JP2016204599A - Thermoplastic resin composition and molded body thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition providing a molded body having high scratch resistance, shock resistance, heat resistance and high quality appearance only by molding without coating, and the molded body thereof.SOLUTION: The thermoplastic resin composition contains an amorphous thermoplastic resin (A) consisting of amorphous polyester and/or aromatic polycarbonate and an additive (B), where the content of the (B) component is over 0.1 pts.mass relative to 100 pts.mass of the (A) component, the (B) component contains a structural unit represented by a specific formula and an all light transmittance measured with thickness of 2.5 mm in accordance with ASTM1003 of 50% or more.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition and a molded body thereof.

  Aromatic polycarbonate has both transparency and excellent impact resistance, and is very widely used in fields requiring high impact resistance, such as housings for portable devices and housings for home appliances. It is also widely used in fields that require heat resistance in addition to the above properties, such as automobile interior parts and glazing.

  In recent years, materials that are visible to the user, such as housings, are strongly demanded for design, and as one of them, there is a field in which the appearance of jet black (piano black) is required. In such fields, conventionally, the method of painting mainly on the surface of resin material has been adopted. However, due to problems such as environmental pollution and high cost due to discharge of volatile organic compounds (VOC), the painting process (clear There is an increasing demand to use an original material that produces a design by mixing a coloring material with a raw material without performing coating.

  However, in order to use it as a raw material, scratch resistance and weather resistance are required without reducing the transparency and impact resistance specific to polycarbonate (PC). Conventionally, as a technique for improving the scratch resistance of PC, for example, in the following Patent Document 1, 0.01 to 1 part by weight of a fatty acid ester having 20 or more carbon atoms in a fatty acid is added to make it slidable. A technique called excellent polycarbonate is disclosed (for example, see Patent Document 1). In addition, a method of blending silicone oil having a viscosity of 1000 to 2000 cP has been proposed (for example, see Patent Document 2). In addition, as a transparent material having excellent scratch resistance, a biopolycarbonate resin mainly composed of isosorbide has also been proposed (see, for example, Patent Document 3).

JP 2008-308606 A JP 2000-143965 A JP 2013-49847 A

  However, in the technique of Patent Document 1, there is a problem that heat resistance and impact resistance are lowered when the content of fatty acid ester is increased. In the technique of Patent Document 2, the blended silicone oil is bleed. There is a problem that the appearance defect of the molded product occurs and the long-term scratch resistance is not sufficient. Furthermore, the technique of Patent Document 3 has a problem that the impact value tends to be lower than that of aromatic polycarbonate, and it is difficult to obtain a sufficient impact value.

  Therefore, at present, no material has been obtained that satisfies all of scratch resistance, impact resistance, heat resistance, and high-quality appearance.

  Therefore, in the present invention, in view of the above-described problems of the prior art, thermoplasticity that can provide a molded body having both high scratch resistance and impact resistance, heat resistance, and high-quality appearance only by molding without painting. It aims at providing a resin composition and its molded object.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a predetermined amorphous polyester and / or an amorphous thermoplastic resin (A) made of an aromatic polycarbonate, and a predetermined ( B) a thermoplastic resin composition containing an additive, wherein the component (B) is composed of a structural unit of an α-olefin and maleic anhydride, and the thermoplastic resin composition conforms to ASTM 1003, A molded product having both high scratch resistance and impact resistance, heat resistance, and high-quality appearance without being painted, because the total light transmittance when measured at a thickness of 2.5 mm is 50% or more. The present invention has been completed.

  That is, the present invention is as follows.

[1]
An amorphous polyester and / or an amorphous thermoplastic resin (A) made of an aromatic polycarbonate, and an additive (B),
The content of the component (B) exceeds 0.1 parts by mass with respect to 100 parts by mass of the component (A),
The component (B) contains structural units represented by the following formulas (1) and (2),
A thermoplastic resin composition having a total light transmittance of 50% or more when measured at a thickness of 2.5 mm in accordance with ASTM 1003.

[式（１）中、Ｒは炭素数が１０〜６０の直鎖又は分岐のアルキル基を表す。]
［２］
前記（Ａ）成分として、少なくとも非晶性ポリエステルを含有する、［１］に記載の熱可塑性樹脂組成物。

[In formula (1), R represents a linear or branched alkyl group having 10 to 60 carbon atoms. ]
[2]
The thermoplastic resin composition according to [1], which contains at least amorphous polyester as the component (A).

[3]
The thermoplastic resin composition according to [2], which contains at least an alicyclic diol as a diol component of the amorphous polyester in the component (A).

[4]
The thermoplastic resin composition according to [2] or [3], wherein the amorphous polyester in the component (A) is a polyester resin containing at least an aromatic dicarboxylic acid and an alicyclic diol.

[5]
The thermoplastic resin composition according to [3] or [4], which contains 2,2,4,4-tetramethyl-1,3-cyclobutanediol as the alicyclic diol in the component (A).

[6]
The thermoplastic resin composition according to any one of [1] to [5], including 0.2 to 1.5 parts by mass of the component (B) with respect to 100 parts by mass of the component (A).

[7]
Further containing a rubber component (C),
The component (C) includes a dispersed phase composed of a graft copolymer (a) and a continuous phase (b), and the graft copolymer (a) comprises a trunk polymer composed of a rubbery polymer, A graft chain graft-polymerized to a trunk polymer, wherein the graft chain includes a vinyl cyanide monomer unit, and one or more monomer units copolymerizable with the vinyl cyanide monomer. The distribution of the content of the vinyl cyanide monomer units in the graft chain-derived component of the graft copolymer (a) has two or more peaks, and the two or more Are at least one peak having a peak top in a range of 0% by mass or more and less than 10% by mass, wherein the content of the vinyl cyanide monomer unit is the first peak, One or more of the different peaks It is the 2nd peak which has a peak top in the range whose content rate of a body unit is 10 mass% or more and less than 55 mass%, and calculates | requires from the integrated value of each peak whole in the said 1st peak and 2nd peak. When the weighted average value is a representative value, the difference between the representative value of the content shown by the first peak and the representative value of the content shown by the second peak is 10% by mass or more. The thermoplastic resin composition according to any one of [1] to [6].

[8]
Furthermore, the thermoplastic resin composition according to [7], wherein the content of rubber components other than the rubber component (C) is less than 1% by mass.

[9]
The thermoplastic resin composition according to any one of [1] to [8], further comprising at least one selected from the group consisting of a colorant, a weathering agent, and a heat stabilizer.

[10]
[1] A molded product comprising the thermoplastic resin composition according to any one of [9].

[11]
The molded body according to [10], wherein the molded body is unpainted.

[12]
The molded body according to [10] or [11], wherein the molded body is an automobile material.

  According to the present invention, a thermoplastic resin composition from which a molded article having both high scratch resistance and impact resistance, heat resistance and high-quality appearance can be obtained by molding without painting, and the thermoplastic resin composition A molded product of the product is obtained.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified within the scope of the gist.
[Thermoplastic resin composition]
The thermoplastic resin composition of the present embodiment is
An amorphous polyester and / or an amorphous thermoplastic resin (A) made of an aromatic polycarbonate, and an additive (B),
The content of the component (B) exceeds 0.1 parts by mass with respect to 100 parts by mass of the component (A),
The component (B) contains structural units represented by the following formulas (1) and (2),
A thermoplastic resin composition having a total light transmittance of 50% or more when measured at a thickness of 2.5 mm in accordance with ASTM 1003.

[式（１）中、Ｒは炭素数が１０〜６０の直鎖又は分岐のアルキル基を表す。]
（（Ａ）非晶性熱可塑性樹脂）
本実施形態の熱可塑性樹脂組成物は、非晶性ポリエステル、及び／又は、芳香族ポリカーボネートからなる非晶性熱可塑性樹脂（Ａ）を含有している。本実施形態の熱可塑性樹脂組成物において、（Ａ）成分を含むことにより、高品位な外観と高い耐衝撃性と、さらに耐熱性にも優れた成形体を得ることができる。

[In formula (1), R represents a linear or branched alkyl group having 10 to 60 carbon atoms. ]
((A) Amorphous thermoplastic resin)
The thermoplastic resin composition of the present embodiment contains an amorphous thermoplastic resin (A) made of amorphous polyester and / or aromatic polycarbonate. By including the component (A) in the thermoplastic resin composition of the present embodiment, it is possible to obtain a molded article having a high-quality appearance, high impact resistance, and excellent heat resistance.

  The amorphous polyester used for the component (A) is not limited to the following, but, for example, an alicyclic diol compound and / or an alicyclic diol compound residue, and / or an alicyclic dicarboxylic acid. Examples thereof include an amorphous polyester containing an acid compound and / or an alicyclic dicarboxylic acid compound residue and / or an aromatic dicarboxylic acid compound and / or an aromatic dicarboxylic acid compound residue. These may be used alone or in combination of two or more.

  As used herein, “residue” means any organic structure incorporated into a polymer from the corresponding monomer by polycondensation and / or esterification reactions. Thus, for example, a dicarboxylic acid residue is derived from a dicarboxylic acid monomer or its related acid halide, ester, salt, anhydride, or mixture thereof.

  The component (A) is particularly preferably an aromatic polycarbonate, an alicyclic diol compound and / or an amorphous polyester containing an alicyclic diol compound residue, or a mixture thereof.

  As the aromatic polycarbonate, either an aromatic homopolycarbonate or an aromatic copolycarbonate can be used.

  The aromatic polycarbonate is prepared by a phosgene method in which phosgene is blown into a bifunctional phenol compound in the presence of caustic alkali and a solvent, a transesterification method in which a bifunctional phenol compound and diethyl carbonate are transesterified in the presence of a catalyst, It can be produced by various methods such as a method of obtaining diethyl carbonate from carbon and alcohol and reacting diethyl carbonate with an aromatic hydroxy compound to obtain an aromatic carbonate.

  Examples of the bifunctional phenol compound include, but are not limited to, for example, 2,2′-bis (4-hydroxyphenyl) propane, 2,2′-bis (4-hydroxy-3,5- Dimethylphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1′-bis (4-hydroxyphenyl) ethane, 2,2′-bis (4-hydroxyphenyl) butane, 2,2′-bis (4 -Hydroxy-3,5-diphenyl) butane, 2,2'-bis (4-hydroxy-3,5-dipropylphenyl) propane, 1,1'-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl- 1,1′-bis (4-hydroxyphenyl) ethane and the like, in particular, 2,2′-bis (4-hydroxyphenyl) propane [bisphenol A] It is preferably used. As said bifunctional phenol type compound, only 1 type may be used independently and 2 or more types may be used together.

  Moreover, the aromatic polycarbonate manufactured above may be used independently, and 2 or more types may be used together.

  The thermoplastic resin composition of the present embodiment preferably contains at least amorphous polyester as the component (A).

  The thermoplastic resin composition of the present embodiment more preferably contains at least an alicyclic diol as the diol component of the amorphous polyester in the component (A).

  Examples of the alicyclic diol component contained in the amorphous polyester include, but are not limited to, ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1 C2-C12 alkylene glycol such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol; 1,2-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexane Examples include alicyclic diols such as dimethanol, 1,4-cyclohexanedimethanol (CHDM), and 2,2,4,4-tetramethylcyclobutanediol (TMCD). Among these, 2,2,4,4-tetramethyl-1,3-cyclobutanediol is preferably included as the alicyclic diol in the component (A). In order to obtain heat resistance in this embodiment, in particular, 1,4-cyclohexanedimethanol (CHDM) and 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) are used in combination. Is preferred. The composition ratio of the diol component is 10 to 70 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residue when the total mol% of the diol component is 100 mol%. More preferably 15 to 65 mol%, still more preferably 20 to 50 mol%, particularly preferably 30 to 45 mol%, and 30 to 90 mol% of 1,4-cyclohexanedimethanol (CHDM) residue, more Preferably it contains 35-85 mol%, More preferably, it is 50-80 mol%, More preferably, it contains 55-70 mol%.

  By including the (TMCD) residue and the (CHDM) residue in the numerical range, the effects of heat resistance and impact resistance can be obtained.

  The contents of the (TMCD) residue and the (CHDM) residue can be measured by NMR.

  As the diols, cis, trans, or a mixture thereof can be used.

  In the present embodiment, one or more reforming diols other than 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol as long as the effects are not impaired. 15 mol% or less, more preferably 10 mol% or less, and still more preferably 5 mol% or less.

  One or more modifying diols other than 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol include diols containing 2 to 16 carbon atoms. Can be mentioned. Although not limited to the following, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1 , 6-hexanediol, p-xylene glycol or a mixture thereof. Among these, a preferred modifying diol is ethylene glycol from the viewpoint of obtaining impact resistance and a high-quality appearance.

  The polyester component contains a dicarboxylic acid component paired with a diol component. Examples of the dicarboxylic acid component include alicyclic dicarboxylic acid and / or alicyclic dicarboxylic acid residue, aromatic dicarboxylic acid and / or aromatic dicarboxylic acid residue, aliphatic dicarboxylic acid and / or aliphatic dicarboxylic acid. Residue. In particular, at least one selected from an aromatic dicarboxylic acid and / or an aromatic dicarboxylic acid residue and an aliphatic dicarboxylic acid and / or an aliphatic dicarboxylic acid residue is preferable. More preferably, an aromatic dicarboxylic acid and / or an aromatic dicarboxylic acid residue is preferred. Among these, the amorphous polyester in the component (A) is preferably a polyester resin containing at least an aromatic dicarboxylic acid and an alicyclic diol.

  As a constituent ratio of the dicarboxylic acid component, when the total mol% of the dicarboxylic acid is 100 mol%, for example, an aromatic dicarboxylic acid having 20 or less carbon atoms and / or an aromatic dicarboxylic acid residue having 20 or less carbon atoms is preferable. Is 70 to 100 mol%, more preferably 80 to 100 mol%, still more preferably 90 to 100 mol%, an aliphatic dicarboxylic acid having 16 or less carbon atoms and / or an aliphatic dicarboxylic acid residue having 16 or less carbon atoms. Is preferably 0 to 10 mol%, more preferably 0 to 5 mol%, still more preferably 0 to 1 mol%.

  Inclusion of an aromatic dicarboxylic acid having 20 or less carbon atoms and / or an aromatic dicarboxylic acid residue having 20 or less carbon atoms and an aliphatic dicarboxylic acid having 16 or less carbon atoms and / or an aliphatic dicarboxylic acid residue having 16 or less carbon atoms By setting the amount within the above numerical range, high heat resistance and impact resistance can be obtained in the thermoplastic resin composition of the present embodiment.

  Content of aromatic dicarboxylic acid and / or aromatic dicarboxylic acid residue having 20 or less carbon atoms, aliphatic dicarboxylic acid having 16 or less carbon atoms and / or aliphatic dicarboxylic acid residue having 16 or less carbon atoms in dicarboxylic acid component Can be measured by NMR.

  Examples of the aromatic dicarboxylic acid and / or aromatic dicarboxylic acid residue include, but are not limited to, for example, terephthalic acid, dimethyl terephthalate, diethyl terephthalate, terephthalic acid and its ester, isophthalic acid, 4 , 4′-biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid, and trans-4,4′-stilbene dicarboxylic acid and mixtures thereof with esters Although mentioned, terephthalic acid and / or a terephthalic acid ester are preferable from a viewpoint of color tone and fluidity.

  Examples of the aliphatic carboxylic acid and / or aliphatic dicarboxylic acid residue include, but are not limited to, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, And dodecanedioic acid.

  The aromatic dicarboxylic acid component may be any of linear, para-oriented, and symmetrical structures, and examples thereof include those having 20 or less carbon atoms, but are not limited thereto.

  The amorphous thermoplastic resin (A) used in the present embodiment preferably has a weight average molecular weight in the range of 10,000 to 200,000, more preferably 10,000 to 100,000, still more preferably 10. In the range of 20,000 to 60,000, even more preferably in the range of 20,000 to 60,000. By setting the weight average molecular weight of the component (A) to 10,000 or more, impact resistance and extrusion stability can be obtained in the thermoplastic resin composition of the present embodiment, and the weight average molecular weight of the component (A). When the value is 200,000 or less, the moldability is improved.

  In the case where two or more kinds of aromatic polycarbonates are used in combination as the component (A), the weight average molecular weight of the mixture is preferably in the above range, and the low weight average molecular weight aromatic polycarbonate and the high weight average molecular weight aromatic are used. Polycarbonate can also be mixed.

  The weight average molecular weight of the component (A) can be calculated by converting from a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample by gel permeation chromatography (GPC) using chloroform as a solvent.

  (A) It is preferable that the glass transition temperature [Tg] of a component is 100-170 degreeC, More preferably, it is 110-170 degreeC, More preferably, it is 120-170 degreeC. By setting the glass transition temperature of the component (A) within the above range, heat resistance can be maintained in the thermoplastic resin composition and the molded body of the present embodiment.

  The glass transition temperature can be measured using a differential scanning calorimeter (DSC) according to JIS K7121.

When the component (A) is a mixture of an aromatic polycarbonate and an amorphous polyester, the proportion of the component (A) is 10 to 90% by mass of the aromatic polycarbonate and 10 to 90% of the amorphous polyester. It is preferable that it is mass%. More preferably, the aromatic polycarbonate is 30 to 90% by mass, the amorphous polyester is 10 to 70% by mass, and further preferably the aromatic polycarbonate is 40 to 80% by mass, and the amorphous polyester is 20 to 60% by mass. . By setting the mass ratio of the component (A) within the above range, heat resistance and high-quality appearance can be obtained in the thermoplastic resin composition and the molded body of the present embodiment.
((B) Additive)
The thermoplastic resin composition of this embodiment contains the additive (B) containing the structural unit shown by following formula (1) and (2).

[式（１）中、Ｒは炭素数が１０〜６０の直鎖又は分岐のアルキル基を表す。]
本実施形態の熱可塑性樹脂組成物において、（Ｂ）成分を含むことにより、耐傷付き性と耐衝撃性と、耐熱性とに優れた成形体を得ることができる。

[In formula (1), R represents a linear or branched alkyl group having 10 to 60 carbon atoms. ]
By including the component (B) in the thermoplastic resin composition of the present embodiment, a molded article excellent in scratch resistance, impact resistance, and heat resistance can be obtained.

  The polymer containing the structural units represented by the above formulas (1) and (2) in the component (B) may be any of a random copolymer, a block copolymer, and an alternating copolymer. It is preferably a coalescence.

In addition, the thermoplastic resin composition of the present embodiment may contain a conventionally known wax as long as the effects of the present invention are obtained. Although not limited to the following, for example, hydrocarbon wax, ester wax, silicone wax and the like can be mentioned. These may be partially modified.
(Other resins)
In addition to the components (A) and (B) described above, the thermoplastic resin composition according to the present embodiment is blended with other resins as required by an arbitrary method as long as the effects of the present invention are not impaired. be able to.

  As other resin, a specific rubber component (C) is mentioned, for example. The specific rubber component (C) includes a dispersed phase composed of a graft copolymer (a) and a continuous phase (b), and the graft copolymer (a) is a trunk polymer composed of a rubbery polymer. And a graft chain graft-polymerized to the trunk polymer, wherein the graft chain is a vinyl cyanide monomer unit, and one or more single monomers copolymerizable with the vinyl cyanide monomer A distribution of the content of the vinyl cyanide monomer units in the graft chain-derived component obtained through oxidative decomposition of the graft copolymer (a) is 2 or more. A first peak having a peak, wherein one or more of the two or more peaks have a peak top in a range where the content of the vinyl cyanide monomer unit is 0% by mass or more and less than 10% by mass. 1 of the peak different from the first peak The above is the second peak having a peak top within the range of the content of the vinyl cyanide monomer unit of 10% by mass or more and less than 55% by mass, in the first peak and the second peak, When the weighted average value obtained from the integral value of each entire peak is a representative value, the representative value of the content ratio indicated by the first peak and the representative value of the content ratio indicated by the second peak This refers to a rubber component having a difference of 10% by mass or more.

  When two or more peaks satisfy the above range, a resin having high transmittance and excellent jetness can be obtained.

  Examples of the rubbery polymer include, but are not limited to, polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-acrylic copolymer, and styrene-butadiene-styrene block copolymer. Conjugated diene rubbers such as polymers, polyisoprene, styrene-isoprene copolymers, and hydrogenated products thereof, acrylic rubbers such as ethyl acrylate and butyl acrylate, ethylene-α-olefin-polyene copolymers, Ethylene-α-olefin copolymer, silicone rubber, silicone-acrylic rubber and the like can be mentioned. These may be used alone or in combination of two or more.

  In particular, polybutadiene, styrene-butadiene copolymer, styrene-butadiene block copolymer and acrylonitrile-butadiene copolymer are preferable from the viewpoint of impact resistance, and polybutadiene is more preferable. The rubbery polymer may have a uniform composition, may contain polymers having different compositions, or may have a continuously changing composition.

  The vinyl monomer is not particularly limited, and examples thereof include aromatic vinyl monomers and vinyl cyanide monomers. Examples of the aromatic vinyl monomer include, but are not limited to, styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, ethyl styrene, pt-butyl styrene, vinyl. Naphthalene is mentioned. Examples of the vinyl cyanide monomer include, but are not limited to, acrylonitrile and methacrylonitrile. These may be used alone or in combination of two or more.

  The distribution of the content of the vinyl cyanide monomer unit in the graft chain-derived component of the graft copolymer (a) is measured by oxidatively decomposing the graft copolymer (a) and then determining the graft chain-derived component. After isolation, the component derived from the graft chain can be determined based on a chromatogram obtained by measurement by HPLC.

  The method of oxidative decomposition is not limited to the following, but, for example, ozonolysis, osmium acid decomposition, or the like can be used. Specifically, a method described in a collection of polymer papers (Fumio Ide et al., Vol. 32, No. 7, PP. 439-444 (July. 1975)) can be used. In this document, the isolated branch polymer corresponds to a component derived from a graft chain in this embodiment.

  More specifically, for example, the distribution of the content of the vinyl cyanide monomer unit in the graft chain-derived component in the graft copolymer (a) can be determined as follows.

  First, the thermoplastic resin composition of the present embodiment is dissolved in chloroform and separated into a chloroform-soluble component and a chloroform-insoluble component. This chloroform insoluble matter (for example, 0.5 g) is mixed with osmium tetroxide (for example, 0.0046 g), t-butyl alcohol (for example, 10.7 g), an organic peroxide (for example, “Perbutyl H-69” (NOF Corporation). (Product name) 9.2 g) is added and, for example, refluxed for 30 minutes, and then concentrated by removing the solvent and dissolved in chloroform. Since a precipitate is obtained by adding methanol thereto, the precipitate is separated and dried. This is weighed (for example, 0.03 g) and dissolved in tetrahydrofuran (for example, 10 mL) to obtain a measurement sample.

  Separately from the above, by using a standard sample (polymer) in which the content of vinyl cyanide monomer units is known by nitrogen analysis, the content of vinyl cyanide monomer units and the retention time in HPLC Create a calibration curve for the relationship.

  After the measurement sample is measured by HPLC to obtain a chromatogram, the distribution of vinyl cyanide (VCN) unit content is determined from the retention time in the chromatogram using the calibration curve.

  The conditions are as follows.

Measuring device: High performance liquid chromatography (manufactured by Shimadzu Corporation)
Sample concentration: Sample 30 mg / THF 10 mL
Column: Silica-based cyanopropyl-treated product (manufactured by Shimadzu Corporation, trade name “Shim-Pak CLC-CN”)
Developing solvent: Tetrahydrofuran / n-hexane (2 liquid gradient measurement)
Detector: Ultraviolet (254 nm)
The graft ratio of the specific rubber component (C) is preferably 250% or less, more preferably 40 to 230%, still more preferably 65 to 220%, still more preferably 80 to 200%, and still more preferably 90. ~ 180%. By setting the graft ratio of the rubber component (C) within the above range, a high-quality appearance can be obtained.

  The graft ratio is (a2) / (a1) × 100, where (a1) is the mass of the rubbery polymer in the graft copolymer (a), and (a2) is the mass of the grafted copolymer. [%] Is defined.

  The refractive index of the other resin is better as the refractive index difference from the amorphous thermoplastic resin (A), which is an essential component in the thermoplastic resin composition of the present embodiment, is smaller from the viewpoint of high-quality appearance. 1.51 to 1.60. More preferably, it is 1.53-1.60, More preferably, it is 1.55-1.60.

  The content of other resins is within a range not exceeding 25% by mass with respect to the total of 100% by mass of the components (A) and (B) from the viewpoint of impact resistance, heat resistance, and high-quality appearance. It is preferably 10% by mass or less, more preferably 5% by mass or less.

In particular, when a rubber component other than the specific rubber component (C) is added, the content of the rubber component other than the rubber component (C) is preferably less than 5% by mass, more preferably 1 It is preferable that it is less than mass%. By setting the content of the rubber component other than the rubber component (C) to less than 5% by mass, a high-quality appearance in the molded body of the present embodiment can be obtained. As the rubber component other than the specific rubber component (C), the distribution of the content of the vinyl cyanide monomer unit in the graft chain-derived component obtained through oxidative decomposition of the graft copolymer (a) Is a rubber component having only one peak.
(Content of (A) component and (B) component)
The contents of the above-described (A) amorphous thermoplastic resin and (B) additive in the thermoplastic resin composition of the present embodiment will be described below.

  First, when the component (A) is 100 parts by mass, the content of the component (B) is preferably more than 0.1 parts by mass and less than 5.0 parts by mass, more preferably 2 to 3.0 parts by mass, more preferably 0.2 to 1.5 parts by mass, even more preferably 0.25 to 1.0 parts by mass, and particularly preferably 0.3 to 0.8 parts by mass. .

By setting the content of the component (A) and the component (B) in the above range, the thermoplastic resin composition and the molded body of the present embodiment can have scratch resistance and a high-quality appearance. .
(Content of each residue in the thermoplastic resin composition)
The content of each monomer residue component constituting the thermoplastic resin composition of the present embodiment will be described below.

  The thermoplastic resin composition of the present embodiment is selected from tetrahydrofuran, trifluoroacetic acid, 1,2-dichloroethane, cyclohexanone, and chlorobenzene as the thermoplastic resin composition as one aspect of the thermoplastic resin composition. When dissolved in at least one solvent, 10-80% by mass of diphenyl carbonate (DPC) residue, 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) ) 1-10% by mass of residues, 3-20% by mass of 1,4-cyclohexanedimethanol (CHDM) residues, and 5-40% by mass of terephthalic acid (TPA) residues are preferred. .

Various residues in the soluble component can be measured by ¹ H-NMR.

When the content of various residues in the soluble content is within the above range, the thermoplastic resin composition and the molded body of the present embodiment have transparency, high-quality appearance, impact resistance, and heat resistance. The property balance of properties is excellent.
(Other additives)
The thermoplastic resin composition of the present embodiment may contain various other additives as necessary in addition to the components (A) and (B) described above, as long as the effects of the present invention are not impaired. It can mix | blend by the method.

  Examples of other additives include plasticizers, lubricants, colorants, brighteners, antistatic agents, various peroxides, antioxidants, weathering agents, light stabilizers, heat stabilizers, and the like. Especially, it is preferable that the thermoplastic resin composition of this embodiment further contains at least 1 sort (s) selected from the group which consists of a coloring agent, a weather resistance, and a heat stabilizer.

  The content of these additives is preferably in a range not exceeding 10% by mass with respect to the thermoplastic resin composition. More preferably, it is 5 mass% or less.

  In order to obtain a high-quality appearance, it is preferable to use a dye as a colorant, and it is preferable to use several kinds of dyes in combination. For example, an organic dye is preferably used in combination, and at least one selected from red, blue, purple, yellow, and green is preferably used in combination. In particular, in order to obtain piano black (jet black), it is preferable to use three or more organic dyes in combination. As the brightening agent, various inorganic materials having a metallic or pearl-like appearance that are preferably used in recent years can be used.

  In order to obtain a molded article having better weather resistance, it is preferable to use an ultraviolet absorber. As a preferable ultraviolet absorber, for example, a benztriazole-based or triazine-based ultraviolet absorber is preferably used. Of these, triazine-based ultraviolet absorbers are more preferable.

  Moreover, it is preferable to use a heat stabilizer from the viewpoint of processing stability. Preferable heat stabilizers include, for example, hindered phenol antioxidants, phosphorus processing heat stabilizers, and sulfur heat stabilizers. More preferably, a hindered phenolic antioxidant and a phosphorus processing heat stabilizer are used in combination.

  The hindered phenol-based antioxidant is not particularly limited. For example, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, etc., but octadecyl-3- ( More preferred is 3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

Although it does not specifically limit as a phosphorus processing heat stabilizer, For example, a tris (2, 4- di-tert- butylphenyl) phosphite, bis (2, 4- dicumyl phenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite and the like can be mentioned, and tris (2,4-di-tert-butylphenyl) phosphite is more preferable.
(Total light transmittance of thermoplastic resin composition)
The thermoplastic resin composition of the present embodiment preferably has a total light transmittance of 50% or more when measured at a thickness of 2.5 mm, more preferably 55% or more, even more preferably, in accordance with ASTM 1003. 60% or more, particularly preferably 70% or more.

  By setting the total light transmittance to 50% or more, the thermoplastic resin composition and the molded body of the present embodiment can obtain a high-quality appearance (jet black).

The method for setting the total light transmittance to 50% or more is not limited to the following, but a method for controlling the amount of the component (B) added to the component (A), and an amorphous property as the component (A). When using polyester and aromatic polycarbonate, the method of controlling the compounding ratio of amorphous polyester and aromatic polycarbonate is also mentioned.
(Form of thermoplastic resin composition)
The morphology of the thermoplastic resin composition of the present embodiment is divided into two phases of a continuous phase and a dispersed phase. The continuous phase is preferably composed of the component (A) and the dispersed phase is composed of the component (B).

  Furthermore, even if the continuous phase is composed of a plurality of components, they are preferably compatible, the component (A) is preferably a single phase, and the dispersed phase (B) component is independent. It is preferable that they exist in a dispersed state.

  In the thermoplastic resin composition of this embodiment, excellent scratch resistance, impact resistance, and heat resistance can be obtained when the form is as described above.

The morphology of the thermoplastic resin composition of the present embodiment can be confirmed by preparing an ultrathin section from a molded body, performing a staining treatment with ruthenium tetroxide, and then performing observation with a transmission electron microscope (TEM). it can.
[Method for producing thermoplastic resin composition]
Next, the manufacturing method of the thermoplastic resin composition of the present embodiment will be described below with an example.

As a manufacturing method of the thermoplastic resin composition of the present embodiment, for example,
(1) A method in which the components (A) and (B) are collectively fed to a twin screw extruder and melt kneaded,
(2) Using a twin-screw extruder provided with an upstream supply port and a downstream supply port, a part of the component (A) is supplied from the upstream supply port, melted and kneaded, and then remaining from the downstream supply port. A method of supplying and melt-kneading the component (A) and the component (B),
(3) When the component (A) is composed of a plurality of components, first, all of the component (A) is supplied to a twin screw extruder and melt-kneaded, and then the melt-kneaded product and the component (B) are newly added to the twin-screw extruder. A method of supplying and melt-kneading twice,
Etc.

  Moreover, it is preferable that the barrel preset temperature of an extruder is 240 to 300 degreeC. By setting it as this range, the morphology mentioned above can be acquired and the effect of this invention can be acquired reliably.

The thermoplastic resin composition of the present embodiment has properties that conflict with high scratch resistance, heat resistance, impact resistance, and high-quality appearance by blending the component (A) and the component (B). be able to.
[Molded body]
The molded body of the present embodiment can be obtained by molding the above-described thermoplastic resin composition.

  Although it does not specifically limit as a manufacturing method of a molded object, For example, injection molding, sheet molding, vacuum molding, blow molding, injection blow molding, inflation molding, T-die molding, press molding, extrusion molding, foam molding, casting method A known method such as molding by the method can be applied.

  A feature of the thermoplastic resin composition of the present embodiment is that a molded body having a high-quality appearance can be produced only by molding without painting.

  In particular, in injection molding, a molded article having a particularly good appearance can be obtained.

  The injection-molded body can be obtained by, for example, using an injection molding machine and setting a cylinder temperature = 260 ° C. to 300 ° C. and a mold temperature = 60 ° C. to 90 ° C. and performing a general injection molding method.

  When manufacturing an injection-molded body, heat and cool molding in which a mold repeats heating / cooling is preferable, and an injection-molded body having a high appearance can be obtained more easily. This is preferably used particularly when a thin molded body or a molded body having a weld portion is manufactured. The mold temperature at that time is preferably 90 ° C. to 180 ° C. during heating and 80 ° C. to 50 ° C. during cooling.

  The injection speed is preferably higher, and the injection pressure is preferably not too high.

The faster the injection speed, the more uniform the surface of the molded body is less likely to cause poor appearance during molding, and the transferability to the mold is improved by adjusting the injection pressure, and the jetness is higher. A high-quality molded article can be obtained.
(Use)
The molded article of the thermoplastic resin composition of the present embodiment is uncoated, has various heat and shock resistance and high quality appearance only by molding, and various housings that are required to have design and impact resistance. It is suitable for automobile materials such as body materials, automobile interior materials, and various automobile interior parts.

Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.
(Raw materials used)
[1]
(A-1) Aromatic polycarbonate trade name “WONDERLITE (registered trademark) PC-110 (MVR; 10 g / 10 min)” manufactured by Kimisha Co., Ltd. was used.

MVR was measured according to ISO1133.
(A-2) Amorphous polyester (A-2-1) Trade name “Tritan TX2000 (inherent viscosity; 0.64 dL / g, Tg; 131 ° C., diol component; TMCD residue 36 mol%, CHDM residue 64) Mol%, dicarboxylic acid component; aromatic dicarboxylic acid residue having 20 or less carbon atoms (100 mol%) ”manufactured by EASTMAN.
(A-2-2) Trade name “EASTAR GN001 (PET-G), (inherent viscosity; 0.75 dL / g, Tg; 85 ° C., diol component; ethylene glycol (EG) residue 30 mol%, CHDM residue 70 mol%, dicarboxylic acid component; aromatic dicarboxylic acid residue having 20 or less carbon atoms (100 mol%) ”manufactured by EASTMAN Co., Ltd. was used.

The inherent viscosity was measured at a concentration of 0.5 g / dL in 60/40 (wt / wt) phenol / tetrachloroethane at 25 ° C. in accordance with the regulations of ISO1628-1: 1998.
(B) Additive (B-1) Trade name “Diacarna 30M”, manufactured by Mitsubishi Chemical Co., Ltd. (B-1) contained structural units represented by the following formulas (1) and (2). .

[式（１）中、Ｒは炭素数が１０〜６０の直鎖又は分岐のアルキル基を表す。]
（Ｂ−２）商品名「リケマールＳ−１００」、理研ビタミン社製
（Ｂ−３）商品名「サンワックス Ｅ−２５０Ｐ」、三洋化成工業社製
（Ｂ−４）商品名「ＮＵＣ−３８１０」、日本ユニカー社製
（Ｂ−５）商品名「シャリーヌＲ−１７０Ｓ」、日信化学工業社製
（Ｂ−６）商品名「ＧＥＮＩＯＰＬＡＳＴＰＥＬＬＥＴ Ｓ」旭化成ワッカーシリコン社製
なお、（Ｂ−２）〜（Ｂ−６）は、上記式（１）及び（２）で示される構成単位を含有していなかった。
（Ｃ−１）ゴム成分
ゴム成分（Ｃ）は、後述するようにゴムラテックス（ゴム質重合体）に所定の単量体単位がグラフト重合されたグラフト共重合体（ａ）と、グラフトされずに連続相（ｂ）となった単量体やその重合体を含むゴム成分を用いた。

[In formula (1), R represents a linear or branched alkyl group having 10 to 60 carbon atoms. ]
(B-2) Product name “Riquemar S-100”, manufactured by Riken Vitamin Co., Ltd. (B-3) Product name “Sun Wax E-250P”, Sanyo Chemical Industries Co., Ltd. (B-4) Product name “NUC-3810” (B-5) product name “Charine R-170S” manufactured by Nihon Unicar Co., Ltd., (B-6) product name “GENIOPLASTPELLET S” manufactured by Asahi Kasei Wacker Silicon Co., Ltd. B-6) did not contain the structural units represented by the above formulas (1) and (2).
(C-1) Rubber component The rubber component (C) is not grafted with a graft copolymer (a) in which a predetermined monomer unit is graft-polymerized on a rubber latex (rubber polymer) as described later. The rubber component containing the monomer and polymer thereof which became the continuous phase (b) was used.

  The method for producing the rubber latex to be the graft copolymer (a); acrylonitrile / butadiene / styrene copolymer (ABS) was as follows.

  18 parts by mass of butadiene, 2 parts by mass of acrylonitrile, 160 parts by mass of deionized water (iron concentration: less than 0.02 ppm), 0.067 parts by mass of potassium rosinate, 0.033 parts by mass of potassium oleate, 1 part by weight, 0.03 part by weight of sodium hydroxide, 0.075 part by weight of sodium persulfate, and 0.10 part by weight of sodium bicarbonate are placed in a pressure vessel equipped with a stirrer degassed in vacuum, Was raised from room temperature to 65 ° C. to initiate polymerization.

  After 2.5 hours from the start of polymerization, over a further 5 hours, 80 parts by mass of butadiene monomer, 0.3 parts by mass of tartarid decyl mercaptan, 0.67 parts by mass of disproportionated potassium rosinate, 0.33 of potassium oleate Part by weight, 0.1 part by weight of sodium persulfate, 0.05 part by weight of sodium hydroxide, 0.15 part by weight of sodium bicarbonate and 50 parts by weight of deionized water were added continuously, and the system was raised to 80 ° C. The mixture was heated and cooled after 14 hours from the start of polymerization to complete the polymerization.

  The solid content (rubber latex: rubbery polymer) in the obtained polymerization liquid was 41.8% by mass, and the solid content was measured with a Microtrac particle size analyzer (trade name: nanotrac 150) manufactured by Nikkiso Co., Ltd. The average particle size was 165 nm.

  95 parts by mass of deionized water (iron concentration: less than 0.02 ppm) is added to 40 parts by mass (solid content) of the rubber latex (rubber polymer) obtained as described above, and the gas phase part is replaced with nitrogen. An aqueous solution prepared by dissolving 0.0786 parts by mass of sodium formaldehyde sulfoxylate, 0.0036 parts by mass of ferrous sulfate, and 0.0408 parts by mass of disodium ethylenediaminetetraacetate was added to 20 parts by mass of deionized water. . Thereafter, the temperature was raised to 70 ° C.

  Subsequently, over 1.5 hours, a monomer mixture composed of 18 parts by mass of styrene and 0.129 parts by mass of cumene hydroperoxide, and 10.5 parts by mass of deionized water were mixed with sodium formaldehyde sulfoxylate 0. An aqueous solution obtained by dissolving 0.0392 parts by mass was added.

  Subsequently, over 3.5 hours, a monomer mixture composed of 14.7 parts by mass of acrylonitrile, 27.3 parts by mass of styrene and 0.14 parts by mass of cumene hydroperoxide, and 24.5 parts by mass of deionized water. An aqueous solution obtained by dissolving 0.0914 parts by mass of sodium formaldehyde sulfoxylate was added to the part.

  After the addition, 0.02 parts by mass of cumene hydroperoxide was further added, and then the polymerization reaction was completed for 1 hour while controlling the reaction vessel at 70 ° C., and 0.5 mass of potassium rosinate was added there. Parts were added. Thus, an ABS rubber latex containing the graft copolymer (a) was obtained.

  After adding 0.07 parts by mass of a silicone resin defoamer and 0.6 parts by mass of a phenolic antioxidant emulsion to 100 parts by mass of the ABS rubber latex, it is removed so that the solid content concentration becomes 10% by mass. After adjusting by adding ionic water and heating to 70 ° C., an aqueous aluminum sulfate solution was added for solidification, and solid-liquid separation was performed with a screw press. The water content at this time was 10% by mass. This was dried to obtain a rubber component (C-1).

The rubber component (C-1) includes a dispersed phase composed of a graft copolymer (a) and a continuous phase (b), and the graft copolymer (a) comprises a trunk polymer composed of a rubbery polymer, And a graft chain graft-polymerized to the trunk polymer, wherein the graft chain is a vinyl cyanide monomer unit and one or more monomers copolymerizable with the vinyl cyanide monomer. Unit. In the component (C-1), the distribution of the content of the vinyl cyanide monomer unit in the component derived from the graft chain obtained through oxidative decomposition of the graft copolymer (a) was measured. One of the two peaks has a peak top at a content of the vinyl cyanide monomer unit of 0.2% by mass, and the other is the vinyl cyanide monomer. When the content rate of the unit has a peak top at 35% by mass and the weighted average value obtained from the integrated value of the entire peak in the first peak and the second peak is a representative value, The difference between the representative value of the content indicated by the first peak and the representative value of the content indicated by the second peak was 34.8% by mass.
(C-2) Rubber component The following graft copolymer was produced according to the method described in JP-A-7-258501. Graft copolymer (a) 70% by mass (47% by mass of butadiene, 23% by mass of graft polymer, 49% of graft rate, the vinyl cyanide monomer unit in the component derived from the graft chain obtained through oxidative decomposition) The distribution of the content of styrene has one peak top at 30% by mass), 30% by mass of the copolymer (b) existing as a continuous phase without being grafted (the content of the vinyl cyanide monomer is 30% by mass) , Aromatic vinyl monomer content; 70% by mass)
(C-3) Rubber component After obtaining a rubber latex in the same manner as the component (C-1), deionized water (iron concentration) was added to 50 parts by mass (solid content) of the obtained rubber latex (rubber polymer). : Less than 0.02 ppm), 95 parts by mass were added, and the gas phase part was replaced with nitrogen, and 20 parts by mass of deionized water, 0.0786 parts by mass of sodium formaldehyde sulfoxylate, and 0.0036 parts by mass of ferrous sulfate. Part, an aqueous solution prepared by dissolving 0.0408 parts by mass of disodium salt of ethylenediaminetetraacetic acid was added. Thereafter, the temperature was raised to 70 ° C.

  Subsequently, over 1.5 hours, a monomer mixture composed of 1.1 parts by weight of acrylonitrile, 13.9 parts by weight of styrene and 0.1 parts by weight of cumene hydroperoxide, and 10.5 parts of deionized water. An aqueous solution obtained by dissolving 0.0392 parts by mass of sodium formaldehyde sulfoxylate was added to parts by mass.

  Subsequently, over 3.5 hours, a monomer mixture consisting of 5.3 parts by weight of acrylonitrile, 29.7 parts by weight of styrene, 0.2 parts by weight of cumene hydroperoxide, and 0.4 parts by weight of tarsia decyl mercaptan. An aqueous solution prepared by dissolving 0.0914 parts by mass of sodium formaldehyde sulfoxylate in 24.5 parts by mass of liquid and deionized water was added.

  After the addition, 0.02 parts by mass of cumene hydroperoxide was further added, and then the polymerization reaction was completed for 1 hour while controlling the reaction vessel at 70 ° C., and 0.5 mass of potassium rosinate was added there. Parts were added. Thus, an ABS rubber latex containing the graft copolymer (a) was obtained.

  After adding 0.07 parts by mass of a silicone resin defoamer and 0.6 parts by mass of a phenolic antioxidant emulsion to 100 parts by mass of the ABS rubber latex, it is removed so that the solid content concentration becomes 10% by mass. After adjusting by adding ionic water and heating to 70 ° C., an aqueous aluminum sulfate solution was added for solidification, and solid-liquid separation was performed with a screw press. The water content at this time was 10% by mass. This was dried to obtain a rubber component (C-3).

The graft copolymer (a) has a trunk polymer composed of a rubbery polymer, and a graft chain graft-polymerized to the trunk polymer, the graft chain comprising a vinyl cyanide monomer unit, And one or more monomer units copolymerizable with the vinyl cyanide monomer. In the component (C-3), the distribution of the content of the vinyl cyanide monomer unit in the component derived from the graft chain obtained through oxidative decomposition of the graft copolymer (a) was measured. One of the two peaks has a peak top at a content of the vinyl cyanide monomer unit of 6.9% by mass, and the other peak is the vinyl cyanide monomer. When the content rate of the unit has a peak top at 15.1% by mass, and the weighted average value obtained from the integrated value of each peak in the first peak and the second peak is a representative value The difference between the representative value of the content indicated by the first peak and the representative value of the content indicated by the second peak was 8.2% by mass.
(Evaluation method)
The evaluation method of each physical property was as follows.
<(1) Measurement of total light transmittance of thermoplastic resin composition>
Using the thermoplastic resin compositions of Examples 1 to 11 and Comparative Examples 1 to 12, which will be described later, by an injection molding machine, conditions of cylinder temperature = 280 ° C. and mold temperature = 80 ° C., 5 cm × 9 cm, thickness 2. A 5 mm flat plate was injection molded.

  Using this flat plate, the total light transmittance was evaluated according to ASTM D1003.

The average value of the three measured values was calculated and used as the total light transmittance value.
<(2) Measurement of Charpy impact strength>
Using the thermoplastic resin compositions of Examples 1 to 11 and Comparative Examples 1 to 12, which will be described later, with an injection molding machine, the cylinder temperature is 280 ° C., the mold temperature is 80 ° C., and the thickness is 4 mm according to ISO 294. A multipurpose specimen A type (length 150 mm, narrow portion width 10.0 mm) was molded.

  The obtained test piece was processed into a shape of 80 × 10 × 4 mm, a notch was given to the processed test piece, and Charpy impact strength was measured according to ISO179.

The average value of 10 measured values was calculated and used as the Charpy impact strength value.
<(3) Measurement of deflection temperature under load (DTUL)>
Using the thermoplastic resin compositions of Examples 1 to 11 and Comparative Examples 1 to 12, which will be described later, with an injection molding machine, under conditions of cylinder temperature = 280 ° C. and mold temperature = 80 ° C., thickness 4 mm according to ISO 294 A multi-purpose test piece A type (length 150 mm, narrow portion width 10.0 mm) was molded.

  The obtained test piece was processed into a shape of 80 × 10 × 4 mm, and the deflection temperature under load (DTUL) was measured according to ISO75.

The average value of the three measured values was calculated and used as the DTUL value.
<(4) Measurement of jet black>
Jet black was evaluated as an index of high-quality appearance.

  A total of 1% by mass of each color (red, yellow, blue, and green) dyes was kneaded into the thermoplastic resin compositions of Examples 1 to 11 and Comparative Examples 1 to 12 described below, and then the cylinder temperature was measured using an injection molding machine. = A flat plate having a size of 5 cm × 9 cm and a thickness of 2.5 mm was injection-molded at a mold temperature = 80 ° C.

  The dyes are: red dye “CI; Solvent Red 179”, yellow dye “CI; Disperse Yellow 160”, blue dye “CI; Solvent Blue 97”, green dye “CI”; Four types of “Green 3” were used.

  Using the obtained flat plate, a multi-light source spectrocolorimeter “CM-2002” (manufactured by Konica Minolta Co., Ltd.), SCE (excluding specular reflection light), D65 light source / 10 ° field of view, L * a * L * was measured in the b * color system.

The average value of the two measured values was calculated and used as the L * value.
<(5) Measurement of scratch resistance>
In Examples 1 to 11 and Comparative Examples 1 to 12, a 5 cm × 9 cm flat plate with a thickness of 2.5 mm used for measurement of jet black is used, and a scratch test is performed 15 times only at a 1 mm interval with a Pin on Disc abrasion tester. Went. The load was 5 kg, the stroke was 50 mm, the speed was 10 mm / sec, and the SUS304 ball (diameter 5 mm) was used as the mating material.

  Using a multi-light source spectrocolorimeter “CM-2002” (manufactured by Konica Minolta Co., Ltd.), the brightness L * of the flat plate was measured before and after the test, and the amount of change ΔL * was confirmed. ΔL * is represented by the following equation.

ΔL * = L * (after scratch resistance) −L * (before scratch resistance)
The average value of the three measured values was calculated. If the average value was 0.5 or less, it was judged as “good”, and when it exceeded 0.5, it was judged as “x”.
<(6) Measurement of weather resistance>
In Examples 1 to 11 and Comparative Examples 1 to 12, using a flat plate of 5 cm × 9 cm and a thickness of 2.5 mm used for measurement of jet black, a sunshine weather meter “SX75” manufactured by Suga Test Instruments Co., Ltd. The temperature was 83 ° C., there was no rainfall, the irradiance was 78 W / m 2, and # 255 was used as the filter. The test time was 300 hours.

The average value of the three measured values was calculated and used as the weather resistance value.
Example 1
The pellet of the thermoplastic resin composition was manufactured as follows using the twin-screw extruder ("TEM-58SS" by Toshiba Machine).

  The supply port was one on the upstream side, and the components (A-1) and (B-1) that were sufficiently dried to remove water were supplied. The cylinder temperature of the extruder at that time was set to 280 ° C. for all stages.

  At this time, the discharge amount of the kneaded material was 300 kg / hour, and the screw rotation speed was 250 rpm. Table 1 shows the types of raw materials and the mixing ratio.

Table 1 shows the results of the above evaluations using the obtained pellets.
(Example 2)
The component (A-2-1) was supplied as the component (A). Other conditions were the same as in Example 1 to obtain pellets. Table 1 shows the types of raw materials and the mixing ratio.

Table 1 shows the results of the above evaluations using the obtained pellets.
(Examples 3 and 5 to 8, Comparative Examples 9 and 10)
As the component (A), the components (A-1) and (A-2-1) were supplied. Other conditions were the same as in Example 1 to obtain pellets. Table 1 shows the types of raw materials and the mixing ratio.

Table 1 shows the results of the above evaluations using the obtained pellets.
Example 4
As the component (A), components (A-1), (A-2-1), and (A-2-2) were supplied. Other conditions were the same as in Example 1 to obtain pellets. Table 1 shows the types of raw materials and the mixing ratio.

Table 1 shows the results of the above evaluations using the obtained pellets.
Example 9
As the component (B), the components (B-1) and (B-2) were supplied. Other conditions were the same as in Example 5 to obtain pellets. Table 1 shows the types of raw materials and the mixing ratio.

Table 1 shows the results of the above evaluations using the obtained pellets.
(Example 10)
(B-1) Pellets were obtained in the same manner as in Example 1 except that the amount of component was changed. Table 1 shows the types of raw materials and the mixing ratio.

Table 1 shows the results of the above evaluations using the obtained pellets.
(Example 11)
Pellets were obtained in the same manner as in Example 5 except that the component (C-1) was additionally supplied. Table 1 shows the types of raw materials and the mixing ratio.

Table 1 shows the results of the above evaluations using the obtained pellets.
(Comparative Example 1)
Only the component (A-1) was supplied, and the component (B) was not supplied. Other conditions were the same as in Example 1 to obtain pellets.

  Table 1 shows the types of raw materials and the mixing ratio.

Table 1 shows the results of the above evaluations using the obtained pellets.
(Comparative Example 2)
Only the component (A-2-1) was supplied, and the component (B) was not supplied. Other conditions were the same as in Example 1 to obtain pellets.

  Table 1 shows the types of raw materials and the mixing ratio.

Table 1 shows the results of the above evaluations using the obtained pellets.
(Comparative Example 3)
As the component (A), the components (A-1) and (A-2-1) were supplied, and the component (B) was not supplied. Other conditions were the same as in Example 1 to obtain pellets.

  Table 1 shows the types of raw materials and the mixing ratio.

Table 1 shows the results of the above evaluations using the obtained pellets.
(Comparative Examples 4 to 8)
Components other than (B-1) were added as component (B). Other conditions were the same as in Example 3 to obtain pellets.

  Table 1 shows the types of raw materials and the mixing ratio.

Table 1 shows the results of the above evaluations using the obtained pellets.
(Comparative Examples 11 and 12)
A pellet was obtained in the same manner as in Example 11 except that the component (C-2) or the component (C-3) was added as the component (C).

  Table 1 shows the types of raw materials and the mixing ratio.

  Table 1 shows the results of the above evaluations using the obtained pellets.

実施例１〜１１においては、耐衝撃性、耐熱性、及び高品位な外観（漆黒）、耐傷性、耐光り性の全ての特性バランスが良好な成形品が得られた。

In Examples 1 to 11, molded articles having good balance of all the characteristics of impact resistance, heat resistance, high-quality appearance (jet black), scratch resistance, and light resistance were obtained.

  The thermoplastic resin composition of the present embodiment can be suitably used for various molded articles.

  For example, the present invention has industrial applicability as various housing materials and automotive interior / exterior parts that are required to have design and impact resistance.

Claims (12)

An amorphous polyester and / or an amorphous thermoplastic resin (A) made of an aromatic polycarbonate, and an additive (B),
The content of the component (B) exceeds 0.1 parts by mass with respect to 100 parts by mass of the component (A),
The component (B) contains structural units represented by the following formulas (1) and (2),
A thermoplastic resin composition having a total light transmittance of 50% or more when measured at a thickness of 2.5 mm in accordance with ASTM 1003.

[In formula (1), R represents a linear or branched alkyl group having 10 to 60 carbon atoms. ]   The thermoplastic resin composition according to claim 1, comprising at least amorphous polyester as the component (A).   The thermoplastic resin composition according to claim 2, comprising at least an alicyclic diol as a diol component of the amorphous polyester in the component (A).   The thermoplastic resin composition according to claim 2 or 3, wherein the amorphous polyester in the component (A) is a polyester resin containing at least an aromatic dicarboxylic acid and an alicyclic diol.   The thermoplastic resin composition according to claim 3 or 4, comprising 2,2,4,4-tetramethyl-1,3-cyclobutanediol as the alicyclic diol in the component (A).   The thermoplastic resin composition according to any one of claims 1 to 5, comprising 0.2 to 1.5 parts by mass of the component (B) with respect to 100 parts by mass of the component (A). Further containing a rubber component (C),
The component (C) includes a dispersed phase composed of a graft copolymer (a) and a continuous phase (b), and the graft copolymer (a) comprises a trunk polymer composed of a rubbery polymer, A graft chain graft-polymerized to a trunk polymer, wherein the graft chain includes a vinyl cyanide monomer unit, and one or more monomer units copolymerizable with the vinyl cyanide monomer. The distribution of the content of the vinyl cyanide monomer units in the graft chain-derived component of the graft copolymer (a) has two or more peaks, and the two or more Are at least one peak having a peak top in a range of 0% by mass or more and less than 10% by mass, wherein the content of the vinyl cyanide monomer unit is the first peak, One or more of the different peaks It is the 2nd peak which has a peak top in the range whose content rate of a body unit is 10 mass% or more and less than 55 mass%, and calculates | requires from the integrated value of each peak whole in the said 1st peak and 2nd peak. When the weighted average value is a representative value, the difference between the representative value of the content shown by the first peak and the representative value of the content shown by the second peak is 10% by mass or more. The thermoplastic resin composition according to any one of claims 1 to 6.   Furthermore, the thermoplastic resin composition of Claim 7 whose content of rubber components other than the said rubber component (C) is less than 1 mass%.   The thermoplastic resin composition according to any one of claims 1 to 8, further comprising at least one selected from the group consisting of a colorant, a weathering agent, and a heat stabilizer.   The molded object containing the thermoplastic resin composition as described in any one of Claims 1-9.   The molded object according to claim 10, wherein the molded object is unpainted.   The molded body according to claim 10 or 11, wherein the molded body is an automobile material.