JP2015137285A - resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition from which a chromatic pearl-tone molded article with suppressed color irregularity can be formed.SOLUTION: The resin composition comprises 100 parts by weight of a polyester resin (A), 1 to 60 parts by weight of a polyolefin resin (B), 1 to 40 parts by weight of an acid-modified styrene block copolymer (C), and a colorant (D). When melt viscosities of the polyester resin (A) and of the polyolefin resin (B) at 270°C and at a shear speed of 240 secare denoted by ηand η, respectively, η/ηis 0.11 or more and 1.60 or less. The colorant (D) comprises at least either of a black colorant showing an average reflectance of 10% or less in a wavelength range from 380 to 750 nm and a chromatic colorant showing a peak of a maximum reflectance of 3% or more in a wavelength range from 380 to 500 nm.

Description

  The present invention relates to a resin composition for molding.

  Generally, resin molded bodies are used for members such as various containers and daily necessities. In many cases, a polyolefin resin or a polyester resin is used for the resin molded body from the viewpoint of moldability, mechanical strength, recyclability, heat resistance, and the like. In recent years, a beautiful appearance and high designability have been demanded for resin moldings, which has become a major appeal point for consumers to purchase products. For example, for shampoo bottles and beverage bottle caps. By adding pearly luster, it creates a high-class feeling.

  As a method for imparting a pearly luster to a resin molded body, in addition to a method of applying a pearly luster exhibiting agent such as a titanium-based pearl pigment to the surface of the molded body or kneading it into the resin molded body, the refractive index differs A method of blending polymers is known. In the former method, light is reflected on the surface of pearly luster (for example, mica), and the pearly luster is exhibited by interference. On the other hand, in the latter method, light is reflected and refracted at a resin interface having a different refractive index, and pearly luster is obtained by interference of these. For the latter method, Patent Document 1 discloses a resin composition in which a polyester resin and a polyolefin resin are blended.

Japanese Patent Laid-Open No. 54-032562

  However, the conventional resin composition blended two types of resins with different refractive indexes and obtained a pearly luster due to the difference in the refractive index, but further blended a colorant to form a colored pearly molded body. In this case, there is a problem that color unevenness occurs and pearly luster is lowered.

  An object of this invention is to provide the resin composition which can shape | mold the colored pearl tone molded object which suppressed the color nonuniformity.

The resin composition of the present invention comprises 100 parts by weight of a polyester resin (A), 1 to 60 parts by weight of a polyolefin resin (B), 1 to 40 parts by weight of an acid-modified styrenic block copolymer (C), and a colorant. (D) and
When the melt viscosity at a temperature of 270 ° C. and a shear rate of 240 sec ⁻¹ of the polyester resin (A) is η _A and the melt viscosity of the polyolefin resin (B) is η _B , η _A / η _B is 0.11. Is 1.60 or less,
Further, the colorant (D) includes at least a black colorant having an average reflectance of 10% or less at a wavelength of 380 to 750 nm, and a chromatic colorant having a peak of a maximum reflectance of 3% or more at a wavelength of 380 to 500 nm. Including either.

  According to the present invention, the molding of the resin composition is performed by setting the ratio of the melt viscosity under the specific conditions of the polyester resin (A) and the melt viscosity under the specific conditions of the polyolefin resin (B) to a specific range. The body was able to greatly suppress color unevenness. Furthermore, by controlling the reflectance of the colorant (D), the texture (gloss and depth) of the molded body was improved, and the effect of further improving the appearance was also obtained.

  The resin composition which can shape | mold the colored pearl tone molded object which suppressed the color nonuniformity by this invention was able to be provided.

The resin composition of the present invention comprises 100 parts by weight of a polyester resin (A), 1 to 60 parts by weight of a polyolefin resin (B), 1 to 40 parts by weight of an acid-modified styrenic block copolymer (C), and a colorant. (D). The melt viscosity at a temperature of 270 ° C. and a shear rate of 240 sec ⁻¹ of the polyester resin (A) is η _A , and the melt viscosity of the polyolefin resin (B) at a temperature of 250 ° C. and a shear rate of 240 sec ⁻¹ is η _B. Η _A / η _B is 0.11 or more and 1.60 or less.
Generally, when a pearl-like molded product is obtained using a resin composition containing a plurality of resins having different melt viscosities, each resin has a different melt viscosity and a different stretching behavior in the molding process. Stretch unevenness occurs and unevenness occurs in the pearly luster of the molded product. However, when a colorant (particularly a colorant with low reflectivity) was blended to form a colored pearl-like molded product, the difference in the stretching behavior was markedly uneven in color, greatly reducing the product quality of the molded product. . Therefore, color unevenness can be suppressed by controlling η _A / η _B to be 0.11 or more and 1.60 or less.

<Polyester resin (A)>
The polyester resin (A) includes dicarboxylic acid components such as terephthalic acid, dimethyl terephthalate, 2,6 naphthalene dicarboxylic acid, and naphthalene dicarboxylic acid, and ethylene glycol, butylene glycol, 1,3 propanediol, 1,4 butanediol, , 4-cyclohexanedimethanol can be obtained by copolymerizing a diol component. Specific examples include polyethylene terephthalate resin, polybutylene terephthalate resin, polymethylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, and polycyclohexane terephthalate resin. Among these, as the polyester resin, a polyethylene terephthalate resin that is inexpensive and excellent in processability and is widely used in various containers and daily necessities is preferable.

  Examples of the polyethylene terephthalate resin include crystalline polyethylene terephthalate (C-PET), amorphous polyethylene terephthalate (A-PET), glycol-modified polyester (PET-G), and glass-reinforced polyethylene terephthalate. Among these, amorphous polyethylene terephthalate (A-PET) and glycol-modified polyester (PET-G) are more amorphous because they are amorphous or have a low degree of crystallinity and are less affected by light scattering (white blur) in the crystal part. preferable.

The melt viscosity of the polyester resin (A) is preferably 10 to 500 Pa · s under the conditions of temperature: 270 ° C. and shear rate: 240 sec ⁻¹ . By adjusting the melt viscosity to a range of 10 to 500 Pa · s, the pearl tone can be further improved. When the colorant (D) is used, the molded article can improve the glitter feeling because the melt viscosity is 10 Pa · s or more. This is because the viscosity of the polyester resin (A), which is the resin to be dispersed (matrix resin), is 10 Pa · s or more, and the shear stress to the polyolefin resin (B), which is the dispersed resin (domain resin), is increased. The dispersibility of the resin (B) is improved. Therefore, the polyolefin resin (B) in the molded body is more finely dispersed and the surface area is increased, whereby the amount of light that interferes at the interface between the two resins is increased. Moreover, the color nonuniformity of a molded object can be reduced as melt viscosity is 500 Pa * s or less. This is because, in a molding method having a mold such as injection molding or blow molding, stretching unevenness due to friction with the mold occurs, but the polyester resin (A) has a melt viscosity of 500 Pa · s or less. It is estimated that the friction with the mold was reduced and the occurrence of color unevenness due to uneven stretching could be suppressed. On the other hand, in a molding method such as extrusion molding that does not use a mold, stretching unevenness due to flow unevenness occurs due to friction between the resin opening portion of the molding machine and the resin. As a result of the resin (A) having a melt viscosity of 500 Pa · s or less that reduces friction with the mold and suppresses uneven stretching, it is presumed that uneven color in the molded product can be suppressed. In the present invention, the melt viscosity is measured using a Capillograph 1D (capillary length: 10 mm, capillary diameter: 1 mm) manufactured by Toyo Seiki Seisakusho at a temperature of 270 ° C. and a shear rate of 240 sec ⁻¹ . Value. Further, the glitter feeling means the intensity of pearly luster.

  Further, the D-line refractive index (JIS K 7142) at 23 ° C. of the polyester resin (A) is preferably 1.40 to 1.8, more preferably 1.50 to 1.7, and 1.55 to 1.55. 1.65 is more preferable. When the D-line refractive index is in the range of 1.40 to 1.80, pearly luster is easily obtained.

<Polyolefin resin (B)>
The polyolefin resin (B) is preferably a single weight body such as ethylene, propylene, butene, and pentene, or one having a copolymer thereof as a main component. Specifically, for example, polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, propylene-vinyl acetate copolymer Polymer, propylene-methyl acrylate copolymer, propylene-methyl methacrylate copolymer, propylene-ethyl acrylate copolymer, polybutene, poly-3-methyl-1-butene copolymer, poly-4-methyl-1-pentene Examples thereof include copolymers and ethylene ionomer resins. These can be used alone or in admixture of two or more. Among these, polypropylene resins and polyethylene resins are preferable because they are inexpensive and excellent in processability and are widely used in various industrial parts and home appliances.

  The polypropylene resin includes, for example, homopolypropylene, block propylene copolymer, random propylene copolymer, ethylene propylene copolymer rubber, polypropylene obtained using a metallocene compound as a polymerization catalyst, maleic anhydride-modified polypropylene, glycidyl Examples thereof include modified polypropylene resins such as (meth) acrylate-modified polypropylene and 2-hydroxyethyl (meth) acrylate-modified polypropylene. Among these, a random propylene copolymer having a low crystallinity and a small influence of light scattering (white blur) in the crystal part is preferable.

  Examples of the polyethylene resin include high-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, linear low-density polyethylene, ultra-high molecular weight polyethylene, polyethylene obtained using a metallocene compound as a polymerization catalyst, cyclic polyethylene, and anhydrous maleate. Examples thereof include modified polyethylene resins such as acid-modified polyethylene, glycidyl (meth) acrylate-modified polyethylene, and 2-hydroxyethyl (meth) acrylate-modified polyethylene. Among these, low density polyethylene, ultra-low density polyethylene, and linear low density polyethylene, which have low crystallinity and are less affected by light scattering (white blur) in the crystal part, are preferable.

  The amount of the polyolefin resin (B) used is preferably 1 to 60 parts by weight and more preferably 3 to 50 parts by weight with respect to 100 parts by weight of the polyester resin (A). By blending 1 to 60 parts by weight, better pearly luster can be obtained.

The melt viscosity of the polyolefin resin (B) is preferably 50 to 1500 Pa · s, more preferably 100 to 1000 Pa · s under the conditions of temperature: 270 ° C. and shear rate: 240 sec ⁻¹ . By adjusting the melt viscosity to a range of 50 to 1500 Pa · s, the pearly luster can be further improved. Even when a coloring agent (D) is used because melt viscosity is 50 Pa.s or more, a molded object can improve a glittering feeling. In addition, the value measured by the same method and conditions as the melt viscosity of the polyolefin resin (A) of the polyolefin resin (B) is shown.

  Further, the D-line refractive index (JIS K 7142) at 23 ° C. of the polyolefin resin (B) is preferably 1.35 to 1.8, more preferably 1.40 to 1.7, and 1.45. 1.55 is more preferable. When the D-line refractive index is in the range of 1.35 to 1.8, pearly luster is easily obtained.

<Acid-modified styrene block copolymer (C)>
In the present invention, the acid-modified styrene block copolymer (C) is used for the purpose of improving the compatibility between the polyester resin (A) and the polyolefin resin (B).
The acid-modified styrene block copolymer (C) is a polymer block obtained by polymerizing the aromatic vinyl compound as X, and a polymer block obtained by polymerizing an olefin compound or a conjugated diene compound partially modified with an acid as Y. When expressed, it can be expressed by the following three structural formulas. Structural formula (1): XY, Structural formula (2): (XY) m [in the structural formula, m represents an integer of 1 to 10], Structural formula (3): (XY) n -X (in the structural formula, n represents an integer of 1 to 10). Among these, an XYX triblock copolymer is preferable.
The compound used for the partial modification with an acid is preferably a saturated or unsaturated carboxylic acid having a carboxyl group and an acid anhydride group-containing compound. Examples of the saturated or unsaturated carboxylic acid having a carboxyl group include acrylic acid and methacrylic acid. Examples of the acid anhydride group-containing compound include maleic anhydride.

  Further, when the block copolymer is represented by X, the polymer block obtained by polymerizing the aromatic vinyl compound is represented by Y, and the polymer block obtained by polymerizing an olefin compound or conjugated diene compound partially modified with an acid is represented by Y, It may be a type in which one or more Ys are grafted to the main chain consisting of X, or a type in which one or more Xs are grafted to the main chain consisting of Y. The latter block copolymer is more preferable from the viewpoint that the compatibility between the polyester resin (A) and the polyolefin resin (B) is easily improved as compared with the former block copolymer.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,3-dimethylstyrene, 2,4-dimethylstyrene, monochlorostyrene, and dichlorostyrene. P-bromostyrene, 2,4,5-tribromostyrene, 2,4,6-tribromostyrene, o-butylstyrene, m-butylstyrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene, and And vinyl anthracene. Of these, styrene and α-methylstyrene are preferred.

  The content of the aromatic vinyl compound unit in the acid-modified styrene block copolymer (C) is preferably 5 to 70% by weight, more preferably 15 to 60% by weight, in 100% by weight of the styrene block copolymer. preferable. By containing 5 to 70% by weight, the compatibility with the polyester resin (A) and the polyolefin resin (B) is further improved, and pearly luster is easily obtained.

  Examples of the olefin compounds partially modified with acid include ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, cyclopentene, 1-hexene, 2-hexene, cyclohexene, and 1-heptene. 2-heptene, cycloheptene, 1-octene, 2-octene, cyclooctene, vinylcyclopentene, vinylcyclohexene, vinylcycloheptene, vinylcyclooctene acid-modified products, and the like.

Examples of the conjugated diene compound partially modified with an acid include acid-modified products of butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like.
The polymer block Y preferably uses at least one of the olefinic compound and the conjugated diene compound, and specifically uses at least one of ethylene, propylene, butene and isoprene. .

  Specifically, the acid-modified styrene block copolymer (C) is, for example, an acid-modified product of polystyrene-polyisoprene diblock copolymer, an acid-modified product of polystyrene-polybutadiene diblock copolymer, or polystyrene-polyisoprene. -Acid modification product of polystyrene triblock copolymer, acid modification product of polystyrene-polybutadiene-polystyrene triblock copolymer, acid modification product of polystyrene-poly (ethylene / butadiene) -polystyrene triblock copolymer, polystyrene-poly Acid modified product of (ethylene / isoprene) -polystyrene triblock copolymer, acid modified product of polystyrene-poly (isoprene / butadiene) -polystyrene triblock copolymer, acid modified product of polyethylene-polystyrene graft copolymer, etc. Is mentioned.

  Moreover, the acid-modified styrene block copolymer (C) may have a functional group other than an acid anhydride group and a carboxyl group and a salt thereof within a range not impairing the gist of the present invention. The functional group is preferably a hydroxyl group, acid anhydride group, amino group, epoxy group, ester group, alkoxy group, aryloxy group, sulfonic acid group, amide group, mercapto group or the like.

  The acid-modified styrenic block copolymer (C) preferably contains 1 to 40 parts by weight, more preferably 3 to 35% by weight, based on 100 parts by weight of the polyester resin (A). By including 1 to 40 parts by weight, the compatibility between the polyester resin (A) and the polyolefin resin (B) is improved, and pearly luster is easily obtained.

The melt viscosity of the acid-modified styrenic block copolymer (C) is preferably 50 to 1500 Pa · s, preferably 100 to 1000 Pa · s at a temperature of 270 ° C. and a shear rate of 240 sec ⁻¹ . More preferred. By adjusting the melt viscosity to a range of 50 to 1500 Pa · s, the pearl tone can be further improved. The melt viscosity of the acid-modified styrene block copolymer (C) is a value measured by the same method and conditions as the melt viscosity of the polyester resin (A) and the polyolefin resin (B).

<Colorant (D)>
Specific examples of the colorant in the present invention include pigments and dyes. Further, it is necessary to include at least one of a black colorant having an average reflectance of 10% or less at a wavelength of 380 to 750 nm and a chromatic colorant having a peak of 3% or more of a maximum reflectance at a wavelength of 380 to 500 nm. . By including at least one kind of colorant exhibiting the reflectance characteristic, the texture (gloss and depth) of the molded body obtained by molding the resin composition is improved, and the appearance can be further improved. This means that the pearly luster emitted by the light interference effect from the molded article obtained by molding the resin composition of the present invention in which the colorant (D) is not blended is slightly bluish while being white. It seems to be caused by. That is, white pearl tone is more enhanced by using a black colorant having an average reflectance of 10% or less at a wavelength of 380 to 750 nm. On the other hand, by using a chromatic colorant having a peak with a maximum reflectance of 3% or more at a wavelength of 380 nm to 500 nm, the chromatic effect of the chromatic colorant is enhanced by the bluish component of pearly luster and the texture is improved. It is thought that it was connected to.

  The reflectance of the pigment can be determined by measuring the reflectance of a sheet prepared by kneading the pigment into polypropylene resin. For example, 0.25 part by weight of pigment and 100 parts by weight of polypropylene resin (manufactured by Prime Polymer Co., random propylene copolymer, J226ED) are mixed, and the measurement sample is 5 by using two rolls heated to 180 ° C. After melt-kneading for 1 minute, it is obtained by producing a press sheet having a thickness of 2 mm using a press molding machine heated to 180 ° C. The reflectance refers to the diffuse reflectance of the measurement sample when the diffuse reflectance of the standard white plate (barium sulfate) is 100% at each wavelength of 300 to 800 nm. Moreover, Shimadzu Corporation UV-3150 was used for the reflectance measuring instrument. In the present invention, “the average reflectance is 10% or less” is defined as an arithmetic average value of the reflectance at each wavelength (every 1 nm) at a wavelength of 380 to 750 nm. In addition, the “peak with a maximum reflectance of 3% or more” means 3% or more that appears within a wavelength range of 380 to 500 nm with respect to the lowest value of reflectance at a wavelength of 300 to 800 nm (the minimum value is a baseline). It is defined as a high maximum peak.

  The reflectance of the dye can be determined by measuring the reflectance of an injection plate prepared by kneading the dye into polyethylene terephthalate resin. In addition, the reflectance of the dye is obtained in the same manner as the reflectance of the pigment.

  Examples of the black pigment include organic black pigments such as aniline black, anthraquinone black, and perylene black, carbon black, lamp black, graphite, fullerene, carbon nanotube, magnetite, iron-titanium composite oxide, cobalt oxide, manganese dioxide, and sulfide. Zinc, copper-chromium composite oxide, tin-antimony composite oxide, titanium-vanadium-antimony composite oxide, cobalt-nickel composite oxide, manganese-iron composite oxide, iron-cobalt-chromium composite oxide, copper- Inorganic black pigments such as chromium composite oxide, iron-cobalt composite oxide, chromium-iron-nickel composite oxide, molybdenum disulfide, low-order titanium oxide, titanium nitride, and chromium oxide. Specific examples of the brown pigment include iron-chromium composite oxide, and the color index number includes C.I. I. Pigment Black 1, 6, 7, 10, 11, 12, 13, 14, 17, 20, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, Pigment Brown 29, and the like. Among these, it is preferable to use Pigment Black 7 which exhibits a low reflectance at a wavelength of 380 to 750 nm.

  The chromatic pigment is preferably a known red pigment, violet pigment, blue pigment, or green pigment. Specific examples in the case where the colorant (D) is a red pigment are naphthol pigments, soluble azo pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, etc. that exhibit a bluish hue. , C.I. I. Pigment Red 31, 48: 2, 48: 4, 122, 177, and 179. Among these, it is preferable to use Pigment Red 122 showing a strong bluish hue.

  Examples of the purple pigment include monoazo pigments, various rhodamines, methyl violet lake, alizarin violet, anthraquinone violet, cobalt violet, cobalt ammonium phosphate, ultramarine violet, manganese violet, quinacridone violet, quinacridone purple, dioxazine violet, and perylene. Violet, benzimidazolone violet, induslen violet, crystal violet, etc., and the color index number is C.I. I. Pigment Violet 1, 1: 1, 1: 2, 2, 2: 2, 3, 3: 1, 3: 2, 3: 3, 5, 5: 1, 7, 13, 14, 15, 16, 17, 18, 19 (β type), 23, 25, 27, 29, 31, 32, 36, 37, 39, 42, 44, 47, 48, 49, 50, 55, 58, and the like. Among these, it is preferable to use Pigment Violet 19 (β type) which is excellent in weather resistance, heat resistance and hue.

  Examples of the blue pigment include Victoria blue, various phthalocyanine blues, brilliant blue lakes, various naphthols, Prussian blues, cobalt blues, ultramarine blues, ash blues, Egyptian blues, smalts, manganese blues, copper sulfides, cerulean blues, and cobalt aluminum blues. , Reflex blue, indanthrene blue, alkali blue, indigo carmine lake, blue zircon, cobalt silicate blue, benzimidazolone dioxazine, etc., and the color index number is C.I. I. Pigment Blue 1, 1: 2, 9, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 15:34, 16, 17, 24, 25, 27, 27: 1, 28, 29, 30, 31, 32, 33, 34, 35, 36, 36: 1, 60, 61, 61: 1, 62, 63, 66, 68, 71, 72, 73, 74, 75, 76, 79, 80, 81, 82, 84, 128, and the like. Among these, it is preferable to use Pigment Blue 15, 15: 1, 15: 3 which is excellent in hue and heat resistance and has high transparency and coloring power.

  Examples of the green pigment include brilliant green lake, first green lake, chlorinated phthalocyanine green, brominated phthalocyanine green, nitroso green, nickel azo yellow, cadmium green, chrome green, zinc green, cobalt chrome green, malachite green, copper ferrocyanide, Chromium cyanine green, cobalt titanium green, Victoria green garnet, nickel green oliveine, etc., and the color index number is C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 26, 36, 38, 39, 41, 42, 45, 48, 50, 51, 55, 56, etc. Among these, it is preferable to use Pigment Green 7 and 36 excellent in heat resistance and hue.

  The pigment is made by preparing an intermediate (also called a masterbatch) containing a high concentration of pigment with various metal soaps, low molecular weight waxes including polyethylene, polypropylene, polystyrene, etc., and diluting and using it. You may obtain a molded object.

  In the present invention, a known dye can be used as the dye.

  In the resin composition of the present invention, the colorant (D) can be used alone or in combination of two or more depending on the desired hue. For example, in order to reproduce green, the blue pigment listed above and an appropriate yellow pigment can be used in combination. Further, a pigment and a dye can be used in combination according to a desired hue.

  The resin composition of the present invention preferably contains 0.0001 to 0.5% by weight of the colorant (D) in the resin composition. When the colorant (D) is in the above-mentioned range, a molded article having a better colored pearl tone and further excellent gloss and depth can be obtained. The colorant (D) is more preferably contained in an amount of 0.001% by weight or more.

  Further, the refractive index of the colorant (D) is preferably 1.35 to 1.75. By making a refractive index into the previous term range, the difference with the refractive index of a polyester resin (A) and polyolefin resin (B) can be reduced. The refractive index is the D-line refractive index (JIS K 7142) at 23 ° C.

  The resin composition of the present invention may further contain an inorganic filler such as talc, mica, and glass fiber in order to enhance physical properties and improve processability. Moreover, you may mix | blend suitably one or more types of additive and an inorganic filler in the range which does not affect the external appearance and workability of a molded object. The additive used is not particularly limited. For example, various commonly used leveling agents, pigment dispersants, ultraviolet absorbers, antioxidants, viscosity modifiers, light stabilizers, metal deactivators, excess surfactants. Oxide decomposing agent, processing stabilizer, nucleating agent, crystallization accelerator, crystallization retarding agent, anti-gelling agent, filler, reinforcing agent, plasticizer, lubricant, flame retardant, rust inhibitor, fluorescent whitening agent , Fluidity modifiers, antistatic agents, and the like.

  Examples of the inorganic filler include glass fiber, carbon fiber, plate-like or scale-like glass, glass flake, glass bead, glass balloon, mica, talc, chlorite, wollastonite, kaolinite, calcined clay, calcium carbonate Heavy calcium carbonate, precipitated barium sulfate, and the like.

  The resin composition of the present invention comprises a polyester resin (A), a polyolefin resin (B), an acid-modified styrenic block copolymer (C), and a colorant (D), and various fillers and additives as necessary. Add agent etc., mix with Henschel mixer, tumbler or disper, etc., kneader, roll mill, super mixer, Henschel mixer, Shugi mixer, vertical granulator, high speed mixer, fur matrix, ball mill, steel mill, sand mill, vibration mill , Mixed in a batch kneader such as an attritor or Banbury mixer, a twin screw extruder, a single screw extruder, a rotor type twin screw kneader, etc., or melt-kneaded and dispersed to form a pellet, powder, granule or A resin composition having a bead shape or the like can be obtained.

  In the production of the resin composition of the present invention, the order of mixing, melting and kneading the polyester resin (A), the polyolefin resin (B), the acid-modified styrene block copolymer (C) and the colorant (D) is particularly limited. However, for example, the polyester resin (A) and the colorant (D) can be mixed, melt-kneaded, and then (B) and (C) can be mixed and melt-kneaded again. Further, (B) and (D) can be mixed, melt-kneaded, and then (A) and (C) can be mixed again and melt-kneaded. Further, (A), (B), and (C) can be mixed, melt-kneaded, and then again mixed with (D) and melt-kneaded. Further, (B), (C) and (D) can be mixed, melt-kneaded and then mixed with (A) again, and melt-kneaded. Further, (A), (C), and (D) can be mixed, melt-kneaded, and then again mixed with (B) and melt-kneaded. Further, (A), (B), (C) and (D) may be mixed, melt-kneaded at a time.

  Further, the resin composition of the present invention may be in the form of a masterbatch containing the colorant (D) at a high concentration.

  The molded product of the present invention is a molded product obtained by molding the resin composition. Preferred molding methods include, for example, injection molding, film molding (T-die molding, inflation molding, calendar molding), sheet molding, tube molding, pipe molding and other extrusion molding, blow molding (direct blow molding, biaxial stretch blow molding). And stretch molding. Particularly preferable molding methods include injection molding, T-die molding, and direct blow molding.

  The molded product of the present invention is characterized by a colored pearly appearance that suppresses color unevenness and is glossy and deep. Therefore, it can be widely used for applications that touch human eyes. Among them, for example, it can be preferably used not only for general decorative products and cosmetic containers but also as various home appliances, interior / exterior parts and housings of electronics, and lamp housings for vehicles.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples without departing from the technical idea of the present invention.

The raw materials used in the examples are shown below.
[Polyester resin]
(A-1): Amorphous copolyester resin (Eastman Chemical Chemical Japan, Esta Copolyester GN001, melt viscosity: 98 Pa · S)
(A-2): Amorphous copolyester resin (Eastman Chemical Chemical Japan, Esta copolyester GN071, melt viscosity 83 Pa · S)
(A-3): Amorphous copolyester resin (Eastman Chemical Chemical Japan, Esta Copolyester AN014, melt viscosity 164 Pa · S)
(A-4): Crystalline polyester resin (Mitsui Chemicals, Mitsui Pet SA135, melt viscosity: 109 Pa · S)
(A-5): Crystalline polyester resin (Toyobo Co., Ltd., Byron GM415, melt viscosity: 82 Pa · S)
The melt viscosity is a value measured under conditions of temperature: 270 ° C. and shear rate: 240 sec ⁻¹ .

[Polyolefin resin]
(B-1): Random propylene copolymer (Nippon Polypro, Novatec EG7F, melt viscosity: 479 Pa · S)
(B-2): Random propylene copolymer (manufactured by Prime Polymer, F-744NP, melt viscosity: 272 Pa · S)
(B-3): Random polypropylene copolymer (manufactured by Prime Polymer Co., Ltd., J226T, melt viscosity: 181 Pa · S)
(B-4): Homopropylene copolymer (manufactured by Prime Polymer Co., Ltd., F-704NP, melt viscosity: 258 Pa · S)
(B-5): High density polyethylene (manufactured by Prime Polymer, Hi-Zex 7700M, melt viscosity: 1014 Pa · s)
(B-6): High density polyethylene (Nippon Polyethylene, Novatec HJ550, melt viscosity: 332 Pa · s)
(B-7): Low density polyethylene (manufactured by Tosoh Corporation, Petrocene 353, melt viscosity: 67 Pa · s)
(B-8): Low density polyethylene (Kuraray Co., Ltd., Mirason 50, melt viscosity: 342 Pa · s)
The melt viscosity is a value measured under conditions of temperature: 270 ° C. and shear rate: 240 sec ⁻¹ .

[Acid-modified styrene block copolymer]
(C-1): modified maleic anhydride of polystyrene-poly (ethylene / butadiene) -polystyrene triblock copolymer (Asahi Kasei Chemicals, Tuftec M1913, styrene content: 30%, melt viscosity: 290 Pa · s)
(C-2): Polystyrene-poly (ethylene / butadiene) -polystyrene triblock copolymer modified with maleic anhydride (manufactured by Asahi Kasei Chemicals Corporation, Tuftec M1943, styrene content: 20%, melt viscosity: 239 Pa · s)

[Pigment]
(D-1): Carbon black (CI Pigment Black 7, average reflectance: 1.6%, average primary particle size: 0.024 μm)
[Pigment]
(D-2): β-type phthalocyanine blue (CI Pigment Blue 15: 3, reflection maximum wavelength: 450 nm, maximum reflectance: 10.5%, average primary particle size: 0.1 μm)
(D-3): Quinacridone red (CI Pigment Red 122, reflection maximum wavelength: 402 nm, maximum reflectance: 5%, average primary particle size: 0.12 μm)
(D-4): Disazo yellow (CI Pigment Yellow 180, no reflection maximum peak at 380 to 500 nm, average primary particle size: 0.23 μm)
(D-5): Ultramarine (CI Pigment Blue 29, reflection maximum wavelength: 424 nm, maximum reflectance: 9%, average primary particle diameter: 2 μm)
The average reflectance indicates an arithmetic average value of the diffuse reflectance of each wavelength at a wavelength of 380 to 750 nm, and the maximum reflectance is a wavelength 380 with respect to the lowest value (baseline) of the reflectance at a wavelength of 300 to 800 nm. It shows a diffuse reflectance of a maximum peak that is 3% or more that appears in the range of ˜500 nm.

[Other]
(E-1): Zinc stearate / calcium stearate mixture (mixing ratio: 1/1)

Example 1
(1) Production of resin composition (A-1) 100 parts by weight, (B-1) 20 parts by weight, (C-2) 10 parts by weight, (D-1) 0.01 parts by weight, (E-1 ) A mixture was obtained by stirring and mixing 0.01 parts by weight with a stirring blade rotating speed of 300 rpm for 3 minutes. The mixture was put into a twin screw extruder (manufactured by Nippon Placon Co., Ltd.) having a set temperature of 270 ° C., and melt kneaded and granulated to obtain a resin composition.

(2) Manufacture of molded body The obtained resin composition is put into an injection molding machine (Toshiki Machine Co., Ltd., IS100 type) with a cylinder set temperature of 270 ° C. and a mold temperature of 40 ° C., and the surface is mirror-finished. A molded body (length 100 mm × width 100 mm × thickness 2 mm) was obtained.

(Examples 2 to 52, Comparative Examples 1 to 14)
Except having changed the raw material and compounding quantity of Example 1 as having described in Tables 1-5, it carried out similarly to Example 1 and obtained the resin composition and its molded object. In addition, the compounding quantity of Tables 1-5 shows the weight part with respect to 100 weight part of polyester resins (A).

  The obtained molded body was evaluated by the following method. The evaluation results are shown in Tables 1-5.

<Pearl luster (shininess)>
Ten testers visually evaluated the intensity of the pearly luster on the mirror surface of the molded article as a glitter feeling. The evaluation criteria are as follows.
4: More than 8 people felt radiance. Are better.
3: 5 to 7 people felt glitter. Good.
2: 2 to 4 people felt glitter. Somewhat good.
1: 1 or less felt radiance. Bad.

<Glossy texture>
Ten testers visually evaluated the pearly luster texture on the mirror surface of the molded article from the viewpoint of glossiness and depth. The evaluation criteria are as follows.
4: More than 8 people felt smoothness and depth. Are better.
3: 5 to 7 people felt smoothness and depth. Good.
2: 2-4 persons felt smoothness and depth. Somewhat good.
1: 1 or less felt smoothness and depth. Bad.

<Color unevenness>
Using a computer color matching system (CCM) (manufactured by Kurashiki Boseki Co., Ltd., AUCOLOR VP-2), the color unevenness of the mirror surface of the molded product is obtained as a ΔE value for any five points under the conditions of standard light source D-65 and diffuse illumination 10 ° Were measured and averaged. The evaluation criteria are as follows.
4: Less than 0.3. More than 8 people felt smoothness and depth. Are better.
3: 0.3 or more and less than 0.5. Good.
2: 0.5 or more and less than 1. Somewhat good.
1: 1 or more. Bad.

<Comprehensive evaluation>
Based on the obtained evaluation results, whether or not the resin composition of the present invention is suitable was evaluated according to the following criteria.
A: All evaluations are 4. Are better.
B: The evaluation includes 1 or more of 2 or 3, and does not include 1. Good C: The evaluation includes 1 or more. Bad

  As is clear from the results of Tables 1 to 5, the molded bodies of Examples 1 to 52 all show strong pearly luster without color unevenness, and the texture is glossy and deep, and has high design properties. I was prepared. Among these, when carbon black (D-1) which is a black pigment, phthalocyanine blue (D-2) or quinacridone red (D-3) showing a bluish hue is used as the colorant (D), Exhibited excellent pearl tone and texture. On the other hand, in the molded product in which the melt viscosity ratio of the polyester resin (A) and the olefin resin (B) shown in Comparative Examples 1 to 5 is 0.10 or less or exceeds 1.60, color unevenness is generated and is emitted from the molded product. The pearly luster was also weak, and the texture was also inferior due to lack of luster and depth. This is because the polyolefin resin (B) cannot form a uniform and finely dispersed state in the polyester resin (A), and the pearl tone and texture are affected. Furthermore, it is considered that unevenness of stretching for each part of the compact tends to occur during molding, and unevenness of color occurs. In addition, the molded product of Comparative Example 15 that did not contain the colorant (D) of the present invention was a result of lack of pearly luster and texture, although color unevenness was not noticeable. This indicates that the pearly luster and texture are affected by the reflectance characteristics of the colorant (D) used.

Claims (3)

100 parts by weight of polyester resin (A), 1 to 60 parts by weight of polyolefin resin (B), 1 to 40 parts by weight of acid-modified styrenic block copolymer (C), and colorant (D),
When the melt viscosity at a temperature of 270 ° C. and a shear rate of 240 sec ⁻¹ of the polyester resin (A) is η _A and the melt viscosity of the polyolefin resin (B) is η _B , η _A / η _B is 0.11. Is 1.60 or less,
Further, the colorant (D) is a black colorant having an average reflectance of 10% or less at a wavelength of 380 to 750 nm, and a chromatic colorant having a peak of a maximum reflectance of 3% or more at a wavelength of 380 to 500 nm. A resin composition containing at least one of the above. 2. The resin composition according to claim 1, wherein the polyester resin (A) has a melt viscosity η _{A of 10} to 500 Pa · s under conditions of a temperature of 270 ° C. and a shear rate of 240 sec ⁻¹ .   The molded object formed by shape | molding the resin composition of any one of Claims 1-2.