at least one filler selected from the group consisting of metallic fillers, non-metallic fillers and carbon-based fillers with (b) 5 to 50 pts.wt. of a saturated or unsaturated aliphatic hydrocarbon group-containing phenol compound, and the thermoplastic elastomer composition is obtained by using the same. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a filler masterbatch and a thermoplastic elastomer composition using the same, and particularly to a filler masterbatch having improved filler dispersibility and a thermoplastic elastomer composition using the same. Regarding

[0002]

2. Description of the Related Art In recent years, a thermoplastic elastomer, which is a soft material having rubber elasticity and which does not require a vulcanization step and has the same moldability and recyclability as a thermoplastic resin, has been used in automobile parts, home electric appliance parts, It is widely used in the fields of wire coating, medical parts, footwear, and sundries. Conventionally, thermoplastic elastomers are sometimes used as styrene-based elastomers or olefin-based elastomers alone, but they are manufactured to have a predetermined hardness by adding oil as a plasticizer and olefin-based resin as a resin component to them. As the oil, paraffinic oil is often used. In addition, many of these thermoplastic elastomers have a filler added, and the filler is not only used as an extender, but also has conductivity, magnetism, thermal conductivity, piezoelectricity, and vibration damping. It is used when imparting the thermoplastic elastomer with functions such as heat resistance, sound insulation, slidability, heat insulation, electromagnetic wave absorption, flame retardancy, and gas barrier properties.

The filler is often added at a high concentration, depending on the use of the thermoplastic elastomer. At that time, it is important to disperse the filler in the thermoplastic elastomer. Particularly, a large amount of paraffin oil or the like is used. In the blended thermoplastic elastomer, its dispersibility is very important in terms of the physical properties of the thermoplastic elastomer. Usually, the filler is added to the thermoplastic elastomer by using a masterbatch, but when the filler is added at a high concentration, the property of the masterbatch is that the filler disperses in the thermoplastic elastomer. There is a problem that the inorganic filler is apt to cause deterioration of mechanical properties and deterioration of moldability due to poor dispersion.

[0004]

SUMMARY OF THE INVENTION In view of the above problems, the present invention provides a filler masterbatch in which the filler is very well dispersed even when the filler is added to the thermoplastic elastomer at a high concentration, and An object is to provide a thermoplastic elastomer composition containing the same.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor found that when a suitable amount of a saturated or unsaturated aliphatic hydrocarbon group-containing phenol is mixed with the filler, By treating the surface with a saturated or unsaturated aliphatic hydrocarbon group-containing phenol, even when a filler is added at a high concentration to the thermoplastic elastomer,
The inventors have found that it is possible to impart the function of the filler without causing deterioration of mechanical properties and deterioration of molding processability, and have completed the present invention.

That is, the first aspect of the present invention is (a)
It is a filler masterbatch obtained by mixing 100 parts by weight of the filler and (b) 5 to 50 parts by weight of the saturated or unsaturated aliphatic hydrocarbon group-containing phenols.

The second invention of the present invention is characterized in that (a) the filler is at least one filler selected from the group consisting of metallic, non-metallic and carbonaceous fillers. The filler masterbatch according to the first invention.

A third aspect of the present invention is characterized in that the filler (a) has an average particle size of 75 μm or less and a BET specific surface area of 0.01 m ² / g or more. It is the filler masterbatch according to the first or second invention.

A fourth aspect of the present invention is that (b) the saturated or unsaturated aliphatic hydrocarbon group-containing phenol is
A mixture of a saturated or unsaturated aliphatic hydrocarbon group-containing phenol in which the number of carbon atoms of the aliphatic hydrocarbon group is 5 to 25, and a polymerized product thereof.
The filler masterbatch according to any one of the inventions.

A fifth aspect of the present invention is that (b) the saturated or unsaturated aliphatic hydrocarbon group-containing phenol is
The filler masterbatch according to any one of claims 1 to 4, which is a mixture of cardanol, curdole, and a polymer thereof.

The sixth aspect of the present invention is (c) 100 parts by weight of thermoplastic elastomer, (a) fillers 3 to 35.
The thermoplastic elastomer composition is characterized by containing 0 part by weight and (b) 0.2 to 120 parts by weight of a saturated or unsaturated aliphatic hydrocarbon group-containing phenol.

The seventh invention of the present invention is the filler masterbatch 5 to 350 according to any one of the first to fifth inventions, based on 100 parts by weight of the thermoplastic elastomer (c).
It is a method for producing a thermoplastic elastomer composition according to the sixth invention, characterized in that parts by weight are blended and kneaded.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Each component used in the filler masterbatch of the present invention, a production method, and a component of a thermoplastic elastomer composition using the same and a production method will be described.

1. Filler Masterbatch The filler (a) used in the present invention is a conventionally known filler used as a modifier for the thermoplastic elastomer composition and can be used without any limitation. Of these, metal-based, non-metal-based, and carbon-based fillers are preferable. The filler in the thermoplastic elastomer composition is not only used as an extender, but also has conductivity, magnetism, thermal conductivity, piezoelectricity, vibration damping, sound insulation, slidability, heat insulation, electromagnetic wave absorption, and difficulty. It is used when imparting functions such as flammability and gas barrier properties to the thermoplastic resin. Specific fillers that impart these functions are listed below.

Examples of the filler that imparts a conductive function include carbon black (acetylene black, Ketjen black, etc.), carbon fiber, carbon whiskers,
Examples thereof include metal foils and powders of silver, copper, aluminum, nickel and the like. Examples of the filler that imparts the magnetic function include various ferrites and magnetic iron oxides. Examples of the filler that imparts thermal conductivity include metal foils and powders of alumina, graphite, magnesium oxide, copper and the like. Examples of the filler that imparts piezoelectricity include barium titanate and lead zirconate titanate.
Examples of the filler for imparting vibration damping property include mica, graphite, montmorillonite, vermiculite, carbon fiber,
Kevlar fiber etc. are mentioned. Examples of the filler that imparts sound insulation include lead powder, iron powder, barium sulfate, and ferrite. Examples of the filler that imparts slidability include graphite, molybdenum disulfide, talc, polytetrafluoroethylene resin powder, and the like. Examples of the filler that imparts heat insulation include glass balloons, shirasu balloons, silica balloons, and the like. Examples of the filler that imparts electromagnetic wave absorption include ferrite,
Examples thereof include graphite, carbon fiber, carbon whiskers and the like.
Examples of the flame-retardant filler include aluminum hydroxide, magnesium hydroxide, antimony oxide, zinc borate, hydrotalcite, red phosphorus and the like. Examples of the filler that provides gas barrier properties include mica, montmorillonite, and catechin.

When the filler used in the present invention is in powder form,
The average particle size is preferably 75 μm or less, and more preferably 0.1 to 50 μm. If the average particle size exceeds 75 μm, the foreign matter effect becomes remarkable and the mechanical properties of the thermoplastic elastomer deteriorate. Here, the average particle size of the filler is a value measured by a laser diffraction / scattering method.

Further, the filler used in the present invention is BET.
Law specific surface area preferably at least 0.01 m ² / g, more preferably 0.05~1300m ² / g. When the BET method specific surface area is 0.01 m ² / g or less, dispersibility is deteriorated due to aggregation and mechanical properties of the thermoplastic elastomer are deteriorated. Here, the BET method specific surface area is a value measured by the N ₂ gas BET 1 point method.

The saturated or unsaturated aliphatic hydrocarbon group-containing phenol (b) used in the present invention is a compound in which the aliphatic hydrocarbon group has 5 to 25 carbon atoms, preferably 10 to 20 carbon atoms, and those compounds. It is a mixture of polymers. The aliphatic hydrocarbon group may be linear or may contain a side chain, but is preferably linear. Among them, more preferable are cardanol, curdole, and a mixture thereof. Cardanol and curdole are saturated or unsaturated aliphatic hydrocarbon group-containing phenols present in cashew nut shell liquid extracted from cashew nut shells, and among them, it is preferable to contain one or more unsaturated bonds. . More preferably, it is 1 to 3. The cashew nut shell liquid containing cardanol as a main component is used as a polymer obtained by polymerizing the monomer thereof into a dimer or more by heating it under an acid catalyst. The degree of polymerization is 2 to 8 on average. When the average degree of polymerization is low, the proportion of the monomers in cashew nut shell liquid increases, and the rash is likely to occur when the skin is touched. On the contrary, when the average degree of polymerization is high, it becomes solid. Therefore, as the polymer of cashew nut shell liquid, one having an average degree of polymerization of 2 to 8 is used, and preferably one having an average degree of polymerization of 2 to 4 is used.
The polymer has a viscosity of 0.5 to 30.
Pa · s is preferable, and 1 to 25 Pa · is more preferable.
s, more preferably about 1 to 20 Pa · s. Further, preferably, the contents of cardanol and curdole are 90% by weight and 10% by weight, respectively. As a concrete commercial product, cashew oil BX-3000 (viscosity: 10 to 20 Pa.
s), D-2000 (viscosity: 0.7 to 10 Pa · s),
PX-750 (0.1 to 0.7 Pa · s) and the like.

The blending amount of the component (b) is 100 parts of the component (a).
It is 5 to 50 parts by weight, and more preferably 5 to 20 parts by weight with respect to parts by weight. If the blending amount is 5 parts by weight or less,
When the dispersibility of the filler is not improved and the blending amount exceeds 50 parts by weight, the amount of alkylphenols becomes too large and the alkylphenols are separated, resulting in poor handleability. Further, when added to the thermoplastic elastomer, odor becomes remarkable.

In the filler masterbatch of the present invention, in addition to the above components, an antiblocking agent, a heat stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a lubricant, a colorant, a thickener, Antiaging agents and the like can be added.

2. Manufacture of Masterbatch The filler masterbatch of the present invention is obtained by adding the above-mentioned components (a) and (b) and, if necessary, additives and the like, and uniformly mixing and kneading. Mixing, the method of kneading is not particularly limited, after generally dry blending with a mixer such as a Henschel mixer, a ribbon blender, a tumbler that is commonly performed, a single-screw extruder,
It can be obtained by kneading using a twin-screw extruder or the like. Also,
It can also be obtained by kneading using a device in which a pressure kneader and an extruder are combined (batch feeding type continuous extrusion device). Here, the kneading temperature is preferably room temperature.

3. Thermoplastic Elastomer Composition The thermoplastic elastomer composition of the present invention is a resin composition containing (c) a thermoplastic elastomer, (b) a filler, and (b) a saturated or unsaturated aliphatic hydrocarbon group-containing phenol. It is a thing. (B) In a thermoplastic elastomer composition in which saturated or unsaturated aliphatic hydrocarbon group-containing phenols are present on the surface of a filler to improve the dispersibility of the filler and to mix a high concentration of the filler. It is possible to exhibit the function of the filler without causing deterioration of mechanical properties and deterioration of molding processability.

The filler (a) used in the thermoplastic elastomer composition of the present invention is the same as the filler used in the above-mentioned masterbatch, and (b) contains a saturated or unsaturated aliphatic hydrocarbon group. As phenols,
It is the same as that used in the above-mentioned masterbatch.

Examples of the thermoplastic elastomer (c) used in the present invention include styrene elastomers such as styrene-butadiene rubber (SBR) and styrene-
Butadiene-styrene rubber (SBS), hydrogenated styrene-butadiene rubber (H-SBR), styrene-ethylene-butene-styrene rubber (SEBS), partially hydrogenated styrene-butadiene-styrene rubber (SBBS), styrene-isoprene-butadiene -Styrene rubber (SIB
S), hydrogenated styrene-isoprene-butadiene-styrene rubber (SEEPS), styrene-isoprene-styrene rubber (SIS), ABS and the like; non-diene rubbers such as olefin elastomers such as ethylene-propylene rubber (EPR), Ethylene-butene rubber (EB
R), ethylene-propylene non-conjugated diene rubber (EPD
M), ethylene-α-olefin copolymers synthesized using a metallocene catalyst, engineering plastic elastomers such as polyester elastomers, polyamide elastomers and polyurethane elastomers. Of the above, styrene elastomers and olefin elastomers are preferably used. In addition, softening agents for rubber, polyolefin resins, other fillers,
It may be one to which a cross-linking agent, a cross-linking auxiliary agent or the like is added.

The mixing ratio of each component in the thermoplastic elastomer composition of the present invention is preferably 3 to 350 parts by weight of (a) filler, and (b) saturated or 100 parts by weight of thermoplastic elastomer (c). 0.2 to 120 parts by weight of unsaturated aliphatic hydrocarbon group-containing phenols are preferable.

4. Production of Thermoplastic Elastomer Composition The production method of the thermoplastic elastomer composition of the present invention is particularly preferably, as long as it contains the above components (a) to (c) and improves the dispersibility of the (a) filler. , Without limitation, (c)
A method of using the above-mentioned filler masterbatch of the present invention in a thermoplastic elastomer is preferable, and a method obtained by blending the filler masterbatch and the thermoplastic elastomer (c) and then kneading them using a kneading device is particularly preferable. preferable.

When a masterbatch is used, it is preferable to mix 5 to 350 parts by weight of the filler masterbatch of the present invention with 100 parts by weight of the thermoplastic elastomer (c) and knead.

Specifically, the filler masterbatch of the present invention and a thermoplastic elastomer are blended to obtain 160-230.
Melt kneading is carried out in a kneading device at a kneading temperature of ° C to obtain a desired thermoplastic elastomer composition. Alternatively, the molded product can be molded by an extrusion molding machine or an injection molding machine having a kneading function. The kneading device used in the present invention includes a pressure kneader, a Banbury mixer, a single screw extruder, a twin screw extruder,
A multi-screw extruder or the like can be used. A kneading method using a batch-type kneading apparatus such as a pressure kneader or Banbury is preferable. In the case of continuous kneading, a method in which a batch-type kneading device and an extruder are combined, for example, a device in which a pressure kneader and an extruder are combined (batch-feed type continuous extruder) is preferable.

[0029]

EXAMPLES The present invention will be specifically described with reference to the following examples and comparative examples, but the present invention is not limited to these examples. The measuring methods of physical properties and samples used in the present invention are shown below.

1. Physical property measuring method (1) Tensile strength: According to JIS K 6251, a 1 mm thick press sheet was punched out into a No. 3 dumbbell type test piece to be used. The pulling speed was 500 mm / min. (Measurement at room temperature and 100 ° C.) (2) 100% elongation stress: According to JIS K 6251, a 1 mm thick press sheet was punched out into a No. 3 dumbbell type test piece for use. Pulling speed is 500mm /
Minutes (3) Elongation at break: According to JIS K 6251, a 1 mm thick press sheet was used as a test piece by punching out a No. 3 dumbbell type test piece. The pulling speed was 500 mm / min. (4) Injection moldability: using an injection molding machine with a mold clamping pressure of 120 tons, molding temperature 220 ° C, mold temperature 40 ° C, injection speed 5
5 mm / sec, injection pressure 600 kg / cm ² , holding pressure 4
1 at 00 kg / cm ² , injection time 6 seconds, cooling time 45 seconds
A 3.5 x 13.5 x 2 mm sheet was molded. The presence or absence of flow marks that delaminate, peel off the surface layer, deform, and significantly deteriorate the appearance was visually evaluated, and evaluated according to the following criteria. ◯: Good ×: Poor (5) Extrudability: A 50 mm × 1 mm sheet was extrusion-molded, and the drawdown property, surface appearance and shape were observed and evaluated according to the following criteria. ○: Good ×: Poor (6) Bleed resistance: The extruded sheet that was bent and fixed with a clip was left at room temperature and 110 ° C. for 168 hours, and visually observed for the presence of bleeding and blooming of low molecular weight substances. It evaluated by the standard of. ○: Good ×: Bad

2. Sample (1) Magnesium oxide (a-1) used in Examples and Comparative Examples: Starmag SL
(MgO; Kamijima Chemical Co., Ltd.), apparent specific gravity;
1.8 g / ml, BET specific surface area; 2 m ² / g (2) Electrolytic copper powder (a-2): CE-115 (Cu; manufactured by Fukuda Metal Foil & Powder Co., Ltd.), apparent specific gravity; 1.53 g /
ml (3) Magnesium hydroxide (a-3): Magcise N-
3 (Mg (OH) ₂ ; manufactured by Kamijima Chemical Industry Co., Ltd.), apparent specific gravity; 0.6 g / ml, average particle diameter; 1.2 μm, B
ET specific surface area; 5 m ² / g (4) Saturated or unsaturated aliphatic hydrocarbon group-containing phenols (b): cashew oil BX-3000 (manufactured by Cashew Co., Ltd.), viscosity (30 ° C.); 16 Pa · s ( 5) Styrenic thermoplastic elastomer (c-1): Actimer AJ-1050S (manufactured by Riken Technos Co., Ltd.), MFR; 2.3 g / 10 min, specific gravity; 0.9
4, hardness; 50A

Examples 1 to 3 and Comparative Examples 1 to 2 Component (a-1), component (a-2), and component (a-3), saturated or unsaturated, aliphatic hydrocarbon groups are used as the filler. As the contained phenols, the component (b) was used, and the amounts shown in Table 1 were mixed, and the mixture was put into a 20-liter pressure kneader, and the vapor pressure was 3.0 kg / cm ² , 1 in gauge pressure.
Kneading was performed for 6 minutes until the temperature reached 10 ° C. Then, L / D = 20 with a rotary cutter at the tip, kneading temperature 5
A masterbatch was obtained with a single-screw extruder at 0 ° C. and a screw rotation speed of 80 rpm, and pelletized. Using a dry blend of 100 parts by weight of the obtained masterbatch and 50 parts by weight of the component (c) styrene-based elastomer, an injection molding apparatus was used to measure (length) 130 mm × (width) 130 mm ×
Test pieces (thickness) of 2 mm were molded under the following conditions and subjected to the respective tests. The evaluation results are shown in Table 1.

[0033] Molding temperature 220 ℃ Mold temperature 30 ℃ Injection speed 15mm / sec Injection pressure 800kg / cm^Two Holding pressure 200 kg / cm^Two Injection time 5 seconds Cooling time 20 seconds

[0034]

[Table 1]

As is clear from Table 1, the styrenic thermoplastic elastomer composition having a high filler concentration using the filler masterbatch of the present invention exhibits excellent physical properties and excellent dispersibility of the filler. It can be seen (Examples 1 to 3).
On the other hand, in the masterbatch which did not use the component (b), the dispersibility of the filler was poor and the surface properties of the injection / extrusion molded product were deteriorated (Comparative Example 1). Further, the masterbatch containing too much component (b) had poor mechanical properties (Comparative Example 2).

[0036]

INDUSTRIAL APPLICABILITY In the masterbatch of the present invention, the surface of the filler is surface-treated with a saturated or unsaturated aliphatic hydrocarbon group-containing phenol. Therefore, when the filler is added to the thermoplastic elastomer at a high concentration. Also in the above, it is possible to obtain an excellent thermoplastic elastomer composition which is excellent in dispersibility of the filler and does not cause deterioration of mechanical properties of the elastomer composition or deterioration of molding processability.

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Claims (7)

[Claims] 1. A weight ratio of (a) 100 parts by weight of a filler and (b) 5 phenols containing a saturated or unsaturated aliphatic hydrocarbon group.
A filler masterbatch obtained by mixing with 50 parts by weight. 2. The filler according to claim 1, wherein the (a) filler is at least one filler selected from the group consisting of metal-based, non-metal-based and carbon-based fillers. Wood masterbatch. 3. The filling according to claim 1, wherein the filler (a) has an average particle diameter of 75 μm or less and a BET specific surface area of 0.01 m ² / g or more. Wood masterbatch. 4. The saturated or unsaturated aliphatic hydrocarbon group-containing phenol (b) is a saturated or unsaturated aliphatic hydrocarbon group-containing phenol in which the aliphatic hydrocarbon group has 5 to 25 carbon atoms. The filler masterbatch according to any one of claims 1 to 3, wherein the filler masterbatch is a mixture of the polymer and a polymer thereof. 5. (b) The saturated or unsaturated aliphatic hydrocarbon group-containing phenols are cardanol, curdole,
The filler masterbatch according to any one of claims 1 to 4, wherein the filler masterbatch is a mixture of the polymer and a polymer thereof. 6. (c) 100 parts by weight of a thermoplastic elastomer, (a) 3 to 350 parts by weight of a filler, and (b) 0.2 of a saturated or unsaturated aliphatic hydrocarbon group-containing phenol.
The thermoplastic elastomer composition is characterized by containing ˜120 parts by weight. 7. (c) 5 to 350 parts by weight of the filler masterbatch according to any one of claims 1 to 5 is mixed with 100 parts by weight of the thermoplastic elastomer and kneaded. The method for producing the thermoplastic elastomer composition according to claim 6.