JP5297808B2 - Masterbatch and manufacturing method thereof - Google Patents

Abstract

A master batch comprising the following components (a) to (d): (a) an ethylene copolymer A having a density of 0.85 to 0.88 g/cm<SUP>3</SUP>, an MI value of 0.1 to 50 g/10 min and a melting point of 30 to 70ºC; (b) an ethylene copolymer B and/or an ethylene homopolymer each having a density of 0.895 to 0.925 g/cm<SUP>3</SUP>, an MI value of 1 to 50 g/10 min and a melting point of 90 to 130ºC; (c) a polypropylene resin having an MI value of 1 to 1000 g/10 min; and (d) an inorganic filler having a primary particle diameter of 1 to 10 µm, wherein the components (a) to (d) are contained at the following mixing ratios (by mass): ((a)+(b)+(c))/((a)+(b)+(c)+(d)) = 0.3 to 0.8; (a)/((a)+(b)+(c)) = 0.35 to 0.65; ((a)+(b))/((a)+(b)+(c)) = 0.5 to 1; (b)/((b)+(c)) = 0.15 to 1; and (b)/((a)+(b)+(c)) = 0.1 to 0.6.

Description

  The present invention relates to a masterbatch for polyolefin resin and a method for producing the same. Specifically, the present invention relates to a master batch used for manufacturing a polyolefin molded body mainly used for an interior / exterior material of an automobile and a manufacturing method thereof.

  Among polyolefin resins, polypropylene resins are excellent in rigidity and impact strength and are widely used. In particular, as an automobile material, a molded product obtained by injection molding or the like of a composition made of a polypropylene resin is frequently used. Molded articles as materials for automobiles are required to have mechanical properties such as rigidity and impact strength and excellent appearance, but at the same time, automobile manufacturers are required to further reduce prices. Therefore, cost reduction at the time of molding is also an important issue.

For example, as a technique for reducing the compounding cost, a highly functional filler masterbatch method and a direct inline compound method have been proposed (see Non-Patent Document 1). In the high-performance filler masterbatch method, materials corresponding to multiple parts can be supplied, and the entire molding plant can be rationalized. In addition, the direct inline compound method can greatly reduce costs by mass production using a polypropylene resin production line.
On the other hand, as a technology related to a master batch (MB: Master Batch) that is highly filled with a filler such as talc, MB that contains a rubber component to improve impact resistance (see Patent Document 1), and also impact resistance MBs containing a polyethylene resin for improvement (see Patent Document 2), or MBs containing a small amount of crystalline polypropylene resin for improving the blocking resistance of MB (see Patent Document 3) have been proposed. .

Future Materials Vol.5 No.10 (9 pages) Japanese Patent No. 3320031 JP-A-10-139949 JP 2002-69204 A

However, the high-performance filler masterbatch method in Non-Patent Document 1 does not have a sufficient cost-cutting effect, and the direct in-line compound method can provide a significant cost-cutting effect. There is a problem that it is difficult to deal with.
Moreover, although the technique of patent document 1 can provide high concentration talc containing MB, since there are many rubber components, there exists a problem that MB pellets block. In addition, the lubricity between MB pellets is poor, and so-called fluidity is also a problem. Similar problems remain in the technique of Patent Document 2, and even the technique of Patent Document 3 does not have sufficient improvement in blocking resistance.
Specifically, after mixing and melt-kneading raw materials to produce MB, pellets are often temporarily collected in a so-called catcher tank, but blocking at this time is a problem. In addition, blocking may occur even after the MB pellet is extracted from the catcher tank and stored in a flexible container or the like (for example, a 500 kg bag). Furthermore, in the dryer incorporated in the injection molding line, a high load is applied in a high temperature state, so that blocking is likely to occur, and blocking in the hopper also becomes a problem. When MB pellets are supplied from the hopper with the quantitative feeder, the so-called abrasion resistance that the MB pellets are rubbed with the rotating plate of the measuring unit and the scraped material adheres to the rotating plate becomes a problem.

  Therefore, an object of the present invention is to provide a masterbatch for polyolefin resin which can contribute to a sufficient cost reduction and which is excellent in blocking resistance, fluidity and shear resistance, and a method for producing the same.

In order to solve the above problems, the present invention is configured as follows.
(1) A master batch comprising the following components (a) to (d):
(A) Ethylene copolymer A having a density of 0.85 to 0.88 g / cm ³ , MI of 0.1 to 50 g / 10 min (190 ° C., 21.18 N), and a melting point of 30 to 70 ° C.
(B) The density is 0. 905-0. 915 g / cm ³ , MI 0.1 to 50 g / min (190 ° C., 21.18 N), melting point 90 to 130 ° C. and / or ethylene homopolymer (c) MI 1 A polypropylene resin (d) that is ˜1000 g / 10 min (230 ° C., 21.18 N), and an inorganic filler whose primary particle diameter is 1 to 10 μm. The mixing ratio (mass ratio) of the components (a) to (d) is as follows: A master batch characterized as follows.
((A) + (b) + (c)) / ((a) + (b) + (c) + (d)) = 0.3 to 0.8
(A) / ((a) + (b) + (c)) = 0.35-0.65
((A) + (b)) / ((a) + (b) + (c)) = 0.5-1
(B) / ((b) + (c)) = 0.15-1
(B) / ((a) + (b) + (c)) = 0.1-0.6

(2) The master batch according to (1), wherein the component (c) is a block polypropylene resin composed of a homopolypropylene part and an olefin copolymer part.

(3) The master batch according to (1) or (2), wherein the component (d) is talc.

(4) A method for producing the master batch according to any one of (1) to (3) above using a continuous biaxial kneader comprising a biaxial part, a kneading part and a short-axis extrusion part, The continuous biaxial kneader is a bi-directional rotating system in which the L / D of the screw of the biaxial portion is both in the range of 12 to 34 and is not meshed with each other, and the cross section of the kneading portion is a double wing. An orifice having a rotor shape and an L / D of the rotor of 6 to 18 and having a downstream cross-sectional end of the kneading section that can change the cross-sectional area of the kneaded melt to adjust the kneading degree. And after passing through the orifice, the kneaded melt is provided to the short-axis extrusion part, and the shear rate of the molten resin in the kneading part is set in the range represented by the following formula. How to make a masterbatch characterized by .
600 × (38 / D) ^{2 to} 2000 × (38 / D) ² (sec ⁻¹ )
(Here, D is the screw diameter (mm) in the kneading part.)

The master batch of the present invention is also excellent in blocking resistance, fluidity, and slip resistance of the master batch itself.
In particular, by setting each raw material of the masterbatch to the above-mentioned predetermined mixing ratio, both physical properties in a so-called trade-off relationship between blocking resistance and impact resistance can be remarkably improved, and further, fluidity and wear resistance can be further improved. An excellent inorganic filler-containing masterbatch can be provided. Conventionally, a method of blending a polypropylene resin (block PP) is known as a method for improving the blocking resistance while maintaining the impact resistance of the masterbatch (for example, Patent Document 3). There was a problem that a polymerization component (EP part) deteriorated blocking resistance. In the present invention, a masterbatch having a good balance between impact resistance and blocking resistance is provided by blending a specific amount of ethylene copolymer B having a specific density range as component (b).
And the masterbatch of this invention can be manufactured efficiently by using the above-mentioned specific continuous biaxial kneading method.
In addition, by using such a master batch and mixing with inexpensive general-purpose polypropylene resin (PP resin for dilution) with excellent productivity, such as instrument panels and door panels with excellent cost reduction effect and impact resistance. It is possible to provide automobile parts.

The figure which shows the masterbatch taking-out condition from a catcher tank in the Example of this invention. The figure which shows the blocking state of a masterbatch in the said Example. The figure which shows the evaluation method of abrasion resistance in the said Example. The figure which shows the evaluation method of abrasion resistance in the said Example. The figure which shows the evaluation method of abrasion resistance in the said Example. The figure which shows an example of the evaluation result of shear resistance in the said Example. The figure which shows an example of the evaluation result of shear resistance in the said Example.

Masterbatch of the present invention, the ethylene copolymer A low density 0.85~0.88g / cm ³ which is a component (a), a density 0.895~0.925g / cm ³ which is component (b) Of ethylene copolymer B and / or ethylene homopolymer, (c) component polypropylene resin, and (d) component inorganic filler.
Hereinafter, these will be described in detail.

[Configuration of master batch]
(A) Component:
As the ethylene copolymer A which is the component (a) of the present invention, what is called an ethylene-based thermoplastic elastomer is suitable in terms of improving impact resistance. As a specific example of such an elastomer, an ethylene / α-olefin copolymer is preferable in terms of imparting impact resistance.
The comonomer α-olefin is preferably one having 4 to 15 carbon atoms, more preferably 4 to 12. An ethylene-propylene copolymer (for example, EPM) using propylene having 3 carbon atoms is not preferable because of insufficient impact resistance.

The density of such an ethylene copolymer A is 0.85 to 0.88 g / cm ³ , preferably 0.855 to 0.875 g / cm ³ . When the density is less than 0.85 g / cm ³ , the master batch is likely to be blocked, and the abrasion resistance is also deteriorated. On the other hand, if the density exceeds 0.88 g / cm ³ , sufficient impact resistance cannot be obtained.
Moreover, MI (190 degreeC, 21.18N) of the ethylene copolymer A is 0.1-50 g / 10min, Preferably it is 0.5-40 g / 10min. When MI is less than 0.1 g / 10 min, dispersibility is deteriorated and impact resistance cannot be obtained. In addition, the resin temperature tends to rise during kneading during the production of the masterbatch, and there is a possibility that the masterbatch may be blocked in the catcher tank, for example. On the other hand, if MI exceeds 50 g / 10 min, for example, the master batch may be blocked in the injection molding line, or the fluidity of the master batch may be deteriorated. Furthermore, the abrasion resistance of the master batch is also deteriorated.

  Furthermore, the melting point of the ethylene copolymer A needs to be 30 to 70 ° C, and preferably 35 to 65 ° C. When a polymer having a melting point of less than 30 ° C. is used, the masterbatch is likely to be blocked, and the abrasion resistance of the masterbatch is also deteriorated. If the melting point exceeds 70 ° C., impact resistance cannot be obtained.

  Such an ethylene copolymer A as the component (a) is, for example, a Ziegler system such as a complex composed of a vanadium compound and an alkylaluminum compound, or a complex composed of a titanium compound such as titanium halide and an alkylaluminum-magnesium. It can manufacture suitably with a catalyst. Moreover, it can superpose | polymerize by the metallocene catalyst (Kaminsky catalyst) etc. which are described in international publication WO91 / 04257 grade | etc.,. As the polymerization method, polymerization can be performed by applying a production process such as a gas phase fluidized bed method, a solution method, or a slurry method.

(B) Component:
The component (b) of the present invention is an ethylene copolymer B and / or an ethylene homopolymer having a density of 0.895 to 0.925 g / cm ³ , but has a high level of impact resistance and blocking resistance of the masterbatch. Therefore, an ethylene / α-olefin copolymer is preferable.
In the case of an ethylene / α-olefin copolymer, the α-olefin preferably has 4 to 15 carbon atoms, more preferably 4 to 12. An ethylene-propylene copolymer using propylene having 3 carbon atoms is not preferable because of insufficient impact resistance.

The density of such ethylene copolymer B or ethylene homopolymer is 0.895 to 0.925 g / cm ³ , preferably 0.9 to 0.92 g / cm ³ , more preferably 0.905 to 0. 915 g / cm ³ . When the density is less than 0.895 g / cm ³ , for example, blocking tends to occur in the catcher tank of the master batch production line. Further, even in the injection molding line, the flowability of the master batch is deteriorated and blocking is likely to occur. Furthermore, the abrasion resistance of the master batch is also deteriorated. On the other hand, if the density exceeds 0.925, the impact resistance deteriorates, which is not preferable.
Moreover, MI (190 degreeC, 21.18N) of ethylene copolymer B or an ethylene homopolymer is 0.1-50 g / 10min, Preferably it is 0.5-40 g / 10min. When MI is less than 0.1 g / 10 min, dispersibility is deteriorated and impact resistance cannot be obtained. In addition, the resin temperature tends to rise during kneading during the production of the masterbatch, and there is a possibility that the masterbatch may be blocked in the catcher tank, for example. On the other hand, if MI exceeds 50 g / 10 min, impact resistance cannot be obtained.
Further, the melting point of the ethylene copolymer B or the ethylene homopolymer needs to be 90 to 130 ° C. If the melting point is less than 90 ° C., blocking tends to occur in the catcher tank of the masterbatch production line. Further, even in the injection molding line, the flowability of the master batch is deteriorated and blocking is likely to occur. Furthermore, the abrasion resistance of the master batch is also deteriorated. On the other hand, if the melting point exceeds 130 ° C., impact resistance cannot be obtained.
Surprisingly, when such an ethylene copolymer B and / or an ethylene homopolymer is used as the component (b) in the present invention, a so-called block usually used by those skilled in the art for improving the blocking resistance of a masterbatch. Compared to polypropylene (block PP), the blocking resistance and impact resistance of the master batch can be further improved. In order to improve blocking resistance, homo PP and block PP having a high melting point are used, but this composition achieves improvement while using a resin different from the common sense of those skilled in the art.

Among the components (b), the ethylene copolymer B is, for example, a gas phase fluidized bed method, a solution method, a slurry method, or a pressure in the presence of an ion polymerization catalyst such as a Ziegler catalyst, a Phillips catalyst, or a Kaminsky catalyst. It can be produced by copolymerizing ethylene and α-olefin by applying a production process such as high pressure ion polymerization of 200 kg / cm ² or more and a temperature of 150 ° C. or more. Such a copolymer is also called LLDPE. The ethylene homopolymer can be produced as a so-called high-pressure low-density polyethylene (LDPE) by polymerizing ethylene alone in the presence of peroxide under high pressure.

(C) Component:
The component (c) of the present invention is a polypropylene resin and may be a propylene homopolymer, but a propylene-propylene / ethylene copolymer (block PP) is preferred from the viewpoint of improving impact resistance. The production method is not particularly limited, and a method generally used for producing a polypropylene resin can be used.
Moreover, MI of polypropylene resin is 1-1000 g / 10min, Preferably, it is 3-600. When MI is less than 1 g / 10 min, the resin temperature tends to rise during kneading in the production of the master batch, and there is a possibility that the master batch may be blocked in the catcher tank, for example. Moreover, the moldability at the time of injection molding deteriorates. On the other hand, when MI exceeds 1000 g / 10 min, impact resistance cannot be obtained.

(D) Component:
The component (d) of the present invention is an inorganic filler, and the shape of the inorganic filler used is not particularly limited, and any shape such as granular, plate-like, rod-like, fibrous, whisker-like can be used. can do. Examples of inorganic fillers include silica, diatomaceous earth, barium ferrite, alumina, titanium oxide, magnesium oxide, beryllium oxide, oxides such as pumice and pumice balloons, water such as aluminum hydroxide, magnesium hydroxide, and basic magnesium carbonate. Oxides, carbonates such as calcium carbonate, magnesium carbonate, dolomite, dawsonite, sulfates or sulfites such as calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass Balloons, glass beads, calcium silicate, montmorillonite, bentonite, kaolinite and other clay minerals and silicates and their organic compounds (organized clay), carbon black, graphite, carbon fibers, carbon hollow spheres and other charcoal S and, molybdenum sulfide, boron fiber, zinc borate, barium metaborate, calcium borate, sodium borate, magnesium oxysulfate, various metal fibers and the like.

These inorganic fillers may be used alone or in combination of two or more. In the polyolefin resin composition for injection molding, among these, talc, mica, calcium carbonate, and glass fiber are preferable, and talc is particularly preferable. As for the size of the inorganic filler, the average particle size (primary particles) by laser method is 1 to 1 from the viewpoint of physical properties such as rigidity, impact resistance, scratch-resistant whitening, weld appearance, gloss unevenness of the molded product obtained. 10 μm, preferably 3 to 8 μm is used. When the average particle size is less than 1 μm, the dispersibility of the inorganic filler cannot be obtained, and not only the appearance of the master batch is deteriorated, but also the impact resistance is not obtained. On the other hand, even if the average particle size exceeds 10 μm, impact resistance cannot be obtained, and heat resistance is also deteriorated. Furthermore, the scratch resistance is also deteriorated. The average aspect ratio is preferably 4 or more.
Further, when talc is used as the inorganic filler, those obtained by processing and pulverization are particularly preferable in terms of physical properties and rigidity. In particular, it is preferable to use so-called compression talc by compressing and degassing talc and increasing the bulk specific gravity to 0.4 to 1, preferably 0.5 to 0.9. When the bulk specific gravity is less than 0.4, talc classification tends to occur when other components and talc are collectively blended and fed to the melt-kneading system, making it difficult to obtain a master batch having a uniform composition. Furthermore, the productivity of the master batch is also deteriorated. On the other hand, if the bulk specific gravity exceeds 1, the resin temperature tends to rise during kneading in the production of the master batch, and there is a risk that the master batch will be blocked in the catcher tank, for example. Further, such a high specific gravity compressed talc also increases the production cost.

About the compounding ratio (mass ratio) of above-described (a)-(d) component, it is necessary for X shown by a following formula to exist in the range of 0.3-0.8.
X = ((a) + (b) + (c)) / ((a) + (b) + (c) + (d))
When X is less than 0.3, the components (a) and (b), which are relatively imparting impact resistance, are insufficient, and impact resistance cannot be obtained when, for example, an injection molded product is obtained. On the other hand, if X exceeds 0.8, the amount of master batch used increases, and a cost reduction effect cannot be obtained. X is more preferably in the range of 0.35 to 0.7.

About the compounding ratio (mass ratio) of above-described (a)-(c) component, it is necessary for Y shown by a following formula to exist in the range of 0.35-0.65.
Y = (a) / ((a) + (b) + (c))
If Y is less than 0.35, impact resistance cannot be obtained. On the other hand, if X exceeds 0.65, the master batch is likely to be blocked and the abrasion resistance of the master batch is also deteriorated. Y is more preferably in the range of 0.4 to 0.6, and still more preferably in the range of 0.45 to 0.55.

About the compounding ratio (mass ratio) of above-described (a)-(c) component, it is necessary for Z shown by a following formula to exist in the range of 0.5-1.
Z = ((a) + (b)) / ((a) + (b) + (c))
If Z is less than 0.5, impact resistance cannot be obtained. Z is more preferably in the range of 0.6 to 1, and still more preferably in the range of 0.7 to 1.

Regarding the blending ratio (mass ratio) of the components (a) to (c) described above, W1 represented by the following formula must be in the range of 0.15 to 1.
W1 = (b) / ((b) + (c))
If W1 is less than 0.15, impact resistance cannot be obtained. In addition, the master batch is easily blocked and the abrasion resistance of the master batch is also deteriorated. As W1, the range of 0.3-1 is more preferable, and the range of 0.4-1 is further more preferable.

About the compounding ratio (mass ratio) of above-described (a)-(c) component, W2 shown by a following formula needs to exist in the range of 0.1-0.6 further.
W2 = (b) / ((a) + (b) + (c)) = 0.1-0.6
When W2 is less than 0.1, blocking resistance and impact resistance cannot be obtained. If W2 exceeds 0.6, impact resistance cannot be obtained. W2 is preferably 0.15 to 0.5, and more preferably 0.2 to 0.4.

[Manufacturing method of masterbatch]
Although the manufacturing method of an above described masterbatch is not specifically limited, It is preferable to use the continuous biaxial kneader provided with a biaxial part, a kneading part, and a short axis extrusion part. For example, the master batch of the present invention can be preferably produced by a continuous twin-screw kneader having a basic structure as shown in FIG. 1 of JP-A-2005-335240.
Specifically, it is preferable that the two-shaft screw L / D is in the range of 12 to 34 and the non-meshing different direction rotation method is used. In addition, the cross section of the kneading section has a two-blade rotor shape, and the L / D of the rotor is 6 to 18, and the kneading melt flow is adjusted at the downstream end of the kneading section to adjust the degree of kneading. It is preferable that an orifice that can change the cross-sectional area of the road is disposed, and that the kneaded melt is provided to the short-axis extrusion portion after passing through the orifice.
As a kneading condition using such a continuous biaxial kneader, it is preferable to set the shear rate of the molten resin in the kneading part in a range represented by the following formula.
600 × (38 / D) ^{2 to} 2000 × (38 / D) ² (sec ⁻¹ )
(Here, D is the screw diameter (mm) in the kneading part.)
If the shear rate of the molten resin in the kneading part is too lower than the lower limit value of this formula, the kneading degree of the master batch becomes insufficient and the impact resistance deteriorates. On the other hand, if the shear rate is too higher than the upper limit value of this equation, the resin temperature will rise too much, and there is a possibility that blocking of master batches (pellets) will occur in the catcher tank or the like.
In addition, 80-250 degreeC is preferable and the preset temperature of a kneading part has more preferable 120-230 degreeC. If the set temperature is less than 80 ° C., kneading becomes unstable and productivity is lowered, which is not preferable. On the other hand, if the set temperature exceeds 250 ° C., the resin temperature rises too much, and there is a possibility that blocking between master batches (pellets) may occur in the catcher tank or the like.

The masterbatch of the present invention described above is finally mixed and molded with a polyolefin resin to form a molded product. In the automotive field, a polypropylene resin (for dilution) is frequently used as a molding polyolefin resin, and the masterbatch of the present invention is most suitable for molding by mixing with a polypropylene resin.
As the polypropylene resin for dilution, it is preferable to use a block polypropylene resin having an ethylene / propylene random copolymer part of 3 to 18% by mass from the viewpoint of improving the impact resistance of the final molded product.
The mixing ratio of the master batch (MB) of the present invention and the polypropylene resin for dilution (PP) is preferably MB: PP = 15 to 55% by mass: 85 to 45% by mass, and more preferably MB: PP = 20 to 50% by mass: 80 to 50% by mass. When the ratio of the master batch exceeds 55% by mass, the cost reduction effect becomes low, and when the ratio of the master batch is less than 15% by mass, the reforming effect by the master batch decreases.

In the mixture of the masterbatch of the present invention and the polyolefin resin, various plastic additives, pigments, crosslinking agents / decomposing agents, flame retardants, and the like can be used in combination.
Additives for plastics include pigments, crosslinking agents, decomposing agents, softeners, mold release agents, antibacterial / antifungal / insect repellents, flame retardants, foaming agents, deodorizing agents, lubricants commonly used in plastics, Examples thereof include an antistatic agent, a heat stabilizer, an ultraviolet absorber, a metal powder, and a ceramic powder. Examples of the metal powder include metal powders such as iron, copper, aluminum, titanium, and stainless steel. Examples of the ceramic powder include oxide ceramic powders such as zirconia and alumina.

  As the pigment, one or more of an organic pigment and an inorganic pigment can be used, and examples of the organic pigment include azo pigments such as azo lake, hansa, benzimidazolone, diarylide, pyrazolone, yellow, and red; Examples thereof include phthalocyanine-based, quinacridone-based, perylene-based, perinone-based, dioxazine-based, anthraquinone-based, isoindolinone-based polycyclic pigments, and aniline black. Examples of the inorganic pigments include inorganic pigments such as titanium oxide, titanium yellow, iron oxide, ultramarine blue, cobalt blue, chromium oxide green, yellow lead, cadmium yellow, and cadmium red, and carbon black.

As a crosslinking agent and a decomposing agent, t-butyl peroxybenzoate, 2,5-dimethyl-2,5-dibutylperoxyhexane, 1,3-bis (t-butylperoxyisobrovir) benzene, 2,2 ′ -Organic peroxides such as azobisisobutyronitrile can be mentioned.
Examples of the antibacterial / antifungal / insect repellent include compounds such as thiosulfamide, thiophthalimide, biszenoxyarsine, thiabetasol, and aminobenzimidazole, and derivatives thereof.
Examples of the flame retardant include compounds such as antimony oxide, organic phosphate ester, chlorendic acid, tetrabromophthalic anhydride, and a polyol containing a phosphorus atom or a halogen atom.
Examples of the blowing agent include compounds such as sodium hydrogen carbonate, dinitrosotetramine, azodicarbonamide, azobisisobutyronitrile, sulfonyl hydrazide, sulfonyl semicarbazide, and derivatives thereof.

  Moreover, you may mix | blend thermoplastic resins other than polyolefin resin with polyolefin resin which mixes the masterbatch of this invention. Examples of the thermoplastic resin include polystyrene resins such as polystyrene, rubber-reinforced polystyrene (HIPS), isotactic polystyrene, and syndiotactic polystyrene; acrylonitrile-styrene resin (AS), acrylonitrile-butadiene-styrene resin (ABS). ) And other polyacrylonitrile resins; polymethacrylate resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene resins, polyphenylene ether resins, polyphenylene sulfide resins, polyphenylene sulfone resins, rosin resins, terpenes Resin, chroman and indene resin, petroleum resin, and the like. In addition, these thermoplastic resins may be used independently and may be used in combination of 2 or more type. As for the compounding quantity of these thermoplastic resins, it is desirable that it is 0.1-100 mass parts with respect to 100 mass parts of polyolefin resin. If it is less than 0.1 part by mass, the improvement effect by the thermoplastic resin cannot be obtained. On the other hand, when it exceeds 100 parts by mass, the characteristics as a polyolefin resin (for example, polypropylene resin) are lost.

  Further, during molding, conventionally known foaming agents, crystal nucleating agents, anti-glare stabilizers, heat-resistant stabilizers and light stabilizers (hereinafter referred to as stabilizers), ultraviolet absorbers, light stabilizers, heat-resistant stabilizers are used as necessary. , Antistatic agent, mold release agent, flame retardant, synthetic oil, wax, electrical property improver, anti-slip agent, anti-blocking agent, viscosity modifier, anti-coloring agent, anti-fogging agent, lubricant, pigment, dye, You may mix | blend additives, such as a plasticizer, a softening agent, anti-aging agent, a hydrochloric acid absorber, a chlorine scavenger, antioxidant, and an anti-tack agent. Stabilizers include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, hindered amine stabilizers and metal salts of higher fatty acids, which can be used as molding resin mixtures (for MB and dilution). (Polyolefin resin) You may mix | blend in the quantity of 0.001-10 mass parts with respect to 100 mass parts.

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.
Specifically, two types of master batches (MB for instrument panel, MB for door panel) having different uses were manufactured and evaluated for blocking resistance, fluidity and abrasion resistance. Furthermore, each master batch was mixed with a dilution resin and injection molded to evaluate the physical properties of the molded product.

[Raw materials]
(A) Component:
The following three types were used as ethylene copolymer A: ENR7447 (ethylene / butene-1 copolymer manufactured by DuPonda Welastomer Co., Ltd.)
Density: 0.865 g / cm ³ , Melting point: 42 ° C., MI: 5 g / 10 min
ENR7467 (ethylene / butene-1 copolymer manufactured by Duponda Welastomer Co., Ltd.)
Density: 0.862 g / cm ³ , Melting point: 36 ° C., MI: 1.2 g / 10 min
EG8200 (ethylene / octene-1 copolymer manufactured by DuPonda Welastomer Co., Ltd.)
Density: 0.870 g / cm ³ , Melting point: 60 ° C., MI: 5 g / 10 min

(B) Component:
The following two types were used as ethylene copolymer B: 1018G (manufactured by Prime Polymer Co., Ltd.)
Density: 0.910 g / cm ³ , Melting point: 117 ° C., MI: 8 g / 10 min
(Ethylene octene-1 copolymer)
・ EG8540 (manufactured by Duponda Welastomer Co., Ltd.)
Density: 0.908 g / cm ³ , Melting point: 103 ° C., MI: 1 g / 10 min
(Ethylene octene-1 copolymer)
For comparison, the following ethylene copolymers were used.
・ EG8401 (manufactured by Duponda Welastomer Co., Ltd.)
Density: 0.885 g / cm ³ , Melting point: 78 ° C., MI: 30 g / 10 min
(Ethylene octene-1 copolymer)

(C) Component:
The following three types of block PP were used as the polypropylene resin. Both are gas phase polymerization products.
・ PP-1
MI: 12 g / 10 min, EP copolymer part: 16% by mass
・ PP-2
MI: 30 g / 10 min, EP copolymer part: 20% by mass
・ PP-3
Homo PP with MI = 30
・ PP-4
MI: 3 g / 10 min, EP copolymer part: 20% by mass

(D) Component:
The following two types were used as talc.
・ MW UPN TT (manufactured by Hayashi Kasei Co., Ltd.)
Compressed talc (degassing talc) with an average particle diameter of 8 μm and a bulk specific gravity of 0.5 by laser method
・ MW UPN TT08 (manufactured by Hayashi Kasei Co., Ltd.)
Compressed talc (degassing talc) with an average particle diameter of 5 μm and bulk specific gravity of 0.8 by laser method

[Material properties measurement method]
The methods for measuring the density, melting point and MI of each raw material are as follows.
Density: measured in accordance with JIS K 7112.
Melting point: measured in accordance with JIS K7121.
MI: Measured according to JIS K 7210.

[Master batch manufacturing apparatus and manufacturing method]
A master batch was produced by the following two methods using a CTM HTM type twin-screw continuous kneading extruder φ65.
(Production Example 1)
・ L / D of biaxial part: 28
L / D of kneading part: 12
-Shear rate of kneading part: 400 sec ^-1
・ Set temperature of kneading section: 210 ° C
(Production Example 2)
・ L / D of biaxial part: 28
-L / D of kneading part: 9
-Shear rate of kneading part: 300 sec ^-1
・ Set temperature of kneading section: 190 ° C

[Master batch evaluation method]
(1) Blocking resistance (fluidity)
Since there is a correlation between the blocking resistance of the master batch (adhesion between MB compounds) and the fluidity of the master batch (fluidity of the MB compound itself), the evaluation item is “blocking resistance” as shown below. As a unified. Specifically, the following four tests, A method to D method, were performed and evaluated.

Method A: (Evaluation in the kneading production line)
After the melt-kneaded strand was cooled in the cooling water tank according to the production example described above, the mastercatch was pelletized by a pelletizer and collected in a catcher tank. After about 3 hours from the start of collection, it was transported by compressed air with hot air at 85 ° C. and then discharged and packed in a 500 kg flexible container. At this time, the evaluation was made based on the presence or absence of blocking substances and the discharge from the tank.
FIG. 1 shows a situation where the master batch is extracted from the catcher tank. In addition, FIG. 2 shows a blocking situation occurring in the master batch.
The case where blocking as shown in FIG. 2 did not occur and MB could be extracted smoothly as shown in FIG. 1 was designated as A, and the case where blocking occurred and extraction could not be performed smoothly was designated as B.

Method B: (Simple test of blocking properties)
This method approximately reproduces blocking at the time of two-stage stacking of 500 kg flexible containers immediately after kneading.
A metal batch having an inner diameter of 46 mmφ was filled with a master batch (pellet) and placed vertically, and a load of 19.6 N (2 kgf) was applied to the filled master batch (0.12 kgf / cm ² ). And it left still at 45 degreeC for 3 days. Thereafter, when this metal pipe was lifted, the master batch was dropped by its own weight, or when the metal pipe was easily unwound and dropped by tapping the metal pipe a few times, it was evaluated as A. Moreover, when the master batches adhered and it did not fall even if it hits a metal pipe, it evaluated as B.

Method C: (Simple test with 25kg bag)
The master batch (pellet) was filled in a 25 kg bag and left standing at 80 ° C. for 12 days with the bag standing. Thereafter, the bag was opened and the blocking state of the MB pellet was observed. A case where no blocking was observed as shown in FIG. 2 was designated as A, and a case where blocking was observed was designated as B.

Method D: (Simple test assuming an injection molding line)
A metal batch having an inner diameter of 46 mmφ was filled with a master batch (pellet) and placed vertically, and a load of 9.8 N (1 kgf) was applied to the filled master batch (0.06 kgf / cm ² ). And it left still at 80 degreeC for 12 hours. Thereafter, when this metal pipe was lifted, the master batch was dropped by its own weight, or when the metal pipe was easily unwound and dropped by tapping the metal pipe a few times, it was evaluated as A. Moreover, when the master batches adhered and it did not fall even if it hits a metal pipe, it evaluated as B.

(2) Wear resistance The wear resistance of the master batch was evaluated assuming an injection molding line.
As shown in FIG. 3A and FIG. 3B, 17 g of a master batch (pellet) is charged into the hole of a weight with a weight of 300 g, and the pellet surface is applied to the electrodeposition coating plate and manually reciprocated three times (FIG. 3C). ), The adhesion state of the pellet to the electrodeposition coated plate was visually evaluated. Specifically, as shown in FIG. 4A, the case where the adhesion of the resin shaved from the pellet is not noticeable is A, and the case where the adhesion of the resin shaved from the pellet as shown in FIG.

[Example 1]
(Examples 1-1 to 1-6, Comparative Examples 1-1 to 1-7)
The masterbatch was manufactured by the manufacture example 1 on the assumption that it used for instrument panel shaping | molding using the above-mentioned raw material, and each above described evaluation was performed. Table 1 and Table 2 show the raw material formulation and the evaluation results.

注）原料には、酸化防止剤としてイルガノックス１０１０（チバスペシャリティー社製）を０．２質量部添加した。

Note) 0.2 parts by mass of Irganox 1010 (manufactured by Ciba Specialty) was added to the raw material as an antioxidant.

注）原料には、酸化防止剤としてイルガノックス１０１０（チバスペシャリティー社製）を０．２質量部添加した。

Note) 0.2 parts by mass of Irganox 1010 (manufactured by Ciba Specialty) was added to the raw material as an antioxidant.

[Example 2]
(Examples 2-1 to 2-4, Comparative Examples 2-1 to 2-4)
A masterbatch was produced according to Production Example 2 on the assumption that the above-described raw materials were used for door panel molding, and each evaluation described above was performed. Table 3 and Table 4 show the raw material formulation and the evaluation results.

注）原料には、酸化防止剤としてイルガノックス１０１０（チバスペシャリティー社製）を０．２質量部添加した。

Note) 0.2 parts by mass of Irganox 1010 (manufactured by Ciba Specialty) was added to the raw material as an antioxidant.

注）原料には、酸化防止剤としてイルガノックス１０１０（チバスペシャリティー社製）を０．２質量部添加した。

Note) 0.2 parts by mass of Irganox 1010 (manufactured by Ciba Specialty) was added to the raw material as an antioxidant.

Example 3
Using each masterbatch manufactured in Example 1, a mixed resin premised on instrument panel molding for automobiles was molded by injection molding to evaluate physical properties. As a raw material for dilution, a block PP (gas phase polymerization product) having an MI of 30 g / 10 min and a copolymer part content of 11% by mass was used.
The injection molding machine and molding conditions used are as follows.
Injection molding machine: FE120 manufactured by Nissei Plastic Industry Co., Ltd.
Molding condition:
Molding temperature: 220 ° C., injection time: 10 seconds, back pressure: 10%, injection speed: 50%
Injection pressure: 15%, mold temperature: 50 ° C., cooling time: 20 seconds, mixing nozzle: yes In addition, MI, IZOD impact strength, and flexural modulus were measured as physical properties of the injection molded product. The measuring method of each physical property is as follows. The MI target value is 20 g / 10 min, the IZOD impact strength target value (minimum reference value) is 20 KJ / m ² , and the flexural modulus target value (minimum reference value) is 2350 MPa.
MI: Measured according to JIS K 7210 (230 ° C., 21.18 N). Specifically, a square plate (80 × 80 × 30 mm) was cut to prepare a sample.
-IZOD: Measured according to ASTM D-256.
-Flexural modulus: measured in accordance with ASTM D-790 (span: 60 mm, bending speed: 5 mm / min).
Table 5 and Table 6 show the raw material formulation and the evaluation results.

Example 4
Using each masterbatch manufactured in Example 2, a mixed resin premised on automobile door panel molding was molded by injection molding, and physical properties were evaluated. Table 7 and Table 8 show the raw material formulation and the evaluation results. In addition, the raw material for dilution, the injection molding machine, the molding conditions, and the evaluation method are the same as those in Example 3. The MI target value is 20 g / 10 min, the IZOD impact strength target value (minimum reference value) is 20 KJ / m ² , and the flexural modulus target value (minimum reference value) is 1650 MPa.

〔Evaluation results〕
From Examples 1 and 2, the master batches of the present invention (Examples 1-1 to 1-6 and 2-1 to 2-4) are all excellent in blocking resistance (fluidity) and shear resistance. I understand that. Furthermore, from Examples 3 and 4, it can be seen that all of the molded products obtained by mixing the master batch of the present invention with the PP for dilution and injection molding are excellent in impact resistance.
On the other hand, Comparative Examples 1-1 to 1-7 and 2-1 to 2-4 are inferior in blocking resistance or abrasion resistance except for Comparative Example 1-3. Moreover, the molded product obtained by mixing the master batch of Comparative Example 1-3 with PP for dilution had an IZOD impact strength as extremely low as 12 KJ / m ^{2 as} shown in Comparative Example 3-3 of Table 6, It can be seen that the impact is very poor.

  INDUSTRIAL APPLICATION This invention can be utilized suitably as a masterbatch used for manufacture of the polyolefin molding used for the interior / exterior material of a motor vehicle, and its manufacturing method.

Claims (4)

A masterbatch comprising the following components (a) to (d):
(A) Ethylene copolymer A having a density of 0.85 to 0.88 g / cm ³ , MI of 0.1 to 50 g / 10 min (190 ° C., 21.18 N), and a melting point of 30 to 70 ° C.
(B) The density is 0. 905-0. 915 g / cm ³ , MI 0.1 to 50 g / min (190 ° C., 21.18 N), melting point 90 to 130 ° C. and / or ethylene homopolymer (c) MI 1 A polypropylene resin (d) that is ˜1000 g / 10 min (230 ° C., 21.18 N), and an inorganic filler whose primary particle diameter is 1 to 10 μm. The mixing ratio (mass ratio) of the components (a) to (d) is as follows: A master batch characterized as follows.
((A) + (b) + (c)) / ((a) + (b) + (c) + (d)) = 0.3 to 0.8
(A) / ((a) + (b) + (c)) = 0.35-0.65
((A) + (b)) / ((a) + (b) + (c)) = 0.5-1
(B) / ((b) + (c)) = 0.15-1
(B) / ((a) + (b) + (c)) = 0.1-0.6 In the masterbatch according to claim 1,
(C) A masterbatch characterized in that the component is a block polypropylene resin composed of a homopolypropylene part and an olefin copolymer part. In the masterbatch according to claim 1 or claim 2,
(D) A master batch characterized in that the component is talc. A method for producing the master batch according to any one of claims 1 to 3 using a continuous biaxial kneader comprising a biaxial part, a kneading part and a short-axis extrusion part,
The continuous biaxial kneader is
The biaxial screw L / D is in the range of 12 to 34, and is a non-meshing different direction rotation system,
While the cross section of the kneading part has a two-blade rotor shape, the L / D of the rotor is 6 to 18,
At the downstream end of the kneading part, an orifice is provided that can change the cross-sectional area of the kneaded melt in order to adjust the degree of kneading, and after passing through the orifice, the kneaded melt is It has a structure that is used for the short shaft extrusion part,
A method for producing a masterbatch, wherein the shear rate of the molten resin in the kneading part is set in a range represented by the following formula.
600 × (38 / D) ^{2 to} 2000 × (38 / D) ² (sec ⁻¹ )
(Here, D is the screw diameter (mm) in the kneading part.)

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