JP2021109882A - Masterbatch for pearl-tone molded article, resin composition and pearl-tone molded article - Google Patents

Abstract

To provide a molded article that has a pearl tone and resists surface peeling, a masterbatch that allows molding of the pearl-tone molded article, and a resin composition.SOLUTION: The present disclosure provides a masterbatch for a pearl-tone molded article that is to mold a pearl-tone molded article using an aromatic polyester (A') as a dilution resin, the masterbatch containing an aromatic polyester (A), a polypropylene (B), and an acid-modified polyolefin (C).SELECTED DRAWING: None

Description

The present invention relates to a masterbatch, a resin composition used for producing a pearl-like molded product using an aromatic polyester as a base polymer, and a pearl-like molded product molded from the resin composition.

Resin molded bodies made of plastic (hereinafter, simply referred to as molded bodies) are widely used for members of various containers, daily necessities, and the like. Polyolefins and polyesters are often used for this molded product from the viewpoints of moldability, mechanical strength, recyclability, heat resistance and the like. In recent years, resin molded products have been required to have a beautiful appearance and high design, which has become a major appeal for consumers to purchase products. Therefore, for example, for shampoo containers and beverage container caps. , A pearly luster is added to create a luxurious feel.

As a method for imparting pearl-like luster to a molded product, in addition to a method of applying a pearl-like material such as a titanium-based pearl pigment to the surface of the molded product or kneading it into a resin composition to obtain a molded product, the refractive index There is known a method of forming a molded product by a resin composition obtained by blending different resins. In the former method, light is reflected on the surface of pearly luster (for example, mica), and they interfere with each other to exhibit pearly luster. However, in this method, the pearl pigment may aggregate depending on the blending amount of the pearl pigment and the molding method, leading to poor appearance. On the other hand, in the latter method, light is reflected and refracted at resin interfaces having different refractive indexes, and these interfere with each other to obtain pearly luster. As the latter method, for example, Patent Document 1 discloses a resin composition in which polyester and polyolefin are blended. According to this method, since the resins are mixed with each other to obtain a brilliant feeling, a molded product having a good appearance without generating agglomerates can be obtained.

Japanese Unexamined Patent Publication No. 11-000981

However, in the conventional resin composition, two kinds of resins having different refractive indexes are blended to obtain a pearl-like luster due to the difference in the refractive indexes. However, the compatibility between the resins is low and the pearl-like texture (for example, luster, There was a problem that it was difficult to obtain luster, depth, etc.). Furthermore, when a container is molded using a conventional resin composition, when a peeling test is performed with an adhesive tape such as cellophane tape (registered trademark), surface peeling occurs due to its low compatibility, and the surface is exposed. It had serious drawbacks such as feathering. This not only affects the adhesive fastness when the label is attached or printed on the surface of the container, but also causes remarkably noticeable scratches due to external factors such as slight rubbing, which leads to spoiling the appearance.

An object of the present invention is to provide a molded product having a pearl tone and suppressing surface peeling, a master batch capable of molding the pearl tone molded product, and a resin composition.

As a result of intensive studies to solve the above problems, the present inventors have obtained a masterbatch for forming a pearl-like molded product using an aromatic polyester as a base polymer, and the aromatic polyester (A). , Polypropylene (B), and Acid-Modified Polyolefin (C). It was done.

The masterbatch for a pearl-like molded product containing the aromatic polyester (A), polypropylene (B), and acid-modified polyolefin (C) of the present invention is used to prepare a molded product using the aromatic polyester (A') as a diluting resin. It is possible to produce a pearl-like molded product having high solubility and having difficulty in surface peeling in a peeling test.

≪Masterbatch≫
The masterbatch of the present invention contains aromatic polyester (A), polypropylene (B), and acid-modified polyolefin (C), and is combined with aromatic polyester (A'), which is a resin diluted at a predetermined magnification at the time of molding the molded product. It is kneaded to obtain a resin composition, which is used for molding a pearl-like molded product.
The masterbatch is preferably in the form of pellets, powder, granules, beads, or the like, and more preferably in the form of pellets.

The masterbatch of the present invention suppresses the generation of swells that occur when the viscosities are not uniform when melt-kneading resins having significantly different melt viscosities, that is, aromatic polyester (A) and polypropylene (B), and acid-modified polypropylene. By using (C) to improve the compatibility between the two, a stable masterbatch can be produced.
As a result, it becomes possible to increase the blending amount of polypropylene (B) in the masterbatch, which has been difficult in the past, and the brilliance of the molded product can be made excellent.

Further, the resin composition of the present invention suppresses surface peeling in the tape peeling test by blending the masterbatch with the aromatic polyester (A') which is a diluted resin and the aromatic polyester (A) having a high affinity. A pearl-like molded product can be produced.

<Aromatic polyester (A)>
The aromatic polyester (A) is an ester of a dicarboxylic acid component and a diol component. The aromatic ring is often contained by a dicarboxylic acid component, but may be contained by a diol component.

Examples of the dicarboxylic acid component include terephthalic acid, dimethyl terephthalate, 2,6 naphthalenedicarboxylic acid, naphthalenedicarboxylic acid and the like.
Examples of the diol component include ethylene glycol, butylene glycol, 1,3 propanediol, 1,4 butanediol, and 1,4 cyclohexanedimethanol.

The aromatic polyester (A) is preferably an aromatic polyester having a flexural modulus of 2000 MPa or more at 23 ° C. As a result, when the resin composition is molded into a container shape, for example, it becomes easy to achieve both mechanical properties and transparency.
Examples of the aromatic polyester (A) include polyethylene terephthalate, polybutylene terephthalate, polymethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexane terephthalate and the like. Among these, polyethylene terephthalate, which has high transparency and is excellent in recyclability, cost, and processability, is preferable.

Examples of polyethylene terephthalate include crystalline polyethylene terephthalate (C-PET), amorphous polyethylene terephthalate (A-PET), glycol-modified polyester (PET-G), and glass-reinforced polyethylene terephthalate.

The D-line refractive index (JIS K 7142) of the aromatic polyester (A) at 23 ° C. is preferably 1.4 to 1.8, more preferably 1.5 to 1.7, and 1.55. ~ 1.65 is more preferable. When the D-line refractive index is in the range of 1.4 to 1.8, it becomes easy to obtain pearly luster.

The content of the aromatic polyester (A) is preferably 10 to 90% by mass, more preferably 40 to 80% by mass, and preferably 50 to 80% by mass in 100% by mass of the masterbatch. Especially preferable. Within the above range, the compatibility between the aromatic polyester (A') which is the diluted resin and the masterbatch can be made better, and the surface peelability can be made excellent.
Above all, when the content of the aromatic polyester (A) is 50% by mass or more in 100% by mass of the masterbatch, it is preferable because the balance between surface peelability and brilliance is excellent.

<Polypropylene (B)>
Examples of polypropylene (B) include propylene homopolymer, ethylene-propylene copolymer, polypropylene obtained by using a metallocene compound as a polymerization catalyst, and the like. Among these, an ethylene-propylene copolymer having a low crystallinity, a small influence of light scattering (white blur) in the crystal portion, and high transparency is preferable. By using the ethylene-propylene copolymer, when the molded product is molded, the light interference effect is likely to occur not only on the surface of the molded product but also inside the molded product, and the pearly texture of the molded product is improved.

The melt viscosity of polypropylene is preferably 1 to 60 (g / 10 minutes), more preferably 7 to 50 (g / 10 minutes) in terms of melt flow rate (MFR). If the MFR exceeds 60 (g / 10 minutes), a masterbatch may not be produced due to the difference in viscosity with the aromatic polyester (A) during melt-kneading. Further, when the MFR is 1 (g / 10 minutes) or more, stretching can be sufficiently performed at the time of molding, and a more excellent brilliant feeling can be obtained. Further, when the MFR is 7 (g / 10 minutes) or more, it becomes easy to follow the stretching during bottle molding, and the peelability is suppressed.
Melt flow rate (MFR) can be measured under the conditions conforming to JIS (Japanese Industrial Standards) K7210: 1999 (ISO1133: 1997).

The content of polypropylene (B) is preferably 5 to 95% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 60% by mass in 100% by mass of the masterbatch. , 30 to 50% by mass is particularly preferable. Within the above range, the peelability can be made better.

<Acid-modified polyolefin (C)>
By using the acid-modified polyolefin (C), the compatibility between the aromatic polyester (A) and the polypropylene (B) can be improved. Therefore, the acid-modified polyolefin preferably has a characteristic group derived from an organic acid. The characteristic group is preferably a hydroxy group, a carbonyl group, a sulfo group, a carboxyl group, a phosphoric acid group, a thiol group or the like, and a saturated or unsaturated carboxylic acid having a carboxyl group is preferable. An acid anhydride group is also preferable. The acid-modified polyolefin (C) can be synthesized, for example, by reacting (modifying) the polyolefin with an organic acid having the above-mentioned characteristic group in the presence of a peroxide.

Examples of saturated or unsaturated carboxylic acids having a carboxyl group include formic acid, acetic acid, propionic acid, acrylic acid, methacrylic acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, phthalic acid, and terephthalic acid. .. Examples of the organic acid having an acid anhydride group include maleic anhydride, acetic anhydride, propionic anhydride, succinic anhydride, phthalic anhydride and the like.

The acid value of the acid-modified polyolefin (C) is preferably 1 to 60 mgKOH / g, more preferably 1 to 50 mgKOH / g. When the acid value is 1 to 60 mgKOH / g, it becomes easy to obtain an appropriate compatibility between polypropylene (B) and aromatic polyester (A). When the acid value is 60 mgKOH / g or less, the hydrolysis of the aromatic polyester can be suppressed, and the compatibility between the aromatic polyester (A) or the aromatic polyester (A') and the polypropylene (B) is high. Therefore, it becomes easy to mold into pellets, and peeling is further suppressed.
The acid value can be measured under the conditions according to JIS K0070.

As described above, the acid-modified polyolefin (C) is preferably synthesized by modifying the polyolefin with an organic acid having the above-mentioned characteristic group in the presence of a peroxide. The polyolefin before modification is, for example, a homopolymer such as ethylene, propylene, butene and pentene, or a copolymer thereof as a main component. The polyolefins are, for example, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, propylene-vinyl acetate copolymer, propylene-. Methyl acrylate copolymer, propylene-methyl methacrylate copolymer, propylene-ethyl acrylate copolymer, polybutene, poly-3-methyl-1-butene copolymer, poly-4-methyl-1-pentene copolymer, etc. Can be mentioned.
The acid-modified polyolefin (C) can be used alone or in combination of two or more.

The performance obtained differs depending on the type of polyolefin, and it is preferable to use acid-modified polyethylene or acid-modified polypropylene. Since the acid-modified polypropylene has a high affinity with polypropylene (B), peeling can be reduced with a small amount. On the other hand, acid-modified polyethylene has a high affinity with colorants such as pigments and can improve color development.

The acid-modified polyolefin (C) preferably contains 0.1 to 500 parts by mass, more preferably 0.1 to 100 parts by mass, with respect to 100 parts by mass of polypropylene (B). By containing 1 to 500 parts by mass, it becomes easy to obtain an appropriate compatibility between the aromatic polyester (A) and the polypropylene (B), and surface peeling is further suppressed in the tape peeling test.

<Colorant>
The masterbatch can further contain a colorant. As a result, the pearl-like molded product can be colored in a desired color. The colorants are preferably pigments and dyes. Examples of the pigment include black pigments and chromatic pigments.
In addition, a pearl pigment can be used in combination if necessary. Since the pearl-like molded product of the present invention has an excellent brilliance without using a pearl pigment, the blending amount can be reduced even when a pearl pigment is used, and the appearance of the molded product can be reduced. Can be made good.
The colorant may be used alone or in combination of two or more.
When a colorant is used, the acid-modified polyolefin (C) can enhance the color-developing property of the pigment, and therefore it is preferable to use acid-modified polyethylene.

Black pigments are organic black pigments such as aniline black, anthraquinone black, and perylene black;
Carbon Black, Lamp Black, Graphite, Fullerene, Carbon Nanotubes, Magnetite, Iron-Titanium Composite Oxide, Cobalt Oxide, Manganese Dioxide, Zinc Sulfide, Copper-Chrome Composite Oxide, Tin-Antimon Composite Oxide, Titanium-Vanadium-Antimon Composite oxide, cobalt-nickel composite oxide, manganese-iron composite oxide, iron-cobalt-chromium composite oxide, copper-chromium composite oxide, iron-cobalt composite oxide, chromium-iron-nickel composite oxide, Inorganic black pigments such as molybdenum disulfide, black titanium dioxide, titanium nitride, and chromium oxide; and the like.

The chromatic pigment is preferably a pigment such as a red pigment, a yellow pigment, an orange pigment, a purple pigment, a blue pigment, a green pigment, or a brown pigment.

Examples of the red pigment include naphthol pigments, azo pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments and the like.

Examples of the yellow pigment include organic pigments such as azo pigments, anthraquinone pigments, isoindolinone pigments, quinophthalone pigments and benzimidazolone pigments; titanium-nickel-antimon composite oxides, zinc-iron composite oxides and the like. Inorganic pigments;

Examples of the orange pigment include naphthol pigments, azo pigments, benzimidazolone pigments, quinacridone pigments, diketrolopyrrole pigments and the like.

Examples of the purple pigment include azo pigments, rhodamine pigments, quinacridone pigments, carbazole pigments, perylene pigments, quinacridone pigments and the like.

Examples of the blue pigment include organic pigments such as phthalocyanine pigments; inorganic pigments such as cobalt-aluminum composite oxide, cobalt-aluminum-chromium composite oxide, and ultramarine blue.

Examples of the green pigment include organic pigments such as phthalocyanine pigments and azo pigments; inorganic pigments such as chromium oxide, cobalt-chromium-aluminum composite oxide, and cobalt-nickel-zinc composite oxide.

Examples of the brown pigment include organic pigments such as azo pigments and benzimidazolone pigments; inorganic pigments such as iron oxides and titanium-chromium-antimony composite oxides.

The dyes are preferably acidic dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, medium dyes, building dyes, sulfide dyes and the like.

Examples of the acid dyes include anthraquinone-based acid dyes, phthalocyanine-based acid dyes, quinoline-based acid dyes, azine-based acid dyes, indigoid-based acid dyes, xanthene-based acid dyes, and triphenylmethane-based acid dyes.

Examples of the direct dye include an azo-based direct dye, a thiazole-based direct dye, an anthraquinone-based direct dye, an oxazine-based direct dye, and a phthalocyanine-based direct dye.

Examples of basic dyes include azo-based basic dyes, azine-based basic dyes, acrydin-based basic dyes, methine-based basic dyes, thiazole-based basic dyes, thiazine-based basic dyes, oxazine-based basic dyes, and anthraquinone. Examples thereof include based basic dyes, xanthene based basic dyes, and triarylmethane based basic dyes.

Examples of oil-soluble dyes include anthraquinone-based oil-soluble dyes, phthalocyanine-based oil-soluble dyes, quinoline-based oil-soluble dyes, azine-based oil-soluble dyes, indigoid-based oil-soluble dyes, methine-based oil-soluble dyes, azo-based oil-soluble dyes, and aminoketones. Examples thereof include based oil-soluble dyes, xanthene-based oil-soluble dyes, and triphenylmethane-based oil-soluble dyes.

Examples of the disperse dye include anthraquinone-based disperse dyes, quinoline-based disperse dyes, indigoid-based disperse dyes, quinophthalone-based disperse dyes, methine-based disperse dyes, azo-based disperse dyes, aminoketone-based disperse dyes, and xanthene-based disperse dyes.

Further, a salt-forming dye such as a salt-forming body of the acid dye and the cationic compound, a salt-forming body of the basic dye and the anionic compound, or a salt-forming body of the acid dye and the basic dye can be used.

The content of the colorant is not particularly limited, but is preferably 0.0001 to 35% by mass, more preferably 0.001 to 20% by mass, based on 100% by mass of the masterbatch. By including the colorant in an appropriate range, a pearl-like molded product having a high pearl-like texture while having coloring can be obtained.

The masterbatch of the present invention has impact resistance, antibacterial property, gas barrier property, conductivity, magnetism, piezoelectricity, vibration damping property, sound insulation property, slidability, electromagnetic wave absorption, flame retardancy, and dehydration property as required. , An inorganic filler can be further blended for the purpose of improving any of the properties such as deodorizing property, anti-blocking property, oil absorption property, water absorption property, and moldability.

Inorganic fillers include, for example, carbon fiber, glass fiber, glass flakes, zeolite, mica, graphite, metal powder, ferrite, alumina, barium titanate, potassium titanate, barium sulfate, Teflon® powder, talc, charcoal. Examples thereof include powder, carbon nanotube (CNT), carbon microcoil (CMC), antimony oxide, aluminum hydroxide, magnesium hydroxide, hydrotalcite, calcium oxide, silica, calcium carbonate and the like.
The inorganic filler is preferably adjusted so as to contain 0.01 to 20% by mass in 100% by mass of the final pearl-like molded product. By including the inorganic filler in an appropriate range, it is easy to maintain the pearly texture while obtaining the characteristics of the inorganic filler.

<Manufacturing method of masterbatch>
The method for producing the masterbatch of the present invention is to add aromatic polyester (A), polypropylene (B), acid-modified polyolefin (C), and if necessary, other optional components, and mix, melt, knead, or the like. It can be produced by doing.
The masterbatch can be produced in the form of pellets, powders, granules, beads, or the like. By blending a colorant at the time of melting and kneading, the pearl-like molded product can be colored in a desired color tone.

For mixing, for example, a known device such as a Henschel mixer, a tumbler, a dispenser, a kneader, a roll mill, a super mixer, a Henschel mixer, a vertical granulator, a high speed mixer, a fur matrix, a ball mill, a steel mill, a sand mill, a vibration mill, and an attritor is used. Can be used.

For melt kneading, known devices such as a Banbury mixer, a twin-screw extruder, a single-screw extruder, a rotor-type twin-screw kneader, and a kneader can be used.

The melt-kneading temperature is preferably 200 to 280 ° C, more preferably 230 to 250 ° C. Melt kneading at 230 to 250 ° C. reduces the difference in melt viscosity between aromatic polyester and propylene, facilitating extrusion.

≪Resin composition≫
The resin composition of the present invention contains a masterbatch for a pearl-like molded product and an aromatic polyester (A'), and is used for forming a pearl-like molded product using the aromatic polyester as a base polymer.
By blending the aromatic polyester (A) contained in the masterbatch with the aromatic polyester (A') having a high affinity as a diluting resin, a pearl-like molded product in which surface peeling is suppressed in a tape peeling test is produced. Can be done.
The resin composition obtained by kneading can be molded into any shape such as pellets, powders, granules or beads. Further, after kneading the masterbatch and the aromatic polyester (A'), a molded product may be formed as it is.

The resin composition of the present invention may further contain the above-mentioned colorant. Others, for example, leveling agents, pigment dispersants, ultraviolet absorbers, antioxidants, viscosity modifiers, light resistance stabilizers, metal deactivators, peroxide decomposing agents, processing stabilizers, nucleating agents, crystallization accelerators, etc. Appropriately known additives such as crystallization retarders, antigels, fillers, reinforcing agents, plasticizers, lubricants, flame retardants, rust preventives, fluorescent whitening agents, fluidity modifiers, antistatic agents, etc. Can be selected and blended.

<Aromatic polyester (A')>
Aromatic polyester (A') is a resin that is a main component of a pearl-like molded product, and is a diluted resin of a masterbatch. As the aromatic polyester (A'), those described in the above-mentioned aromatic polyester (A) can be used. The aromatic polyester (A') used in the resin composition of the present invention may be the same as or different from the aromatic polyester (A) used for forming the masterbatch. It is preferable to use the same aromatic polyester (A') and aromatic polyester (A) because the affinity is further enhanced and peeling is suppressed.

<Manufacturing method of resin composition>
The method for producing the resin composition of the present invention is not particularly limited, and the same method as the masterbatch described above can be used.

≪Pearl-like molded body≫
The pearl-like molded product of the present invention is molded using a resin composition, and aromatic polyester is the base polymer.
The method for producing a pearl-like molded product is to melt-knead a master batch containing aromatic polyester (A), polypropylene (B), and acid-modified polyolefin (C) with aromatic polyester (A') and mold the molded product. Can produce a pearl-like molded product.
For example, a bottle molded product having a good brilliant feeling can be obtained by forming a preform from a master batch and an aromatic polyester (A') and then stretching the preform with air or the like.
When the pearl-like molded product of the present invention is produced by the above-mentioned production method, the compatibility between the aromatic polyester (A) and polypropylene (B) becomes higher, and the resistance to surface peeling becomes higher, which is preferable.

The melt-kneading temperature is preferably 200 to 370 ° C, more preferably 220 to 350 ° C. Further, for the melt kneading, the apparatus already described can be used.

Blow molding (biaxial stretch blow molding, direct blow molding, etc.) is preferable as the molding method for obtaining a pearl-like molded product in the present invention. This molding method is preferable because the master batch dispersed in the aromatic polyester (A') is stretched or oriented to further improve the pearly texture.
Further, since the more stretched the molded product is, the more remarkable surface peeling is likely to occur in the tape peeling test, it is preferable to prepare the pearl-like molded product by the above manufacturing method.

The composition of the aromatic polyester (A') and the masterbatch of the present invention is preferably 100: 1 to 100: 20, and more preferably 100: 3 to 100:10 in terms of mass ratio. By containing one or more parts of the masterbatch with respect to 100 parts by mass of the aromatic polyester (A'), it is possible to suppress variations in the molded product. In addition, by reducing the number of master batches to 20 or less, the cost can be significantly reduced as compared with the case of compounding.

In the pearl-like molded product of the present invention, the resin provides a pearl-like texture that cannot be obtained without blending a pearl-like pigment such as a pearl pigment or mica. This pearl-like molded body is not only for general decorations and containers that require high texture, but also for exterior parts of various home appliances, personal computers, smartphones, tablet terminals, digital cameras and other electronic devices, housing building material parts, ships, and aircraft. , Can be widely used as interior / exterior parts inside the vehicle.

Above all, a container is preferable as the form of the pearl-like molded product of the present invention. Specifically, various skin lotions such as moisturizing lotion, massage lotion, skin lotion, cleansing lotion, emollient lotion, baby oil, skin cream such as makeup cream, vanishing cream, emollient cream, and various face care products such as liquid foundation. Skin care, body care, make-up cosmetics, shampoo, rinse, hair conditioner, perma lotion, hair color and other hair care products, whole body cleanser, liquid hand soap and other body care, hand care products, liquid clothing detergent, decoction, It is suitable as a container for filling glass cleaners, lotions, softeners, glues, dishwashing detergents, cleansers, various household detergents, other foodstuffs, pharmaceuticals, etc. that generally require a good appearance.

As a method for molding the container, a method of molding by stretching is preferable. For example, injection blow molding and direct blow molding are mentioned as the method, and injection blow molding having a large stretch is preferable.
As the injection blow molding, either the hot parison method or the cold parison method may be used, and it is sufficient that the injection blow molding is stretched at least 1.1 times in the uniaxial direction at the time of molding.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. Further, "part" in the embodiment means a mass part, and "%" means a mass%.
In addition, the compounding amount in the table is a part by mass, and the blank indicates that the compound is not blended.
Moreover, the formulation in the table shows only the formulation of the masterbatch, and does not describe the formulation of aromatic polyester (A').

[Melting viscosity of polypropylene (B)]
The melt viscosity (melt flow rate (MFR)) of polypropylene is a value measured under conditions conforming to JIS (Japanese Industrial Standards) K7210: 1999 (ISO1133: 1997).
[Acid value of acid-modified polyolefin (C)]
The acid value is a value measured under the conditions according to JIS K0070.

The raw materials used in the examples are shown below.
[Aromatic polyester (A)]
(A-1): Amorphous polyethylene terephthalate (A-PET, manufactured by Mitsui Chemicals, SA135)
(A-2): Glycol-modified polyester (PET-G, manufactured by Eastman Chemical Company, GN001)

[Polypropylene (B)]
(B-1): Ethylene-propylene copolymer (manufactured by Prime Polymer Co., Ltd., J226T, MFR = 20 g / 10 min)
(B-2): Propylene homopolymerization (manufactured by SunAllomer Ltd., PM600A, MFR = 7.5 g / 10 min)
(B-3): Ethylene-propylene copolymer (manufactured by Prime Polymer Co., Ltd., J704UG, MFR = 5 g / 10 min)

[Acid-modified polyolefin (C)]
(C-1): Maleic anhydride-modified polypropylene (manufactured by Sanyo Chemical Industries, Ltd., Youmex 1001, acid value: 26 mgKOH / g)
(C-2): Acid-modified polyethylene (manufactured by Honeywell, AC poly 316A, acid value: 16 mgKOH / g)
(C-3): Maleic anhydride-modified polypropylene (manufactured by Sanyo Chemical Industries, Ltd., Youmex 1010, acid value: 52 mgKOH / g)

[Pigment]
(D-1): Blue organic pigment (β-type phthalocyanine blue CI Pigment Blue 15: 3, average primary particle size: 0.1 μm)
(D-2): Pearl pigment (Merck & Co., Ltd., Iriodin120 Luster Satin, particle size 5 μm to 25 μm, titanium oxide coating amount 38%)

[others]
(E-1): Zinc stearate / calcium stearate mixture (mixing ratio: 1/1, manufactured by Dainichi Chemical Industry Co., Ltd., Daiwax ZCF)

(Example 1)
(1) Production of Masterbatch 60 parts by mass of aromatic polyester (A-1), 35 parts by mass of polypropylene (B-1), and 5 parts by mass of acid-modified polyolefin (C-1) were mixed at a rotation speed of 300 rpm for 3 parts. A mixture was obtained by stirring and mixing for 1 minute. The mixture was put into a twin-screw extruder (manufactured by Nippon Placon Co., Ltd.) having a set temperature of 230 ° C. and melt-kneaded and granulated to obtain a pellet-shaped masterbatch.

(2) Manufacture of pearl-like molded article As aromatic polyester (A'), 100 parts by mass of aromatic polyester (Mitsui PET SA135, manufactured by Mitsui Chemicals Co., Ltd.) and 4 parts by mass of the obtained masterbatch were used at a cylinder set temperature of 280. It was put into a biaxial stretching blow molding machine at ° C. to obtain a preform (diameter 2.5 cm, length 7.5 cm, thickness 9 mm). The obtained preform was kept warm at 120 ° C. and stretched in a blowing die having a mold temperature control temperature of 15 ° C. to obtain a pearl-like molded product having a diameter of 7.5 cm, a length of 15 cm and a thickness of 3 mm.

(Examples 2 to 19, Comparative Examples 1 to 3, Reference Example 1)
A masterbatch was prepared in the same manner as in Example 1 except that the raw materials and the blending amount (parts by mass) of Example 1 were changed as shown in Table 1, and the aromatic polyester (A') was fragrant. A resin composition and a pearl-like molded product were obtained using a group polyester (Mitsui PET SA135, manufactured by Mitsui Chemicals, Inc.).
In Comparative Example 3, a molded product could not be formed.

The obtained molded product was tested by the following method. The evaluation results are shown in Table 1.

<Surface peelability>
A cellophane tape having a width of 15 mm was attached to the surface of the container produced by biaxial stretching blow molding, and the surface condition when peeled off was evaluated. The evaluation criteria are as follows.

3: No peeling is seen on the surface 2: There is a slightly peeled part 1: The peeling is so remarkable that the surface becomes fluffy

The above evaluation was performed on 10 containers, and the average value was calculated.
A: 2.7 or more (90% or more does not peel) Good B: 2.4 or more and less than 2.7 (80% or more does not peel) Practical use C: 1.0 or more and less than 2.4 Practical use

<Pearl-like luster (brilliance)>
Twenty testers visually evaluated the superiority or inferiority of the pearly luster on the surface of the obtained molded product with respect to the molded product using the pearl pigment, which is a reference example. The evaluation criteria are as follows.

A: More than 18 people felt that it was equal to or better than the reference example. Very good B: 15 to 17 people felt that it was equal to or better than the reference example. Good C: 11 to 14 or less felt equal to or better than the reference example. Practical use D: I felt that 10 or less people were equal to or better than the reference example. Impractical

As is clear from the results in Tables 1 and 2, all of the molded products of Examples 1 to 19 were difficult to peel off on the surface in the tape peeling test, and excellent pearly luster was obtained.
Among them, when the masterbatch contains a colorant, Examples 14 and 18 in which the acid-modified polyethylene (C-2) is used as the acid-modified polyolefin (C) are not only brilliant but also have acidity. It was superior to the case of using modified polypropylene.
On the other hand, in Comparative Examples 1 to 3, good pearl-like texture and peeling resistance could not be obtained.

Claims (10)

A masterbatch for forming a pearl-like molded product using aromatic polyester (A') as a diluting resin.
A masterbatch for pearl-like molded articles, which comprises aromatic polyester (A), polypropylene (B), and acid-modified polyolefin (C). The masterbatch for a pearl-like molded product according to claim 1, wherein the acid value of the acid-modified polyolefin (C) is 1 to 60 mgKOH / g. The masterbatch for a pearl-like molded product according to claim 1 or 2, wherein the polypropylene (B) has a melt viscosity of 7 to 50 g / 10 minutes. The masterbatch for a pearl-like molded product according to any one of claims 1 to 3, wherein the content of the aromatic polyester (A) is 50% by mass or more in 100% by mass of the masterbatch. The master batch for a pearl-like molded product according to any one of claims 1 to 4, further comprising a colorant. The masterbatch for a pearl-like molded product according to any one of claims 1 to 5, wherein the acid-modified polyolefin (C) is acid-modified polyethylene. A resin composition containing the masterbatch for a pearl-like molded product according to any one of claims 1 to 6 and an aromatic polyester (A'). A pearl-like molded product formed from the resin composition according to claim 7. The pearl-like molded product according to claim 8, which is a pearl-like container. A pearl-like molded product in which a masterbatch for a pearl-like molded product containing aromatic polyester (A), polypropylene (B), and acid-modified polyolefin (C) and an aromatic polyester (A') are melt-kneaded and molded. Manufacturing method.