JP5914318B2 - Method for producing thermoplastic resin composition - Google Patents

Description

  The present invention relates to a method for producing a thermoplastic resin composition. More specifically, the present invention relates to a method for producing a thermoplastic resin composition in which a polyamide resin is dispersed and contained in a polyolefin resin.

  Conventionally, it has been devised to obtain a mixed resin that exceeds the characteristics that each resin can exhibit independently by mixing different kinds of resins. For example, a combination of polyamide resin and polyolefin resin can be used to improve the characteristics of the mixed resin. A technique to be improved is known in Patent Document 1 below. In recent years, there is a social demand for the use of raw materials corresponding to environmental friendliness.

Japanese Patent Laid-Open No. 06-234897

When the mixture of the polyamide resin (A), the polyolefin resin (B) and the compatibilizer (ie, modified polyolefin) (C) is kneaded, all the raw materials (A) to (C) are simultaneously mixed by dry blending. Generally, after mixing, the mixture is put into a twin screw extruder or the like and kneaded. Patent Document 1 discloses a blow molding composition in which a polyamide resin (A), a polyolefin resin (B), and a compatibilizing agent (C) are mixed. It may be difficult to strengthen the strength.
The present invention has been made in view of the above circumstances, and is a method for producing a thermoplastic resin composition in which a polyamide resin (A), a polyolefin resin (B), and a compatibilizer (C) are mixed. Another object of the present invention is to provide a method for producing a thermoplastic resin composition that can improve the mechanical strength more reliably.

In order to solve the above problems, the method for producing a thermoplastic resin composition according to claim 1 is a method for producing a thermoplastic resin composition in which a polyamide resin is dispersed and contained in a polyolefin resin. ,
A mixing step of melting and mixing the mixed resin in which the polyamide resin (A) and the compatibilizer (C) are melt-mixed and the polyolefin resin (B);
The compatibilizer (C) is a modified polyolefin resin (C1) modified with maleic anhydride ,
The resin constituting the skeleton of the modified polyolefin resin (C1) is an olefin-based thermoplastic elastomer,
The gist of the olefinic thermoplastic elastomer is an ethylene / propylene copolymer (EPR ) .
The method for producing a thermoplastic resin composition according to claim 2 is the method according to claim 1, wherein the total amount of the polyamide resin (A), the polyolefin resin (B) and the compatibilizer (C) is 100% by mass. If
The blending ratio of the polyamide resin (A) is 10 to 50% by mass,
The content of the compatibilizer (C) is 3 to 30% by mass.
The method for producing a thermoplastic resin composition according to claim 3 is the method according to claim 1, wherein the total amount of the polyamide resin (A), the polyolefin resin (B) and the compatibilizer (C) is 100% by mass. If
The blending ratio of the polyamide resin (A) is 10 to 30% by mass,
The content of the compatibilizer (C) is 3 to 50% by mass.
The method for producing a thermoplastic resin composition according to claim 4 is the method according to claim 3, wherein the total amount of the polyamide resin (A), the polyolefin resin (B) and the compatibilizer (C) is 100% by mass. If
The blending ratio of the polyamide resin (A) is 10 to 30% by mass,
The content of the compatibilizer (C) is 3 to 30% by mass.
The manufacturing method of the thermoplastic resin composition according to claim 5 is characterized in that, in any one of claims 1 to 4 , the polyolefin resin (B) is a polypropylene resin.

According to the method for producing a thermoplastic resin composition of the present invention, in a thermoplastic resin composition in which a polyamide resin (A), a polyolefin resin (B), and a compatibilizer (C) are mixed, a more reliable mechanical Strength can be improved. That is, it is possible to obtain a thermoplastic resin composition from which a molded article having excellent mechanical strength can be obtained.
Since the compatibilizer (C) is a modified polyolefin resin (C1) modified with maleic anhydride , a more excellent mechanical strength improvement effect can be obtained.

It is a graph of the experimental Examples 1 and Comparative Examples 1 and 2. It is a graph of the experimental example 2 and Comparative Examples 3-4. Is an image obtained by enlarging the fracture surface of the thermoplastic resin composition according to Experiment Example 2.

  The items shown here are exemplary and illustrative of the embodiments of the present invention, and are the most effective and easy-to-understand explanations of the principles and conceptual features of the present invention. It is stated for the purpose of providing what seems to be. In this respect, it is not intended to illustrate the structural details of the present invention beyond what is necessary for a fundamental understanding of the present invention. It will be clear to those skilled in the art how it is actually implemented.

The method for producing a thermoplastic resin composition of the present invention is a method for producing a thermoplastic resin composition in which a polyamide resin is dispersed and contained in a polyolefin resin,
It is characterized by comprising a mixing step of melt-mixing the mixed resin in which the polyamide resin (A) and the compatibilizer (C) are melt-mixed and the polyolefin resin (B).

<1> About Each Component The “polyamide resin (A)” is a polymer having a chain skeleton formed by polymerizing a plurality of monomers via an amide bond (—NH—CO—). The thermoplastic resin composition according to the present invention is a resin that forms a dispersed phase with respect to the polyolefin resin (B) described later.

  As monomers constituting the polyamide resin (A), amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, ε-caprolactam, undecane lactam, ω-lauryllactam And lactam. These may use only 1 type and may use 2 or more types together.

  Furthermore, the polyamide resin (A) can also be obtained by copolymerization of a diamine and a dicarboxylic acid. In this case, the diamine as a monomer includes ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, , 9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1, 16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 2-methyl-1,5-diaminopentane, 2-methyl -Aliphatic diamines such as 1,8-diaminooctane, cyclohexanediamine, bis- 4-amino-cyclohexyl) cycloaliphatic diamines such as methane, and aromatic diamines such as xylylenediamine (such as p- phenylenediamine and m- phenylenediamine) can be mentioned. These may use only 1 type and may use 2 or more types together.

  Furthermore, dicarboxylic acids as monomers include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, Aliphatic dicarboxylic acids such as tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid Etc. These may use only 1 type and may use 2 or more types together.

  In this method, it is preferable to use a polyamide resin containing an amide bond-containing unit having 11 carbon atoms in the main chain as the polyamide resin (A). That is, a polyamide resin containing a structural unit derived from a monomer having 11 carbon atoms is preferable, and a polymer using 11-aminoundecanoic acid or undecane lactam as a monomer (hereinafter referred to as this heavy polymer). The coalescence is also referred to as “PA11 resin”. In particular, 11-aminoundecanoic acid is a monomer obtained from castor oil, and is therefore desirable from the viewpoint of environmental protection (particularly from the viewpoint of carbon neutral). It is preferable that the structural unit derived from the monomer having 11 carbon atoms is 50% or more of all the structural units in the PA11 resin. That is, a structural unit derived from a monomer having a carbon atom number of less than 11 and / or a structural unit derived from a monomer having a carbon atom number of 12 or more are all structural units in the PA11 resin. It can contain less than 50% of them. Further, the PA11-based resin may be a structural unit derived from a monomer having all the structural units of 11 carbon atoms. That is, the polyamide resin (A) may be polyamide 11 (PA11).

Further, in the present method, as the preferred polyamide (A) other than the PA11 resin, for example, polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 614, polyamide 12, polyamide 6T, polyamide 6I, polyamide 9T, polyamide M5T, polyamide 1010, polyamide 1012, polyamide 10T, polyamide MXD6, polyamide 6T / 66, polyamide 6T / 6I, polyamide 6T / 6I / 66, polyamide 6T / 2M-5T, polyamide 9T / 2M-8T, and the like.
In addition, these polyamide (A) may be used individually by 1 type, and may be used in combination of 2 or more type.

Moreover, when using together PA11 type | system | group resin and another polyamide, when the whole polyamide resin is 100 mass%, the content rate of another polyamide can be made into less than 40 mass%.
In the polyamide resin (A), more than half (50% or more) of carbon atoms constituting the main chain constitute a chain skeleton. That is, the polyamide resin (A) may contain an aromatic skeleton, but the carbon atoms constituting the aromatic skeleton are preferably less than half (less than 50%) of the carbon atoms constituting the main chain. .

  The molecular weight of the polyamide resin (A) is not particularly limited, but the weight average molecular weight is preferably 5,000 to 100,000, more preferably 7,500 to 50,000, and 10,000 to 50. Is particularly preferred. The weight average molecular weight is measured by GPC method (standard polystyrene conversion).

The “polyolefin resin (B)” is a resin that forms a continuous phase with respect to the polyamide resin (A) in the thermoplastic resin composition according to the present invention.
The polyolefin resin (B) is not particularly limited, and various polyolefins can be used. For example, propylene homopolymer (including isotactic propylene homopolymer), ethylene-propylene copolymer (including ethylene-propylene block copolymer, etc.), ethylene homopolymer, and ethylene-α-olefin copolymer A polymer etc. are mentioned. These may use only 1 type and may use 2 or more types together.

  Among the above, the α-olefin forming the ethylene-α-olefin copolymer is usually an unsaturated hydrocarbon compound having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1 -Hexene, 1-heptene, 3-methyl-1-butene, 4-methyl-1-pentene and the like. That is, the ethylene-α-olefin copolymer includes ethylene-1-butene copolymer, ethylene-propylene copolymer, ethylene-propylene-1-butene copolymer, ethylene-propylene-diene copolymer, ethylene -A hexene copolymer, an ethylene-octene copolymer, etc. are mentioned. These may use only 1 type and may use 2 or more types together.

  The molecular weight of the polyolefin resin (B) is not particularly limited, but the weight average molecular weight is preferably 10,000 to 500,000, more preferably 100,000 to 400,000, and 250,000 to 350. Is particularly preferred. The weight average molecular weight is measured by GPC method (standard polystyrene conversion).

  The polyolefin resin (B) is a polyolefin that has no affinity for the polyamide resin (A) and has no reactive group that can react with the polyamide resin (A). In this respect, it is different from the polyolefin component as a compatibilizer included in the compatibilizer (C) described later.

The "compatibilizer (C)" is modified polyolefin resin (C1) having a reactive group capable of reacting with Polyamide resin (A) Ru der.

Examples of the reactive group capable of reacting with the polyamide resin (A) include an acid anhydride group (—CO—O—OC—), a carboxyl group (—COOH), and an epoxy group {—C ₂ O (two carbon atoms and A three-membered ring structure composed of one oxygen atom)}, an oxazoline group and the like.
Examples of the modified polyolefin resin (C1) include a copolymer of a polymerizable olefin and various monomers for introducing the reactive group, an oxidative degradation product of polyolefin, and a graft polymer of an organic acid to polyolefin. Can be mentioned. These may use only 1 type and may use 2 or more types together. Among these, as various monomers for introducing a reactive group, a monomer having a polymerizable unsaturated bond and an acid anhydride group, a monomer having a polymerizable unsaturated bond and a carboxyl group, Examples thereof include a monomer having a polymerizable unsaturated bond and an epoxy group.
In the present invention, a modified polyolefin resin modified with maleic anhydride is used as the modified polyolefin resin (C1).

Furthermore, an olefinic thermoplastic elastomer is used as a resin constituting the skeleton of the modified polyolefin resin (C1) (hereinafter referred to as “skeleton resin”). Specifically, an ethylene / propylene copolymer (EPR) is used.

The molecular weight of the compatibilizer (C) is not particularly limited, but the weight average molecular weight is preferably 10,000 to 500,000, more preferably 35,000 to 500,000, and 35,000. Particularly preferred is ~ 300,000. The weight average molecular weight is measured by GPC method (standard polystyrene conversion).
Further, the amount of the acid group of the compatibilizer (C) is not particularly limited.

<2> Mixing Step The “mixing step” is a step of melting and mixing the mixed resin and the polyolefin resin (B). In this step, as will be described later, the polyamide resin (A) and the compatibilizer (C) for obtaining the mixed resin (first mixed resin described later) are melt-mixed to obtain the first The process of obtaining the mixed resin is hereinafter referred to as the second mixing process while being referred to as the first mixing process.

As described above, the compatibilizer (C) can be made to function more effectively by using the first mixed resin prepared in advance. That is, by mixing the compatibilizer (C) in advance with the polyamide resin (A), which is a resin that becomes a dispersed phase and has a small blending amount with respect to the matrix resin, the polyolefin resin (B) It is considered that the compatibilizer (C) can be prevented from being dispersed alone without diffusing into the water. In particular compatibilizer as (C), for using the modified polyolefin resin (C1) having a reactive group capable of reacting with the polyamide resin (A), the reaction more efficiently polyamide resin The reactive group (A) In the second mixing step, it can be suppressed that only the compatibilizing agent (C) is dispersed alone in the polyolefin resin (B).

  The mixing method in the second mixing step is not particularly limited. For example, a kneading apparatus such as an extruder (single screw extruder, twin screw kneading extruder, etc.), a kneader and a mixer (high-speed flow mixer, paddle mixer, ribbon mixer, etc.), etc. Can be used. These apparatuses may use only 1 type and may use 2 or more types together. Moreover, when using 2 or more types, you may drive | operate continuously and may operate | move batchwise (batch type). Further, the first mixed resin and the polyolefin resin (B) may be mixed together, or one of them may be added and charged (multi-stage blending) in a plurality of times.

  Moreover, the mixing temperature in this 2nd mixing process is not specifically limited, What is necessary is just to be able to perform melt mixing. That is, it is preferable to set the temperature appropriately depending on the types of the polyamide resin (A) and the compatibilizer (C) contained in the first mixed resin and the type of the polyolefin resin (B). It is preferable that the resin is mixed in a molten state. For example, mixing can be performed at a temperature of 190 to 350 ° C. This temperature can further be 200-330 ° C., in particular 205-310 ° C.

  On the other hand, the mixing method for the first mixing step of mixing the polyamide resin (A) and the compatibilizer (C) for obtaining the first mixed resin is not particularly limited. For example, an extruder (uniaxial) A screw extruder, a twin-screw kneading extruder, etc.), a kneader and a mixer (high-speed flow mixer, paddle mixer, ribbon mixer, etc.) can be used. These apparatuses may use only 1 type and may use 2 or more types together. Moreover, when using 2 or more types, you may drive | operate continuously and may operate | move batchwise (batch type). Furthermore, the polyamide resin (A) and the compatibilizer (C) may be mixed together, or any one of them may be added and added (multistage blending) in a plurality of times.

  Further, the first mixed resin may be mixed with the polyolefin resin (B) again after being mixed, or may be mixed again with the polyolefin resin (B). After mixing the polyamide resin (A) and the compatibilizer (C) on the side, the polyolefin resin (B) is added on the downstream side in the same apparatus, and the first mixed resin and the polyolefin resin (B) Mixing may be performed.

  The blending ratio of the polyamide resin (A), the polyolefin resin (B) and the compatibilizer (C) in this method is not particularly limited, but usually when the total of these is 100% by mass, the polyamide resin (A) Is preferably 1 to 90% by mass, more preferably 10 to 50% by mass, and particularly preferably 15 to 30% by mass. 1-90 mass% of polyolefin resin (B) is preferable, 10-80 mass% is more preferable, 40-70 mass% is especially preferable. 1-50 mass% is preferable, as for a compatibilizer (C), 3-30 mass% is more preferable, and 5-15 mass% is especially preferable.

In this method, in the range which does not inhibit the objective of this invention, other components other than a polyamide resin (A), polyolefin resin (B), and a compatibilizer (C) can be contained. As other components, thermoplastic resins other than the above, flame retardants, flame retardant aids, fillers, colorants, antibacterial agents, antistatic agents and the like can be blended. These may use only 1 type and may use 2 or more types together.
Examples of the other thermoplastic resins include polyester resins (polybutylene terephthalate, polyethylene terephthalate, polycarbonate, polybutylene succinate, polyethylene succinate, polylactic acid) and the like.

Examples of the flame retardant include halogen flame retardant (halogenated aromatic compound), phosphorus flame retardant (nitrogen-containing phosphate compound, phosphate ester, etc.), nitrogen flame retardant (guanidine, triazine, melamine, and these Derivatives), inorganic flame retardants (metal hydroxides, etc.), boron flame retardants, silicone flame retardants, sulfur flame retardants, red phosphorus flame retardants and the like.
Examples of the flame retardant aid include various antimony compounds, metal compounds containing zinc, metal compounds containing bismuth, magnesium hydroxide, and clay silicates.
Examples of the filler include glass components (glass fibers, glass beads, glass flakes, etc.), silica, inorganic fibers (glass fibers, alumina fibers, carbon fibers), graphite, silicate compounds (calcium silicate, aluminum silicate, kaolin, talc, Clay), metal oxides (iron oxide, titanium oxide, zinc oxide, antimony oxide, alumina, etc.), carbonates and sulfates of metals such as calcium, magnesium, zinc, organic fibers (aromatic polyester fibers, aromatic polyamides) Fiber, fluororesin fiber, polyimide fiber, vegetable fiber, etc.)
Examples of the colorant include pigments and dyes.

<3> Molded product The thermoplastic resin composition obtained by the present method may be molded in any manner, and the method is not particularly limited. The shape, size, thickness and the like of the molded product of the present invention are not particularly limited, and the use thereof is not particularly limited. As a molded object, it uses as exterior materials, interior materials, structural materials, etc., such as a motor vehicle, a rail vehicle, a ship, and an airplane, for example. Among these, examples of the automobile supplies include automobile exterior materials, automotive interior materials, automotive structural materials, and engine room components. Specifically, bumper, spoiler, cowling, front grill, garnish, bonnet, trunk lid, fender panel, door panel, roof panel, instrument panel, door trim, quarter trim, roof lining, pillar garnish, deck trim, tonneau board, package Tray, dashboard, console box, kicking plate, switch base, seat back board, seat frame, armrest, sun visor, intake manifold, engine head cover, engine under cover, oil filter housing, automotive electronic components (ECU, TV monitor, etc.) And the like. Furthermore, for example, interior materials such as buildings and furniture, exterior materials, and structural materials may be mentioned. That is, a door cover material, a door structure material, a cover material of various furniture (desk, chair, shelf, bag, etc.), a structural material, etc. are mentioned. In addition, a package, a container (such as a tray), a protective member, a partition member, and the like can be given. In addition, it can also be used as a housing and a structure of a home appliance (a thin TV, a refrigerator, a washing machine, a vacuum cleaner, a mobile phone, a portable game machine, a notebook computer, etc.).

Hereinafter, the present invention will be described more specifically with reference to examples.
[1] Preparation of the production and test pieces of the thermoplastic resin composition <Experiment Example 1 (Reference Example)>
(1) First mixing step PA11 (nylon 11 resin, manufactured by Arkema Co., Ltd., product name “Rilsan BMN O”, weight average molecular weight 18,000, melting point 190 ° C.) is used as a polyamide resin (A), and a compatibilizer ( As C), maleic anhydride-modified polypropylene (manufactured by Sanyo Kasei Kogyo Co., Ltd., “Yumex 1001”, weight average molecular weight 40,000, acid value 26) was used, and these pellets were dried so as to have the composition shown in Table 1. After blending, the mixture is put into a twin-screw melt kneading extruder (manufactured by Technobel Co., Ltd., screw diameter 15 mm, L / D = 59), kneading temperature 210 ° C., extrusion speed 2.0 kg / hour, screw rotation speed 200 revolutions / minute. The first mixed resin extruded using a pelletizer was cut to produce pellets of the first mixed resin. .

(2) Second mixing step Next, a polypropylene resin (manufactured by Prime Polymer Co., Ltd., product name “J-3057HP”, block polymer, weight average molecular weight 255,000, melting point 185 ° C.) is used as the polyolefin resin (B). After dry-blending with the first mixed resin pellet obtained in Table 1 and blending as shown in Table 1, it was put into a biaxial melt-kneading extruder (manufactured by Technobel, screw diameter 15 mm, L / D = 59). , kneading temperature 210 ° C., an extrusion rate of 2.0 kg / time, and mixed and the conditions of a screw speed of 200 revolutions / minute, further, the experiment example by cutting a thermoplastic resin composition extruded by using a pelletizer 1 A pellet of the thermoplastic resin composition was prepared.
(3) molding step then pellets of the obtained thermoplastic resin composition of Experiment Example 1 was poured into the hopper of an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd. 40-ton injection molding machine), the set temperature 210 A test piece for measuring physical properties, which will be described later, was injection-molded under injection conditions of ℃ and mold temperature of 60 ℃.

<Comparative Example 1> (comparison to Experiment Example 1)
The experiment example 1 and the same polyamide resin (A), the using compatibilizer (C) and the polyolefin resin (B), they simultaneously upon were dry blended, in the same manner as Experiment Example 1, dual axis forging A kneading extruder (manufactured by Technobel Co., Ltd., screw diameter 15 mm, L / D = 59) is charged and mixed under conditions of a kneading temperature of 210 ° C., an extrusion speed of 2.0 kg / hour, and a screw speed of 200 rpm. Furthermore, the thermoplastic resin composition extruded using a pelletizer was cut to produce pellets of the thermoplastic resin composition of Comparative Example 1. Thereafter, the same molded process as Experimental Example 1, were injection molded for measuring physical properties test piece of Comparative Example 1.

<Comparative Example 2> (comparison to Experiment Example 1)
And instead of the polyamide resin (A) the polyolefin resin (B), after mixing the compatibilizer (C), a resin mixture obtained, except that mixed with the polyamide resin (A), Experimental Example 1 In the same manner, pellets of the thermoplastic resin composition of Comparative Example 2 were produced. Thereafter, the same molded process as Experimental Example 1, were injection molded for measuring physical properties test piece of Comparative Example 2.

<Experimental Example 2 (Example)>
(1) First mixing step PA11 (nylon 11 resin, manufactured by Arkema Co., Ltd., product name “Rilsan BMN O”, weight average molecular weight 17,000, melting point 190 ° C.) is used as a polyamide resin (A), and a compatibilizer ( As C), maleic anhydride-modified EPR (manufactured by Mitsui Chemicals, Inc., product name “Tafmer MP0620”, weight average molecular weight 199,000) was used, and after dry blending these pellets to have the composition shown in Table 2, Put into a twin-screw melt kneading extruder (Technobel Co., Ltd., screw diameter 15 mm, L / D = 59), mixing under conditions of kneading temperature 210 ° C., extrusion speed 2.0 kg / hour, screw rotation speed 200 rpm Furthermore, the 1st mixed resin extruded using the pelletizer was cut | judged, and the pellet of the 1st mixed resin was produced.

(2) Second mixing step Next, as the polyolefin resin (B), a polypropylene resin (manufactured by Nippon Polypro Co., Ltd., product name “NOVATEC MA1B”, homopolymer, melting point: 165 ° C.) was used to obtain the first mixed resin previously obtained. After dry blending with the pellets and the formulation shown in Table 2, the mixture was put into a biaxial melt kneading extruder (manufactured by Technobell, screw diameter 15 mm, L / D = 59), kneading temperature 210 ° C., extrusion speed 2.0 kg / time, and mixed and the conditions of a screw speed of 200 rev / min, further, pellets of the thermoplastic resin composition a thermoplastic resin composition was cut experiment example 2 was extruded using a pelletizer Was made.
Thereafter, likewise forming process as Experimental Example 1, were injection molded for measuring physical properties test piece.

<Comparative Example 3> (comparison to Experiment Example 2)
The experiment example 2 and the same polyamide resin (A), the using compatibilizer (C) and the polyolefin resin (B), they simultaneously upon were dry blended, in the same manner as Experiment Example 2, dual axis forging A kneading extruder (manufactured by Technobel Co., Ltd., screw diameter 15 mm, L / D = 59) is charged and mixed under conditions of a kneading temperature of 210 ° C., an extrusion speed of 2.0 kg / hour, and a screw speed of 200 rpm. Furthermore, the thermoplastic resin composition extruded using a pelletizer was cut to produce pellets of the thermoplastic resin composition of Comparative Example 3. Thereafter, the same molded process as Experiment Example 2, were injection molded for measuring physical properties test piece of Comparative Example 3.

<Comparative Example 4> (comparison to Experiment Example 2)
And instead of the polyamide resin (A) the polyolefin resin (B), after mixing the compatibilizer (C), a resin mixture obtained, except that mixed with the polyamide resin (A), Experimental Example 2 In the same manner, pellets of the thermoplastic resin composition of Comparative Example 3 were produced. Thereafter, the same molded process as Experiment Example 2, were injection molded for measuring physical properties test piece of Comparative Example 4.

[2] Performance Evaluation of Thermoplastic Resin Composition (1) Measurement of Charpy Impact Strength JIS K7111-1 using each test piece of Experimental Examples 1-2 and Comparative Examples 1-4 obtained in [1] above. The Charpy impact strength was measured according to the above. The results are shown in Tables 1 and 2. In this Charpy impact strength measurement, a test piece having a notch (type A) was used, and the impact was measured by an edgewise test method at a temperature of 23 ° C.

(2) Measurement of flexural modulus The flexural modulus was measured according to JIS K7171 using the test pieces of Experimental Examples 1-2 and Comparative Examples 1-4 obtained in [1] above. The results are shown in Tables 1 and 2. This bending elastic modulus is measured at a speed of 2 mm from an action point (curvature radius 5 mm) arranged at the center between the fulcrums while supporting each test piece at two fulcrums (curvature radius 5 mm) with a distance (L) between the fulcrums of 64 mm. The measurement was performed by applying a load at / min.

(3) the Moruforuji observed above [2] fracture surface Experiment Example 2 of specimens subjected to the measurement of the Charpy impact strength (1), a scanning electron microscope (manufactured by JEOL Ltd.), enlarged 5000 times The image obtained in this way is shown in FIG.

[3] Effect of Example From the results of Table 1 and FIG. 1, it can be seen that a significant difference in mechanical strength is caused by the mixing method. In particular, when the polyolefin resin (B) serving as the mother phase and the compatibilizer (C) were previously melt-mixed (Comparative Example 2) showed the lowest mechanical strength, three types were mixed simultaneously. In the case (Comparative Example 1), an improvement of about 14% in the Charpy impact strength and about 4% in the flexural modulus was observed. In contrast, when produced by the process of the present invention (Experiment Example 1), relative to Comparative Example 2, about 37% in the Charpy impact strength is observed improvement of about 6% in the flexural modulus. From these facts, it is understood that the impact resistance strength is remarkably improved when the compatibilizer (C) functions more effectively.

Moreover, from the results of Table 2 and FIG. 2, when the polyolefin resin (B) and the compatibilizer (C) as the mother phase are previously melt-mixed (Comparative Example 4) and when the three types are mixed simultaneously ( Comparative example 3), for most of the difference is not observed in the flexural modulus, when produced by the process of the present invention (experiment example 1), compared with Comparative example 4, the flexural modulus It can be seen that the improvement is about 11%. Furthermore, when produced by the process of the present invention (Experiment Example 1), compared with Comparative Example 3, about 55% of significant improvement in the Charpy impact strength is observed. From these facts, it is understood that the impact resistance strength is remarkably improved when the compatibilizer (C) functions more effectively.

Furthermore, from the results of FIG. 3, it can be seen that the test piece of Experimental Example 2 and has a sea-island structure. Furthermore, it can be seen that the island phase (that is, the polyamide resin that is the dispersed phase) is uniformly finely dispersed in the submicron order within the sea phase (that is, the polypropylene resin that is the mother phase). It is believed that the structure effectively improved both the flexural modulus and Charpy impact strength characteristics.

  As described above, the polyamide resin (A) constituting the dispersed phase and the compatibilizer (C) having a reactive group having reactivity with the polyamide resin (A) are melt-mixed in advance. The compatibilizer (C) is efficiently reacted with the polyamide resin (A), and more compatibilizer (C) can effectively exert a compatibilizing action. That is, the compatibilizer (C) can be efficiently present at the interface of the polyamide resin (A) which is the dispersed phase, whereby the particle size of the dispersed phase can be suppressed small, and this structure has excellent mechanical strength, However, it is considered that particularly high impact resistance can be obtained.

  The foregoing examples are for illustrative purposes only and are not to be construed as limiting the invention. Although the invention has been described with reference to exemplary embodiments, it is to be understood that the language used in the description and illustration of the invention is illustrative and exemplary rather than limiting. As detailed herein, changes may be made in its form within the scope of the appended claims without departing from the scope or spirit of the invention. Although specific structures, materials and examples have been referred to in the detailed description of the invention herein, it is not intended to limit the invention to the disclosure herein, but rather, the invention is claimed. It covers all functionally equivalent structures, methods and uses within the scope.

Claims (5)

A method for producing a thermoplastic resin composition in which a polyamide resin is dispersed and contained in a polyolefin resin,
A mixing step of melting and mixing the mixed resin in which the polyamide resin (A) and the compatibilizer (C) are melt-mixed and the polyolefin resin (B);
The compatibilizer (C) is a modified polyolefin resin (C1) modified with maleic anhydride ,
The resin constituting the skeleton of the modified polyolefin resin (C1) is an olefin-based thermoplastic elastomer,
The method for producing a thermoplastic resin composition, wherein the olefinic thermoplastic elastomer is an ethylene / propylene copolymer (EPR ) . When the total of the polyamide resin (A), the polyolefin resin (B) and the compatibilizer (C) is 100% by mass,
The blending ratio of the polyamide resin (A) is 10 to 50% by mass,
The method for producing a thermoplastic resin composition according to claim 1, wherein a blending ratio of the compatibilizer (C) is 3 to 30% by mass. When the total of the polyamide resin (A), the polyolefin resin (B) and the compatibilizer (C) is 100% by mass,
The blending ratio of the polyamide resin (A) is 10 to 30% by mass,
The method for producing a thermoplastic resin composition according to claim 1, wherein a blending ratio of the compatibilizer (C) is 3 to 50% by mass. When the total of the polyamide resin (A), the polyolefin resin (B) and the compatibilizer (C) is 100% by mass,
The blending ratio of the polyamide resin (A) is 10 to 30% by mass,
The method for producing a thermoplastic resin composition according to claim 3, wherein a blending ratio of the compatibilizer (C) is 3 to 30% by mass. The method for producing a thermoplastic resin composition according to any one of claims 1 to 4, wherein the polyolefin resin (B) is a polypropylene resin.