JP5220332B2 - Master batch for resin additives - Google Patents

Description

  The present invention relates to a resin additive masterbatch, a method for producing the same, a thermoplastic resin composition containing the resin additive masterbatch, and a molded article obtained therefrom.

When kneading two or more kinds of resins with an extruder or the like, a compatibilizing agent is often used in order to mix them uniformly. However, when two or more kinds of resins and a compatibilizing agent are added to the extruder and kneaded, depending on the combination of the resins, they may not be uniformly kneaded. A molded body obtained from such a kneaded product has many variations in properties, and a product having desired properties cannot be obtained.
JP 2004-346148 A JP 2005-298774 A

  This invention makes it a subject to provide the masterbatch for resin additives which is excellent in compatibility with 2 or more types of resin, and its manufacturing method.

  Another object of the present invention is to provide a thermoplastic resin composition containing the resin additive masterbatch capable of imparting desired properties without variation in properties and a molded product obtained therefrom. To do.

  The present invention provides a master batch for resin addition containing a polyamide resin, which contains a thermoplastic resin and a polymer having a maleimide monomer unit.

  Furthermore, this invention is a manufacturing method of the masterbatch for resin additives in any one of Claims 1-5, Comprising: The polyamide-type resin which knead | mixes the polymer which has a thermoplastic resin and a maleimide-type monomer unit in a molten state The manufacturing method of the masterbatch for resin additives containing is provided.

  Furthermore, the present invention relates to a thermoplastic resin composition comprising 99 to 50% by mass of a thermoplastic resin containing a polyamide resin as a base material and 1 to 50% by mass of a master batch for a resin additive produced in claim 6. I will provide a.

  Furthermore, this invention provides the molded object obtained from the thermoplastic resin composition of Claim 7 or 8.

  By using the master batch for resin additive containing the polyamide-based resin of the present invention, two or more types by kneading two or more thermoplastic resins (including polyamide-based resin) and the master batch for resin additive. Compared with the case where these thermoplastic resins and their compatibilizers are kneaded, two or more kinds of thermoplastic resins can be kneaded more uniformly. For this reason, it is possible to impart desired physical properties with small variations to the molded body obtained from the resin composition after kneading.

<Master batch for resin additive and its production method>
Thermoplastic resins include polyamide resins, acrylate resins, cellulose resins, vinyl alcohol resins, polyether resins, olefin resins, styrene resins, polyphenylene ether resins, polybutylene terephthalate resins and polyethylene. One or two or more selected from polyester resins such as terephthalate resins, liquid crystal polymers, polyphenylene sulfide resins, polyacetal resins, and polycarbonate resins can be mentioned, and among these, styrene resins are preferable.

  Polyamide resins include nylon 66, polyhexamethylene sebamide (nylon 6 · 10), polyhexamethylene dodecanamide (nylon 6 · 12), polydodecamethylene dodecanamide (nylon 1212), polymetaxylylene azide Pamide (nylon MXD6), polytetramethylene adipamide (nylon 46) and mixtures and copolymers thereof; nylon 6/66, nylon 66 / 6T in which 6T component is 50 mol% or less (6T: polyhexamethylene) Terephthalamide), copolymers such as nylon 66 / 6I (6I: polyhexamethylene isophthalamide), nylon 6T / 6I / 66, nylon 6T / 6I / 610, etc. whose 6I component is 50 mol% or less; polyhexa Methylene terephthalamide (nylon 6T), polyhexamethylene isophthal Copolymers such as imide (nylon 6I), poly (2-methylpentamethylene) terephthalamide (nylon M5T), poly (2-methylpentamethylene) isophthalamide (nylon M5I), nylon 6T / 6I, nylon 6T / M5T In addition, copolymer nylon such as amorphous nylon may be used, and examples of amorphous nylon include polycondensates of terephthalic acid and trimethylhexamethylenediamine.

  Further, a ring-opening polymer of cyclic lactam, a polycondensate of aminocarboxylic acid, and a copolymer comprising these components, specifically, nylon 6, poly-ω-undecanamide (nylon 11), poly-ω-dodecanamide. (Nylon 12) and other aliphatic polyamide resins and copolymers thereof, and copolymers with polyamides comprising diamines and dicarboxylic acids, specifically nylon 6T / 6, nylon 6T / 11, nylon 6T / 12, Mention may be made of nylon 6T / 6I / 12, nylon 6T / 6I / 610/12, and mixtures thereof.

  Among the polyamide-based resins, PA (nylon) 6, PA (nylon) 66, and PA (nylon) 6/66 are preferable among the above.

  Examples of the styrenic resin include polymers of styrene and styrene derivatives such as α-substituted and nucleus-substituted styrene. Also included are copolymers composed mainly of these monomers and monomers of vinyl compounds such as acrylonitrile, acrylic acid and methacrylic acid and / or conjugated diene compounds such as butadiene and isoprene. For example, polystyrene, high impact polystyrene (HIPS) resin, acrylonitrile-butadiene-styrene copolymer (ABS) resin, acrylonitrile-styrene copolymer (AS resin), styrene-methacrylate copolymer (MS resin), styrene-butadiene A copolymer (SBS resin) etc. can be mentioned.

  Further, the polystyrene resin may include a styrene copolymer in which a carboxyl group-containing unsaturated compound for increasing compatibility and reactivity with the polyamide resin is copolymerized. The styrene-based copolymer in which the carboxyl group-containing unsaturated compound is copolymerized in the presence of the rubber-like polymer, the carboxyl group-containing unsaturated compound and, if necessary, other monomers copolymerizable therewith Is a copolymer obtained by polymerizing

Specific examples of ingredients include
1) In the presence of a rubbery polymer copolymerized with a carboxyl group-containing unsaturated compound, a monomer having an aromatic vinyl monomer as an essential component or an aromatic vinyl and a carboxyl group-containing unsaturated compound as an essential component A graft polymer obtained by polymerizing monomers,
2) A graft copolymer obtained by copolymerizing a monomer having an aromatic vinyl and a carboxyl group-containing unsaturated compound as essential components in the presence of a rubbery polymer;
3) A mixture of a rubber-reinforced styrene-based resin in which a carboxyl group-containing unsaturated compound is not copolymerized, a copolymer of monomers having a carboxyl group-containing unsaturated compound and an aromatic vinyl as essential components,
4) A mixture of the above 1), 2), a carboxyl group-containing unsaturated compound and a copolymer essentially comprising an aromatic vinyl,
5) There is a mixture of the above 1) to 4) and a copolymer containing aromatic vinyl as an essential component.

  In the above 1) to 5), styrene is preferable as the aromatic vinyl, and acrylonitrile is preferable as the monomer copolymerized with the aromatic vinyl. The carboxyl group-containing unsaturated compound is preferably 0.1 to 8% by mass, more preferably 0.2 to 7% by mass in the styrene resin.

  The polymer having a maleimide monomer unit may be a polymer of a maleimide monomer unit or a copolymer of a maleimide monomer unit and another monomer unit.

  Maleimide monomers that are maleimide monomer units are maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-toluylmaleimide, N- One or more selected from xylylmaleimide, N-naphthylmaleimide, Nt-butylmaleimide, N-orthochlorophenylmaleimide, and N-orthomethoxyphenylmaleimide are preferable.

Examples of other monomer units include aromatic vinyl compounds such as styrene, α-methyl styrene, vinyl ketone, and t-butyl styrene, maleic anhydride, methyl maleic anhydride, 1,2-dimethyl maleic anhydride, anhydrous ethyl maleic acid, and unsaturated dicarboxylic acid anhydride such as phenyl maleic acid.

  The polymer having a maleimide monomer unit is preferably a copolymer comprising a maleimide monomer, an aromatic vinyl monomer, and an unsaturated dicarboxylic anhydride monomer. When combining these three types of monomers, the following ratio is preferred.

  The proportion of the maleimide monomer unit is preferably 10 to 80% by mass, more preferably 30 to 60% by mass, still more preferably 40 to 55% by mass; the proportion of the aromatic vinyl monomer unit is preferably 10 to 10% by mass. 80 mass%, more preferably 30-60 mass%, still more preferably 40-55 mass%; the proportion of unsaturated dicarboxylic anhydride monomer units is preferably 0.1-10 mass%, more preferably 0 0.5 to 5% by mass, more preferably 0.5 to 3% by mass. When the ratio of the unsaturated dicarboxylic acid anhydride monomer unit is 10% by mass or less, the fluidity is improved, and when it is 0.1% by mass or more, the impact strength is increased.

The ratio of the thermoplastic resin and the polymer having maleimide monomer units in the master batch for resin additive is
The thermoplastic resin is preferably 95 to 10% by mass, more preferably 80 to 20% by mass, still more preferably 70 to 30% by mass,
The polymer having a maleimide monomer unit is preferably 5 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 70% by mass.

  The master batch for a resin additive of the present invention can be obtained by kneading a predetermined amount of a thermoplastic resin and a polymer having a maleimide monomer unit in a molten state using a known single or twin screw extruder. The form of the master batch for a resin additive of the present invention is not particularly limited, but is preferably in the form of a pellet because of easy handling.

  The master batch for a resin additive of the present invention has good compatibility with a thermoplastic resin, and acts as a compatibilizing agent for them when kneaded with two or more thermoplastic resins.

<Thermoplastic resin composition and molded product obtained therefrom>
As the thermoplastic resin used as the base material in the composition of the present invention, the same resins as those mentioned in the master batch for resin additives can be used, but polyamide resins and styrene resins are preferred.

  The base thermoplastic resin can be a combination of two or more resins, in which case one of the two or more thermoplastic resins is the same as the thermoplastic resin contained in the resin additive masterbatch. Preferably there is.

The ratio of the thermoplastic resin as a base material in the composition and the master batch for the resin additive is
The thermoplastic resin is preferably 99 to 50% by mass, more preferably 95 to 60% by mass, still more preferably 90 to 70% by mass,
1-50 mass% is preferable, as for the masterbatch for resin additives, More preferably, it is 5-40 mass%, More preferably, it is 10-30 mass%.

  The composition of the present invention can be blended with other necessary components depending on the required properties and applications. For example, various inorganic fillers or organic fillers can be blended from the viewpoint of increasing mechanical strength, and ultraviolet absorbers and heat stabilizers can be blended from the viewpoint of increasing light resistance and heat resistance. .

  The composition of the present invention can be obtained by kneading a predetermined amount of a thermoplastic resin and a resin additive masterbatch in a molten state using a known single or twin screw extruder. Since the composition of the present invention includes a master batch for a resin additive that acts as a compatibilizer for two or more resins, the two or more resins are uniformly kneaded.

  The molded body of the present invention can be obtained by applying a known resin molding method such as an injection molding method to the composition of the present invention.

  When the molded body of the present invention is obtained from a composition containing, for example, two types of thermoplastic resins (polyamide and ABS resin), a resin phase (polyamide phase) serving as a matrix (sea) and a resin phase serving as an island It is considered that a polymer having a maleimide monomer unit contained in the master batch for resin additive exists at the interface with (ABS resin phase), and maleimide in the resin phase (polyamide phase) that becomes the sea. The polymer having a monomer unit is finely dispersed. For this reason, even when the resin molded body used for plating in the present invention is obtained from a composition containing two or more thermoplastic resins, the molded body is homogeneous and there is no variation in properties.

  The details of each component and measurement method used in Examples and Comparative Examples are as follows.

(Thermoplastic resin)
PA-1: Standard polyamide (Polyamide 6, Ube Industries, UBE nylon 6 1013B, water absorption 1.8%, melt flow index at 230 ° C 1 kg: 17)
PA-2: Highly flowable polyamide (Polyamide 6, Ube Industries, UBE nylon 6 1011FB, water absorption 1.8%, melt flow index at 230 ° C 1kg: 50)
PS-1: ABS resin (styrene content 45% by mass, acrylonitrile 15% by mass, rubber content 40% by mass)
PS-2: Standard AS resin (styrene content 75% by mass, acrylonitrile 25% by mass, melt flow index 30 at 10 ° C. at 220 ° C .: 30)
PS-3: High fluidity AS resin (styrene content 75% by mass, acrylonitrile 25% by mass, melt flow index at 220 ° C. and 10 kg: 60)
(Polymer having maleimide monomer units)
Styrene-N-phenylmaleimide-maleic anhydride copolymer (47% by mass of styrene, 51% by mass of N-phenylmaleimide, 2% by mass of maleic anhydride, weight average molecular weight of 145,000, 265 ° C., 10 kg) : 2).

(Measuring method)
Charpy impact strength: Measured according to ISO179.

Examples 1 to 8 (Manufacture of a master batch for resin addition)
After mixing each component shown in Table 1 with a V-shaped tumbler, it was melt-kneaded in a twin-screw extruder (manufactured by Nippon Steel, TEX30, cylinder temperature 230 ° C., rotation speed 350 rpm, discharge rate 30 kg / hr), Examples 1 to 8 masterbatch pellets were obtained.

Examples 9 to 16 (thermoplastic resin composition)
In Examples 9 to 16, the thermoplastic resin shown in Table 2 and the pellets of the resin addition masterbatch obtained in Examples 1 to 4 were mixed with a V-shaped tumbler, and then a twin-screw extruder (manufactured by Nippon Steel, TEX30, The mixture was melt-kneaded at a cylinder temperature of 230 ° C., a rotational speed of 350 rpm, and a discharge rate of 30 kg / hr) to obtain pellets of the composition of the present invention.

  In Comparative Examples 1 to 8, a thermoplastic resin shown in Table 2 and a polymer having a maleimide monomer unit were mixed with a V-type tumbler, and then a twin screw extruder (manufactured by Nippon Steel, TEX30, cylinder temperature 230 ° C., rotation speed 350 rpm And a discharge rate of 30 kg / hr) to obtain a comparative composition pellet.

  Next, each composition of Examples 9 to 16 and Comparative Examples 1 to 8 was used for injection molding by an injection molding machine (cylinder temperature 240 ° C., mold temperature 60 ° C.) to produce an ISO dumbbell molded product. The Charpy strength of the obtained molded product was measured. The results are shown in Table 2.

  Further, a transmission electron micrograph (upper) of a molded product (an injection molded product produced in the same manner as described above) obtained from the composition of Example 9 and a conceptual diagram (lower) (FIG. 1) for explaining it. And a transmission electron micrograph (upper) of a molded article obtained from the composition of Comparative Example 1 and a conceptual diagram (lower) (FIG. 2) for explaining it.

As is clear from FIG. 1, the molded body 1 obtained from the composition of Example 9 has the ABS phase (island) 3 dispersed in the PA phase (sea) 2 and has maleimide monomer units in the PA phase 2. The polymer 4b has a finely dispersed structure. Although not clear from the transmission electron micrograph of FIG. 1, the resin additive is added to the interface between the PA phase 2 and the ABS phase 3 as shown in the figure because of the fact that the ABS phase is dispersed in the PA phase. It is considered that there is a polymer 4a having a maleimide monomer unit contained in the master batch for use.

  As is apparent from FIG. 2, in the molded article 11 obtained from the composition of Comparative Example 1, the ABS phase (island) 13 is dispersed in the PA phase (sea) 12, and the resin is formed at the interface between the PA phase 12 and the ABS phase 13. A polymer 14a having a maleimide monomer unit contained in the additive masterbatch exists, and a polymer 4b having a maleimide monomer unit in the ABS phase 13 is contained.

  The transmission electron micrograph was taken by the following method. An ultrathin section of about 200 nm was cut out from the vicinity of the surface of an injection molded product sample (business card size of 2 mm thickness) using a microtome, and then stained with phosphotungstic acid at 80 ° C. for 1 hour. Using this dyed sample, observation with a transmission electron microscope and photography were carried out.

  As is clear from Table 2, compositions obtained from the thermoplastic resins of Examples 9 to 16 and the master batch for resin addition, compositions obtained from the thermoplastic resins of Comparative Examples 1 to 8 and a compatibilizer, and As a result, a remarkable difference was observed in the obtained molded bodies. These results show that the kneadability of the two types of thermoplastic resins was improved by using the resin addition masterbatch.

10 is a transmission electron micrograph of a molded product obtained from the composition of Example 9. FIG. Transmission electron micrograph of a molded article obtained from the composition of Comparative Example 1

Claims (7)

A masterbatch for resin addition containing a polyamide resin containing a thermoplastic resin and a polymer having a maleimide monomer unit,
The thermoplastic resin is polyamide 6;
The polymer having a maleimide monomer unit is an aromatic vinyl monomer selected from maleimide monomers, styrene, α-methyl styrene, vinyl ketone, and t-butyl styrene, maleic anhydride, methyl maleic anhydride, 1,2- A copolymer comprising an unsaturated dicarboxylic anhydride monomer selected from dimethylmaleic acid, ethylmaleic anhydride, and phenylmaleic anhydride,
The resin addition masterbatch containing a polyamide resin, wherein the resin containing the polyamide resin is a resin containing polyamide 6 and a styrene resin. A masterbatch for resin addition containing a polyamide resin containing a thermoplastic resin and a polymer having a maleimide monomer unit,
The thermoplastic resin is an AS resin;
The polymer having a maleimide monomer unit is an aromatic vinyl monomer selected from maleimide monomers, styrene, α-methyl styrene, vinyl ketone, and t-butyl styrene, maleic anhydride, methyl maleic anhydride, 1,2- A copolymer comprising an unsaturated dicarboxylic anhydride monomer selected from dimethylmaleic acid, ethylmaleic anhydride, and phenylmaleic anhydride,
The resin addition masterbatch containing a polyamide resin, wherein the resin containing the polyamide resin is a resin containing a polyamide resin and a styrene resin.   The maleimide monomer is maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-toluylmaleimide, N-xylylmaleimide, N A masterbatch for resin addition containing a polyamide resin according to claim 1 or 2, which is selected from -naphthylmaleimide, Nt-butylmaleimide, N-orthochlorophenylmaleimide, and N-orthomethoxyphenylmaleimide.   The master for resin addition containing the polyamide resin according to any one of claims 1 to 3, comprising 95 to 10% by mass of the thermoplastic resin and 5 to 90% by mass of a polymer having the maleimide monomer unit. batch.   It is a manufacturing method of the masterbatch for resin additives of any one of Claims 1-4, The polyamide resin which knead | mixes the said thermoplastic resin and the polymer which has the said maleimide-type monomer unit in a molten state is included. A method of manufacturing a master batch for resin addition.   A thermoplastic resin composition comprising 99 to 50% by mass of a thermoplastic resin containing the polyamide-based resin and 1 to 50% by mass of a master batch for a resin additive produced in claim 5.   The molded object obtained from the thermoplastic resin composition of Claim 6.