JP6322000B2 - Thermoplastic resin composition, molded article thereof, and production method thereof - Google Patents

Description

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

  Alloy (PC / ABS) of acrylonitrile / butadiene / styrene copolymer (ABS resin) and aromatic polycarbonate has both excellent moldability of ABS and excellent impact resistance of PC. Widely used in fields requiring high impact resistance, such as housings for home appliances. It is also widely used in fields that require heat resistance in addition to the above characteristics, such as automobile interior parts.

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 a field, conventionally, a method of painting mainly on the surface of a resin material has been adopted.
Further, while a high design appearance is required, there is an increasing demand for not performing the coating process due to problems such as environmental pollution and high cost due to discharge of volatile organic compounds (VOC).

However, although PC / ABS is a material that is excellent in impact resistance and heat resistance, it is a cloudy material, so even if it contains a dye / pigment, it becomes whitish, and it is as high as piano black. It is difficult to obtain a quality appearance.
PC / ABS also has a problem of poor weld appearance in which a weld portion generated during molding is conspicuous on the design surface.
Furthermore, PC / ABS has a problem of high molding shrinkage and low dimensional stability.
Here, when the weld appearance defect is a molded body having a multi-point gate, a hole or a window, the portion where the flow ends where the fountain flow occurs is different in resin flow from the other portions. A phenomenon that forms a line. If there is a poor weld appearance, there is a problem that even if the color is excellent as a material, the sense of quality as a product is lost.
From the above, there has been a strong demand for materials that can achieve high appearance without painting and have mechanical properties such as impact resistance and heat resistance.

Conventionally, as a technique for improving the design properties of PC / ABS, for example, Patent Document 1 listed below includes the presence of a rubbery polymer having a refractive index in the range of 1.52 to 1.58, such as a styrene-butadiene-based polymer. Under the above, a vinyl monomer containing an aromatic vinyl compound is polymerized, and then a polycarbonate is alloyed to obtain a rubber-reinforced copolymer resin (PC / ABS), and further, an amorphous polyester is added. A technique is disclosed in which PC / ABS, which is normally cloudy, is made translucent by lowering the refractive index of the continuous phase and approaching the refractive index of the dispersed phase (see, for example, Patent Document 1).
On the other hand, by limiting the graft ratio of the graft copolymer to a specific range, the refractive index of the dispersed phase is increased, and by approaching the refractive index of the continuous phase, high color development and scratch resistance are sought. A technique is disclosed (for example, see Patent Document 2).

JP 2006-328355 A JP 2013-18950 A

However, in the techniques described in Patent Document 1 and Patent Document 2, although transparency is improved, while maintaining heat resistance and impact resistance, deep piano black (jet black), molding shrinkage ratio, No product satisfying the weld appearance has been obtained.
In addition, a highly transparent resin such as PC and PMMA / ABS can obtain a high-grade appearance such as piano black by adding a dye / pigment, but PC is fluid, PMMA / ABS has a defect that it is inferior in impact resistance and heat resistance, and until now, no material satisfying all of heat resistance, impact resistance, and high-quality appearance has been obtained.

  Therefore, in the present invention, in view of the above-described problems of the prior art, it has both high heat resistance, impact resistance, and high-quality appearance (jet black, high-definition, good weld appearance) only by molding without painting. It aims at providing the thermoplastic resin composition from which a molded object is obtained, and its molded object.

As a result of intensive studies to solve the above problems, the present inventors have found a thermoplastic resin composition containing a dispersed phase composed of a graft copolymer (A) and a predetermined continuous phase (B). The graft copolymer (A) has a trunk polymer composed of a rubbery polymer, and a graft chain graft-polymerized to the trunk polymer, and the graft chain includes a vinyl cyanide monomer unit and The graft chain-derived component having one or more monomer units copolymerizable with the vinyl cyanide monomer and obtained through oxidative decomposition of the graft copolymer (A). The distribution of the content of vinyl cyanide monomer units is specific, and a thermoplastic resin composition having a specific glass transition point is high heat resistance and impact resistance only by molding without coating. High-quality appearance (black, high-definition, good quality Found that field appearance) can produce a molded body having both, and have completed the present invention.
That is, the present invention is as follows.

[1]
A dispersed phase comprising a graft copolymer (A);
Continuous phase (B);
Including,
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 has a vinyl cyanide monomer unit and one or more monomer units copolymerizable with the vinyl cyanide monomer,
The distribution of the content ratio of the vinyl cyanide monomer unit in the component derived from the graft chain obtained through oxidative decomposition of the graft copolymer (A) has two or more peaks,
One or more of the two or more peaks have a content of the vinyl cyanide monomer unit of 0.
A first peak having a peak top in a range of not less than 10% by mass and less than 10% by mass,
One or more of the peaks different from the first peak is a second peak having a peak top in a range where the content of the vinyl cyanide monomer unit is 10% by mass or more and less than 55% by mass,
When 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 shown by the first peak and the representative value of the content shown by the second peak is 10% by mass or more,
Each having one or more glass transition points at less than 20 ° C and above 20 ° C,
The glass transition point of the 20 ° C. or higher is 100 ° C. or higher, and the thermoplastic resin composition has one or more glass transition points in the range of 120 to 140 ° C.
[2]
The thermoplastic resin composition is
Each having one or more glass transition points at less than 20 ° C and above 20 ° C,
The glass transition point of 20 ° C. or higher is in the range of 100 ° C. to 150 ° C., and 12
The thermoplastic resin composition according to [1], wherein there is one or more glass transition points within a range of 0 to 140 ° C.
[3]
The thermoplastic resin composition is
Each having one or more glass transition points at less than 20 ° C and above 20 ° C,
The glass transition point of 20 ° C. or higher is two, one in the range of 120 to 140 ° C., 10
The thermoplastic resin composition according to [1] or [2], which has one in the range of 0 to 115 ° C.
[4]
The thermoplastic resin composition according to any one of [1] to [3], wherein the continuous phase (B) contains an amorphous thermoplastic resin.
[5]
The thermoplastic resin composition according to any one of [1] to [4], wherein the continuous phase (B) contains at least a vinyl cyanide monomer.
[6]
[1] to [5], wherein the continuous phase (B) contains an aromatic polycarbonate residue and a 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residue.
The thermoplastic resin composition according to any one of the above.
[7]
The thermoplastic resin composition according to any one of [1] to [6], wherein the graft ratio of the graft copolymer (A) is 150 to 200%.
[8]
Of the content distribution of the component derived from the vinyl cyanide monomer in the component derived from the graft chain obtained through oxidative decomposition of the graft copolymer (A),
The heat according to any one of [1] to [7], wherein the peak top of the second peak is in the range of vinyl cyanide monomer unit content of 25% by mass or more and 40% by mass or less. Plastic resin composition.
[9]
The thermoplastic resin composition according to any one of [1] to [8], further including a colorant.
[10]
The molded object containing the thermoplastic resin composition as described in any one of said [1] thru | or [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 interior material.
[13]
The method for producing a molded article according to any one of [10] to [12],
The manufacturing method of a molded object which has the process of shape | molding the metal mold | die temperature at the time of shaping | molding as 120 degreeC or more.

  According to the present invention, a thermoplastic resin composition capable of obtaining a molded body having both high heat resistance and impact resistance and a high-quality appearance (jet black, high-definition, good weld appearance) only by molding without painting, And the molded object of the said thermoplastic resin composition is obtained.

The schematic diagram of the distribution of the content rate of the vinyl cyanide-type monomer unit in the component derived from the graft chain obtained through the oxidative decomposition of a graft copolymer is shown.

  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
A dispersed phase comprising a graft copolymer (A);
Continuous phase (B);
Including,
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 has 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 obtained through oxidative degradation of the graft copolymer (A) has two or more peaks,
One or more of the two or more peaks is a first peak having 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,
One or more peaks different from the first peak are second peaks having a peak top in a range where the content of the vinyl cyanide monomer unit is 10% by mass or more and less than 55% by mass,
When 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 shown by the first peak and the representative value of the content shown by the second peak is 10% by mass or more,
Each having one or more glass transition points at less than 20 ° C and above 20 ° C,
The glass transition point of the 20 ° C. or higher is 100 ° C. or higher, and the thermoplastic resin composition has one or more glass transition points in the range of 120 to 140 ° C.

(Graft copolymer (A) which is a dispersed phase)
The thermoplastic resin composition in the present embodiment includes a graft copolymer (A) (hereinafter referred to as graft), which includes a trunk polymer composed of a rubbery polymer, and a graft chain graft-polymerized to the trunk polymer. A copolymer (A), a component (A), and (A)).

Examples of the rubber polymer that is the trunk polymer include, but are not limited to, diene rubber, acrylic rubber, and ethylene rubber. Specifically, polybutadiene, styrene-butadiene copolymer, block copolymer of styrene-butadiene, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, polyisoprene, butadiene-methyl methacrylate copolymer , Butyl acrylate-methyl methacrylate copolymer, butadiene-ethyl acrylate copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-isoprene copolymer and ethylene-methyl acrylate A copolymer is mentioned.
These may be used individually by 1 type and may be used in combination of 2 or more type.
Of these, one or more rubbery polymers selected from the group consisting of polybutadiene, styrene-butadiene copolymer, styrene-butadiene block copolymer, and acrylonitrile-butadiene copolymer are used from the viewpoint of impact resistance. preferable.

When the rubbery polymer is a copolymer, the composition (distribution) of each constituent unit in the rubbery polymer may be uniform, non-uniform, or continuously. The composition may be changed.
The composition of each structural unit can be confirmed by a Fourier transform infrared spectrophotometer (FT-IR).

In the thermoplastic resin composition of the present embodiment, the rubbery polymer in the graft copolymer (A) is dispersed in the continuous phase (B). The plastic resin composition has a sea-island structure in which a graft copolymer (A) having a rubber polymer as a trunk polymer is used as an island and a continuous phase (B) described later is used as a sea.
The shape of the dispersed phase having a dispersed rubbery polymer is not particularly limited, and examples thereof include an indeterminate shape, a rod shape, a flat plate shape, and a particle shape. In these, a particulate form is preferable from the point of impact resistance.
The dispersed phase may be dispersed individually one by one in the continuous phase (B) described later, or may be dispersed in the state of an aggregate in which several dispersed phases are aggregated. From this point of view, it is preferable that each one is dispersed independently.

In the thermoplastic resin composition of the present embodiment, the size of the graft copolymer dispersed in the continuous phase (B) is a mass average when the shape of the graft copolymer (A) is particulate. The particle diameter is preferably 0.10 μm or more from the viewpoint of impact resistance, and preferably 0.80 μm or less from the viewpoint of transparency.
The mass average particle diameter of the graft copolymer (A) is more preferably 0.10 to 0.60 μm, still more preferably 0.10 to 0.35 μm.
The distribution of the mass average particle diameter of the graft copolymer (A) can take various dispersion forms such as monodisperse, polydisperse, or bimodal distribution according to the intended physical properties. Here, the particle diameter of the graft copolymer (A) corresponds to the diameter when the shape of the graft copolymer (A) is spherical, and when it is not spherical, the longest diameter and the shortest diameter The average value of
For example, there may be a non-uniform structure containing a rubber component and a resin component, such as a structure containing an occlusion in which the resin component is phase-separated inside the graft copolymer (A). The mass average particle diameter of the graft copolymer (A) in the case of having a structure containing ss is measured in a state including occlusion.

The mass average particle diameter of the graft copolymer (A) is determined as follows.
First, an ultrathin section is manufactured from the molded article of the thermoplastic resin composition of the present embodiment, and the ultrathin section is dyed with a staining agent such as osmium tetroxide or ruthenium tetroxide.
Thereafter, the stained ultrathin section can be obtained by photographing with a transmission electron microscope (TEM) and analyzing an image of an arbitrary range (15 μm × 15 μm) of the ultrathin section.
The image can be analyzed using, for example, image analysis software “A Image-kun” (manufactured by Asahi Kasei Engineering Corporation).

In the graft copolymer (A), the vinyl cyanide monomer contained in the graft chain graft-polymerized to the rubber polymer as the trunk polymer is not limited to the following, but, for example, acrylonitrile And methacrylonitrile.
In the graft copolymer (A), at least a part of the vinyl cyanide monomer unit is copolymerized with one or more monomer units copolymerizable therewith.
Examples of the monomer copolymerizable with the vinyl cyanide monomer include, but are not limited to, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, and ethylstyrene. , Aromatic vinyl monomers such as pt-butylstyrene and vinylnaphthalene; (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate; Acrylic acids such as (meth) acrylic acid; N-substituted maleimide monomers such as N-phenylmaleimide and N-methylmaleimide; and glycidyl group-containing monomers such as glycidyl (meth) acrylate. These may be used alone or in combination of two or more.
Among these, from the viewpoint of strength and heat resistance, styrene, α-methylstyrene, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, N-phenylmaleimide, and glycidyl methacrylate are preferable, and from the viewpoint of strength. Styrene is more preferable, and N-phenylmaleimide is more preferable from the viewpoint of heat resistance.

In the thermoplastic resin composition of the present embodiment, the graft copolymer (A) as a dispersed phase is obtained by oxidative decomposition of the graft copolymer (A), and vinyl cyanide in a component derived from a graft chain. The content of the component derived from the monomer (hereinafter, “the content of the vinyl cyanide monomer unit in the component derived from the graft chain” may be simply expressed as “the content of the VCN unit” in some cases). The distribution has two or more peaks.
One or more of the two or more peaks is a peak having a peak top within the range of the VCN unit content of 0% by mass or more and less than 10% by mass (hereinafter referred to as “first peak”). Among the two or more peaks, one or more peaks different from the first peak have a peak having a peak top in the range where the VCN unit content is 10% by mass or more and less than 55% by mass (hereinafter, "Second peak").

In the thermoplastic resin composition of this embodiment, the peak top of the first peak contains less than 10% by mass of VCN units in order to obtain a preferable molding shrinkage ratio, good appearance of the weld part, and better jet black. The VCN unit content is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 3% by mass or less.
The peak top of the second peak is within the range of the VCN unit content of 10% by mass or more and less than 55% by mass from the viewpoint of obtaining impact resistance and a more excellent jet black.
The peak top of the second peak is preferably in the range of VCN unit content of 15% by mass or more and 50% by mass or less, and in the range of VCN unit content of 20% by mass or more and 45% by mass or less. Is more preferable, and it is more preferable that the VCN unit content is in the range of 25% by mass to 40% by mass.

In the thermoplastic resin composition of this embodiment, in order to obtain high impact resistance, excellent weld appearance, and jet black, the representative value of the VCN unit content shown by the first peak and the second peak are Difference from representative value (C) of VCN unit content shown = (| (second peak) − (first peak) |) is 10% by mass or more, and 15% by mass or more. Is more preferable, more preferably 22% by mass or more, and still more preferably 25% by mass or more.
Here, the representative value of the VCN unit content indicated by each of the first peak and the second peak is a weighted average obtained from an integrated value of the entire peak of each of the second peak and the second peak. Mean value.

FIG. 1 is a schematic diagram showing an example of the distribution of the content of vinyl cyanide monomer units (VCN units) in the graft chain-derived component obtained by oxidative decomposition of the graft copolymer (A). Show.
FIG. 1 shows a case where there is one each of the first peak and the second peak described above.
In FIG. 1, the horizontal axis indicates the VCN unit content (% by mass), and the vertical axis indicates the peak intensity. This peak intensity is an index indicating the abundance ratio of the components derived from the graft chain.
The distribution of the VCN unit content is obtained based on a chromatogram obtained by measuring a component derived from a graft chain obtained from a thermoplastic resin composition by a predetermined pretreatment described later by HPLC (high performance liquid chromatography). .
This distribution of the VCN unit content is obtained as the total amount (mass basis) of graft chains having the VCN unit content with respect to the VCN unit content. Details will be described later.
In the distribution of the VCN unit content, whether or not it is a peak is determined within the range of the noise level in an HPLC detector (for example, an ultraviolet-visible light detector manufactured by Shimadzu Corporation, trade name “SPD-20A”). It is determined by whether or not.
In addition, even when the distribution of the VCN unit content has a plurality of first peaks and / or a plurality of second peaks, the representative value of the VCN unit content indicated by the first peak is the entire first peak. The representative value of the VCN unit content indicated by the second peak means the weighted average value obtained from the integral value of the entire second peak.
In addition, when a plurality of peaks partially overlap (including the case where a shoulder peak exists), each of the overlapped peaks is considered to be a normal distribution, and each peak is obtained based on a peak obtained by separation processing. Determine the above items.

In general, when two or more types of monomers are graft-polymerized to the rubbery polymer, each monomer is charged for the purpose of narrowing the distribution of the monomer unit content in the graft chain. Graft polymerization is carried out at a constant ratio.
On the other hand, the content of each constituent unit in the component derived from the graft chain of the graft copolymer (A) by changing the charging ratio of each monomer to be graft polymerized continuously or stepwise, For example, the distribution of the VCN unit content can be controlled, and in this embodiment, in particular, the content of the VCN monomer unit has a peak top in the range of 0% by mass or more and less than 10% by mass. It is assumed that there is one peak and there is a second peak having a peak top in the range of 10% by mass or more and less than 55% by mass.
Specifically, the rubbery polymer is graft polymerized with a monomer other than the vinyl cyanide monomer, and then two or more monomers including the vinyl cyanide monomer are graft polymerized. Thus, there is a method for controlling the distribution of the content of VCN units, and this method is preferred.
In the distribution of the content of VCN units, each peak may be monodispersed or polydispersed.

The distribution of the VCN unit content in the graft copolymer (A) is measured by isolating the graft chain-derived component after oxidative decomposition of the graft copolymer (A), and then converting the graft chain-derived component by HPLC. It can be determined based on a chromatogram obtained by measurement.
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 the component derived from the graft chain in the present embodiment.

More specifically, for example, the distribution of the content of VCN units 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 VCN unit content is obtained 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)

  From the viewpoint of impact resistance, the graft ratio in the graft copolymer (A) contained in the thermoplastic resin composition of the present embodiment is preferably 40% or more and 260% or less, more preferably 75 to 220. %, More preferably 120 to 200%, still more preferably 150 to 200%.

The graft ratio of the graft copolymer (A) is defined by the ratio of the mass of the graft chain to the mass of the rubber polymer that is the trunk polymer.
The method for measuring the graft ratio is as follows.
The thermoplastic resin composition of the present embodiment is dissolved in chloroform and separated into a chloroform-soluble component and a chloroform-insoluble component.
At this time, the components insoluble in chloroform are a trunk polymer made of a rubbery polymer and a graft chain graft-polymerized to the trunk polymer, and include the graft copolymer (A) in this embodiment.
The component soluble in chloroform contains the continuous phase (B) described later.
By analyzing a component insoluble in chloroform with a Fourier transform infrared spectrophotometer (FT-IR), the composition ratio of the backbone polymer and the graft chain is obtained, and the graft ratio is obtained based on the result. Can do.

The content of the rubbery polymer in the graft copolymer (A) is preferably 27 to 72% by mass, and preferably 31 to 56% by mass based on the mass of the graft copolymer (A). More preferably, it is 35-46 mass%.
It is preferable from the viewpoint of impact resistance of the thermoplastic resin composition of the present embodiment that the content of the rubbery polymer in the graft copolymer (A) is not less than the above lower limit and not more than the above upper limit.
The content ratio of the rubbery polymer in the graft copolymer (A) is defined by the ratio of the trunk polymer to the graft copolymer (A). Therefore, it can obtain | require from the ratio of the trunk | polymer obtained by the measuring method of the said graft ratio.

From the viewpoint of impact resistance of the thermoplastic resin composition of the present embodiment, the reduced viscosity (ηsp / c) of the graft chain component contained in the graft copolymer (A) is 0.05 to 1.50 dL / The range of g is preferable. This reduced viscosity is more preferably 0.10 to 1.30 dL / g, and still more preferably 0.15 to 1.10 dL / g.
By setting the reduced viscosity of the graft chain to 0.05 dL / g or more, in the thermoplastic resin composition of the present embodiment, high impact resistance and strength can be obtained, and the reduced viscosity is 1.50 dL / g or less. As a result, practically sufficient formability can be obtained.
As described above, the reduced viscosity is obtained by oxidatively decomposing the graft copolymer (A), which is an unnecessary component in chloroform, and then reprecipitating with methanol, and adding 0.50 g of the precipitate component to 100 mL of 2-butanone. The solution dissolved in can be obtained by measuring the outflow time in a Cannon-Fenske type capillary under a temperature condition of 30 ° C. or lower.

In the graft copolymer (A) of this embodiment, the content ratio of vinyl cyanide monomer units in all monomer units (100% by mass) other than the rubbery polymer is the thermoplasticity of this embodiment. From the viewpoint of impact resistance, jet black and weld part appearance of the resin composition, it is preferably 8% by mass or more, and from the viewpoint of transparency, it is preferably less than 40% by mass, more preferably 10 to 35% by mass. %, More preferably 15 to 30% by mass.
Furthermore, the difference between the representative value of the VCN unit content indicated by the second peak and the content ratio of the vinyl cyanide monomer units in all the monomer units (100% by mass) other than the rubber polymer. Is preferably more than 0% by mass and less than 20% by mass, more preferably more than 4% by mass and less than 20% by mass, from the viewpoint of impact resistance of the thermoplastic resin composition of the present embodiment. Preferably it exceeds 4 mass% and is less than 15 mass%.

((A) Graft copolymer production method)
First, the method for producing the rubbery polymer contained in the graft copolymer (A) is not particularly limited, and examples thereof include a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and a bulk suspension weight. Methods such as combination method and emulsion polymerization can be used. Among these, a particle-like rubbery polymer is obtained, and the particle diameter can be easily controlled. Therefore, an emulsion polymerization method, a suspension polymerization method, and a bulk suspension polymerization method are preferably used.
When a rubbery polymer is produced by emulsion polymerization, a thermal decomposition type initiator that generates radicals by heat or a redox type initiator can be used.
Alternatively, a rubber polymer obtained by emulsion polymerization may be used, and a method of graft polymerization of a vinyl monomer may be used.
As the graft chain obtained here, those having good compatibility with the continuous phase (B) are preferable from the viewpoint of impact resistance of the thermoplastic resin composition of the present embodiment. If the compatibility is poor, the interface strength between the dispersed phase and the continuous phase is insufficient, and the required impact properties cannot be obtained.
In addition, after producing the particulate rubbery polymer, the above graft polymerization may be carried out continuously in the same reactor. After the rubbery polymer is isolated as a rubber latex, the graft polymerization is carried out again. May be.

For example, a polybutadiene latex obtained by emulsion polymerization is made from a group consisting of a vinyl cyanide monomer, and an aromatic vinyl monomer and an acrylic monomer copolymerizable with the vinyl cyanide monomer. The graft copolymer (A) is obtained by radical polymerization of at least one selected monomer.
Examples of the one or more monomers include styrene and acrylonitrile; styrene and methyl methacrylate; styrene; methyl methacrylate; and acrylonitrile.
In particular, when two or more monomers are graft-polymerized to the rubbery polymer, the graft ratio in the graft copolymer (A) can be changed by changing the charging ratio of each monomer continuously or stepwise. It is preferable to control the distribution of the chain monomer content.
Further, the rubbery polymer may be a polymer obtained by synthesis with a constant charge ratio of each monomer, or a polymer obtained by synthesis with varying the charge ratio of each monomer. It may be a polymer, or may be a polymer obtained by synthesis in which the charging ratio of each monomer is continuously changed.
The graft copolymer (A) is obtained by a known method such as emulsion polymerization, bulk polymerization, suspension polymerization, suspension bulk polymerization, or solution polymerization according to the production method described in JP-A-7-258501. Can be manufactured.

At this time, an ungrafted copolymer is automatically generated in addition to the graft copolymer (A).
In [Example] described later, the graft copolymer (A) is a grafted copolymer, but the graft unreacted components are the continuous phases (IB-1) to (IB-6). Thus, together with the graft copolymers (IA-1) to (IA-6), a “resin composition” is formed.

(Continuous phase (B))
The thermoplastic resin composition of the present embodiment contains a continuous phase (B) (hereinafter sometimes referred to as “continuous phase (B), (B) component, (B)”).
The resin component of the continuous phase (B) constituting the thermoplastic resin composition of the present embodiment preferably has a weight average molecular weight (Mw) in the range of 10,000 to 200,000. More preferably, it is in the range of 10,000 to 100,000, more preferably 10,000 to 60,000, still more preferably 20,000 to 50,000, and still more preferably 2,000 to 40,000.
By setting the weight average molecular weight of the resin component of the continuous phase (B) to 10,000 or more, the thermoplastic resin composition of the present embodiment can obtain a high appearance without impact resistance and MD (mold deposit). If it is 200,000 or less, the moldability is improved.
When using a mixture of two or more thermoplastic resins as the resin component of the continuous phase (B), it is preferable that the weight average molecular weight of the mixture of the resins is in the above range, a component having a low weight average molecular weight, A component having a high weight average molecular weight can also be mixed.
The measuring method of the weight average molecular weight of the resin component of a continuous phase (B) is as follows. That is, as described above, GPC (Gel Permeation Chromatography) (HLC-8220GPC, Tosoh Corporation) using the resin component of the continuous phase (B) extracted from the thermoplastic resin composition of the present embodiment with chloroform as a solvent. After obtaining a chromatogram by measurement according to (manufactured), it can be calculated from the retention time in the chromatogram, converted from a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample. The conditions are as follows.
Column: Column for ultra-high speed SEC (manufactured by Tosoh Corporation)
Sample concentration: 1 mg / ml (chloroform)
Detector; RI

In addition, it is preferable that a continuous phase (B) contains an amorphous thermoplastic resin from a viewpoint of maintaining high external appearance properties, such as impact resistance and jet black and a molding shrinkage rate.
Examples of the amorphous thermoplastic resin include a copolymer containing a vinyl cyanide monomer, a copolymer containing a methyl methacrylate monomer, a polycarbonate resin, an amorphous polyester, and an aromatic polyether resin. Can be mentioned.
These may be used alone or in combination of two or more.

Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile.
At least a part of the vinyl cyanide monomer unit may be copolymerized with one or more monomer units copolymerizable therewith.
The methyl methacrylate monomer may be copolymerized alone or with one or more monomer units copolymerizable therewith.

Monomers that can be copolymerized with a vinyl cyanide monomer or a methyl methacrylate monomer are not limited to the following, but include, for example, styrene, α-methylstyrene, o-methylstyrene, p- Aromatic vinyl monomers such as methyl styrene, ethyl styrene, p-t-butyl styrene, vinyl naphthalene; (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate Acrylic acid esters such as (meth) acrylic acid; N-substituted maleimide monomers such as N-phenylmaleimide and N-methylmaleimide; and glycidyl group-containing monomers such as glycidyl (meth) acrylate. .
These may be used individually by 1 type and may be used in combination of 2 or more type.
Among these, from the viewpoints of strength and heat resistance, styrene, α-methylstyrene, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, N-phenylmaleimide, and glycidyl methacrylate are preferable, and from the viewpoint of strength. Styrene is preferred, and N-phenylmaleimide is preferred from the viewpoint of heat resistance.
When the acrylate monomer is included, the content of the acrylate monomer is preferably 5% by mass or less when the component (B) is 100% by mass from the viewpoint of heat resistance. More preferably, it is 3 mass% or less.

  The polycarbonate resin is not limited to the following, and for example, any of aromatic homopolycarbonate and aromatic copolycarbonate can be used.

The amorphous polyester contains a diol residue and a dicarboxylic acid residue as constituent components.
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, the dicarboxylic acid residue can be derived from a dicarboxylic acid monomer or its related acid halide, ester, salt, anhydride, or mixtures thereof.
Examples of the diol residue constituting the amorphous polyester include, but are not limited to, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, 1,4-cyclohexanedimethanol (CHDM), 2,2,4,4-tetramethyl-1,3- Cyclobutanediol (TMCD) or mixtures thereof.
The dicarboxylic acid residue constituting the amorphous polyester is preferably an aromatic dicarboxylic acid residue. For example, terephthalic acid, a mixture of terephthalic acid and its ester, isophthalic acid, isophthalic acid and its ester, A mixture is mentioned.

  Examples of the aromatic polyether resin include, but are not limited to, aromatic polyetherimide, aromatic polyether ketone, and aromatic polyether sulfone.

As the resin component of the continuous phase (B) constituting the thermoplastic resin composition of the present embodiment, among the above-mentioned resins, two kinds of blends preferably made of polycarbonate and amorphous polyester, vinyl cyanide-based single component are used. Three kinds of blends of a copolymer containing a monomer, polycarbonate, and amorphous polyester can be preferably used.
More preferably, a blend of three kinds of styrene-acrylonitrile copolymer, polycarbonate, and amorphous polyester is more preferably used from the viewpoint of impact resistance, heat resistance, jet black, and weld appearance.

The styrene-acrylonitrile copolymer as the resin component of the continuous phase (B) preferably has a vinyl cyanide monomer content of 15 to 55% by mass relative to 100% by mass of the styrene-acrylonitrile copolymer. More preferably, it is 20-50 mass%, More preferably, it is 20-45 mass%, More preferably, it is 30-40 mass%.
By setting the content of the vinyl cyanide monomer in the styrene-acrylonitrile copolymer within the above range, it is possible to obtain excellent jet black and weld part appearance in the thermoplastic resin composition and the molded body of the present embodiment. it can.
In the case where an acrylic ester monomer such as butyl acrylate or butyl methacrylate is included as a monomer copolymerizable with the other vinyl cyanide monomer or methyl methacrylate monomer, the content thereof Is preferably a small amount from the viewpoint of heat resistance.

  The polycarbonate resin is not particularly limited as long as it satisfies the weight average molecular weight required for the resin component of the continuous phase (B) described above.

As the non-crystalline polyester, the diol residue has a 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residue of 10 when the total mol% of the diol component is 100 mol%. -70 mol%, preferably 15-65 mol%, more preferably 20-50 mol%, still more preferably 30-45 mol%, 30-90 mol% 1,4-cyclohexanedimethanol (CHDM) residue , Preferably 35 to 85 mol%, more preferably 50 to 80 mol%, still more preferably 55 to 70 mol%.
Furthermore, the dicarboxylic acid residue is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, still more preferably 90 to 100 mol, when the total mol% of the dicarboxylic acid is 100 mol%. The aromatic dicarboxylic acid residue having a mol% of 20 or less carbon atoms is preferably 0 to 30 mol%, more preferably 0 to 20 mol%, still more preferably 0 to 10 mol%, and an aliphatic dicarboxylic acid having 16 or less carbon atoms. The residue is preferably contained in an amount of 0 to 10 mol%, more preferably 0 to 5 mol%, still more preferably 0 to 1 mol%. Thereby, in the thermoplastic resin composition and molded object of this embodiment, high heat resistance and high impact resistance can be obtained. The diol component may be either a cis type or a trans type, and a mixture thereof can also be used.
The resin component of the continuous phase (B) in this embodiment preferably has an aromatic polycarbonate residue and a 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residue. When measured with a resonance apparatus ( ¹ H-NMR), the proton peak (1) in the benzene ring in the aromatic polycarbonate residue (present between 7.1 to 7.3 ppm) and 2,2,4 , 4-tetramethyl-1,3-cyclobutanediol (TMCD) residue in the proton peak (2) of the methyl group (present between 1.28 and 1.34 ppm) ((1) / ( 2)) is preferably in the range of 2.0 to 10.0. More preferably, it is in the range of 2.5 to 8.0. Even more preferably, it is in the range of 3.0 to 5.5.
(1) / (2) are aromatic polycarbonate in the continuous phase (B) and 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residue and 1,4 as diol residues. -Cyclohexanedimethanol (CHDM), showing the blending ratio of amorphous polyester having terephthalic acid residue as dicarboxylic acid residue, and in the thermoplastic resin composition and molded product of this embodiment, A thing excellent in heat resistance, jet black, and weld part appearance can be obtained.

The measuring method of (1) / (2) in the resin component of the continuous phase (B) is as follows.
The continuous phase (B) was used as a chloroform solvent, and the spectrum was measured by ¹ H-NMR (JOEL-ECA500, manufactured by JEOL Ltd.), and integrated values of (1) and (2) were obtained, from which (1) / (2) can be calculated.
The conditions are as follows.
Observation nucleus: 1H (500MHz)
Number of scans: 500 Measurement temperature: Room temperature Sample: 75 mg (chloroform dissolution concentration: 100 mg / ml)

(Method for producing continuous phase (B))
The continuous phase (B) may be formed of one type of thermoplastic resin, or may be a blend of two or more types.
The blend obtained by combining two or more types means a product kneaded and melted in an extruder in which the cylinder temperature is set to be equal to or higher than the melting temperature of the thermoplastic resin contained in the continuous phase (B).

Below, the manufacturing method of the thermoplastic resin which forms a continuous phase (B) is demonstrated.
The copolymer containing the vinyl cyanide monomer is not particularly limited, and examples thereof include a bulk polymerization method, a solution polymerization method, a suspension polymerization method, a bulk suspension polymerization method, and an emulsion polymerization method. In order to produce a copolymer of two or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers and acrylic monomers, it is produced by radical polymerization. Is preferred. Moreover, the copolymer containing a vinyl cyanide monomer may be produced together with the production of the graft copolymer (A). For example, when the graft copolymer (A) is produced, the monomer itself added for graft polymerization to the rubber polymer is polymerized to form a copolymer containing a vinyl cyanide monomer. May be.
The polycarbonate resin is a phosgene method in which phosgene is blown into a bifunctional phenolic compound in the presence of an alkali metal hydroxide and a solvent, or transesterification in which a bifunctional phenolic compound and diethyl carbonate are transesterified in the presence of a catalyst. Various methods such as a method, a method of obtaining diethyl carbonate from carbon dioxide and alcohol, and a method of obtaining diethyl carbonate by reacting diethyl carbonate with an aromatic hydroxy compound can be applied.
Here, the bifunctional phenol-based compound is not limited to the following, and examples thereof include 2,2′-bis (4-hydroxyphenyl) propane and 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, a compound having a structure in which 2,2′-bis (4-hydroxyphenyl) propane [bisphenol A] or the like is used as a base and a functional group capable of imparting hardness is introduced is preferable.
The said bifunctional phenol type compound may be used individually by 1 type, and may use 2 or more types together. Moreover, the aromatic polycarbonate manufactured by the said various methods may be used individually by 1 type, and may use 2 or more types together.

(Other resins)
The thermoplastic resin composition according to the present embodiment is not limited to the dispersed phase and the continuous phase (B) made of the above-described graft copolymer (A), and may be other as necessary as long as the effects of the present invention are not impaired. The resin may be contained.
The other resin is preferably in a range not exceeding 25% by mass, more preferably 10% by mass with respect to 100% by mass in total of the dispersed phase composed of the graft copolymer (A) and the continuous phase (B). Hereinafter, it is more preferably 5% by mass or less, and still more preferably 3% by mass or less.
Examples of other resins include, but are not limited to, crystalline polyesters such as polybutylene terephthalate and polytrimethylene terephthalate, and amorphous polyesters in which a diol residue has a cyclo ring.

(Content of (A) component and (B) component)
The contents of the graft copolymer (A) and the continuous phase (B), which are the above-described dispersed phases, in the thermoplastic resin composition of the present embodiment will be described below.
When the total of the graft copolymer (A) and the continuous phase (B) as the dispersed phase is 100% by mass, the content of the graft copolymer (A) is preferably 10 to 50% by mass, more preferably Is 10-40 mass%, More preferably, it is 15-35 mass%.
By setting the content ratio of the graft copolymer (A) to 10% by mass or more, high impact resistance can be obtained. On the other hand, high heat resistance is obtained by making the content rate of a graft copolymer (A) 50 mass% or less.
In addition, when a blend of amorphous polyester, polycarbonate and other resin is used as the resin component of the continuous phase (B), when the entire continuous phase (B) is 100% by mass, the content ratio of the polycarbonate is The content of the amorphous polyester is preferably 20% by mass or more, more preferably 20% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. Preferably it is 40 mass% or more, More preferably, it is 50 mass% or more. By setting it as this content rate, in the thermoplastic resin composition of this embodiment, the outstanding impact resistance, heat resistance, jet black, and a weld part external appearance are obtained.
Furthermore, the composition of constituent units other than the rubbery polymer in the graft copolymer (A) (meaning the type and content of constituent units; the same shall apply hereinafter) and the composition of the continuous phase (B). When the compatibility is increased by controlling, the dispersion state of the rubbery polymer can be further improved, and the balance of the impact resistance, jet black, weld part appearance, and molding shrinkage ratio of the molded body can be further improved. Can do. In order to increase the compatibility, for example, the type of the structural unit other than the rubbery polymer in the graft copolymer (A) and the type of the structural unit of the continuous phase (B) may be the same, Although the method of making the content rate of a structural unit close, and making each compatibility parameter close is mentioned, The method of making it the same thing is especially preferable.

(Additive)
The thermoplastic resin composition of the present embodiment may contain various additives as necessary within the range not impairing the effects of the present invention, in addition to the components (A) and (B) described above. Good.
Examples of the additive include plasticizers, lubricants, sliding agents, colorants, antistatic agents, various peroxides, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, and the like.
The content of these additives is preferably in a range not exceeding 10% by mass with respect to the thermoplastic resin composition of the present embodiment. More preferably, it is 5 mass% or less.
In order to obtain a high-grade appearance in the thermoplastic resin composition of the present embodiment, it is preferable to use a dye as a colorant, and the dye is not limited to the following, for example, a nitroso dye , Nitro dye, azo dye, stilbene azo dye, ketoimine dye, triphenylmethane dye, xanthene dye, acridine dye, quinoline dye, methine / polymethine dye, thiazole dye, indamine / indophenol dye, azine dye, oxazine dye, thiazine dye , Sulfur dyes, aminoketone / oxyketone dyes, anthraquinone dyes, indigoid dyes, and phthalocyanine dyes. These dyes are preferably used in combination of several kinds, for example, preferably two or more kinds selected from red, blue, purple, yellow and green are used in combination.
Furthermore, for the purpose of imparting excellent appearance, the molded article of the present embodiment preferably uses, for example, an inorganic pigment, an organic pigment, and a metallic pigment (including a pearl pigment) together with a dye.
Examples of the inorganic pigment include, but are not limited to, titanium oxide, carbon black, titanium yellow, iron oxide pigments, ultramarine blue, cobalt blue, chromium oxide, spinel green, lead chromate pigments, cadmium. Based pigments.
Examples of the organic pigment include, but are not limited to, azo pigments such as azo lake pigments, benzimidazolone pigments, diarylide pigments, and condensed azo pigments, phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, Examples thereof include condensed polycyclic pigments such as indolinone pigments, quinophthalone pigments, quinacridone pigments, perylene pigments, anthraquinone pigments, perinone pigments, and dioxazine violet.
Examples of the metallic pigment include, but are not limited to, for example, a flake-like aluminum metallic pigment, a spherical aluminum pigment used for improving the weld appearance, and a mica for a pearl metallic pigment. Examples include powders and other polyhedral particles of inorganic substances such as glass coated with metal by plating or sputtering.

[Glass transition point of the thermoplastic resin composition of the present embodiment]
The thermoplastic resin composition of the present embodiment preferably has one glass transition point between at least 120 and 140 ° C.
The thermoplastic resin composition of the present embodiment may be a single thermoplastic resin having a glass transition point that satisfies the above range, or may be one or more other thermoplastic resins that do not satisfy the above range. You may use resin which controlled the glass transition point to the said range by making it compatible with resin.
Moreover, the thermoplastic resin composition in this embodiment has one or more glass transition points at less than 20 ° C. and 20 ° C. or more, respectively, and the glass transition points of 20 ° C. or more are both 100 ° C. or more. Moreover, it is preferable that the glass transition point of 20 degreeC or more exists in the range of 100 degreeC-150 degreeC, respectively, and there exists one or more glass transition points between 120-140 degreeC.
Furthermore, it has two glass transition points of 20 degreeC or more, and it is more preferable to have one between 120-140 degreeC and one between 100-115 degreeC.
The glass transition point of less than 20 ° C is preferably -60 ° C or less, more preferably -80 ° C or less.
By making the glass transition point of the thermoplastic resin composition of this embodiment into the said range, in this embodiment, the high heat resistance and impact resistance, and the jet black appearance which was excellent can be obtained.

The measuring method of the glass transition point of the thermoplastic resin composition of this embodiment is as follows.
A sample obtained by predrying the thermoplastic resin composition of the present embodiment is put into a measurement pan of DSC (Differential Scanning Calorimeter) (DSC8500, manufactured by PerkinElmer), and measurement is performed under the following conditions. The glass transition point is obtained from the obtained 2ndScan chart.
In addition, the glass transition point in the present embodiment indicates an intermediate glass transition temperature.
Temperature increase / decrease rate: 10 ° C / min
Temperature condition: Temperature rise from -120 ° C to 180 ° C (1stScan)
Temperature drop from 180 ° C to -120 ° C (3min hold)
Temperature rise from -120 ° C to 180 ° C (2ndScan)
Atmosphere: In a nitrogen stream (50 ml / min)
Measurement sample: 10 mg

[Method for producing thermoplastic resin composition]
The manufacturing method of the thermoplastic resin composition of this embodiment is demonstrated below.
The thermoplastic resin composition of the present embodiment is not limited to the following, for example, an open roll, an intelligent mixer, an internal mixer, a kneader, a continuous kneader with a twin-screw rotor, an extruder, etc. It can be produced by a melt kneading method using a machine. As the extruder, either a single screw or a twin screw extruder can be used.
Examples of the method for producing the thermoplastic resin composition of the present embodiment are shown in the following (1) to (6). 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 equipped with an upstream supply port and a downstream supply port, supply component (B) from the upstream supply port, melt knead, and then supply component (A) from the downstream supply port Melting and kneading,
(3) Using a twin-screw extruder equipped with an upstream supply port and a downstream supply port, supply a part of the components (A) and (B) from the upstream supply port, melt knead, and then supply the downstream side A method of melt-kneading the remainder of the component (B) from the mouth,
(4) First, the component (B) is supplied to a twin-screw extruder and melt-kneaded, and then the component (A) and the once melt-kneaded component (B) are melt-kneaded in a single-screw extruder. Method,
(5) First, the component (B) is supplied to a twin-screw extruder and melt-kneaded, and then once melt-kneaded from the upstream supply port using a twin-screw extruder provided with an upstream supply port and a downstream supply port. After supplying the component (B) and melt-kneading again, then supplying the component (A) from the downstream supply port and melt-kneading,
(6) First, after the component (B) is supplied to the twin screw extruder and melt-kneaded, a twin screw extruder further having an upstream supply port and a downstream supply port is used, and from the upstream supply port (A) A method of supplying a part of the component and the component (B) once melt-kneaded and melt-kneading again, and then supplying the remainder of the component (B) from the downstream supply port and melt-kneading,
Etc.
From the viewpoint of impact resistance of the thermoplastic resin composition of the present embodiment, the methods (1), (2), and (3) are more preferable.
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 of the sea island form mentioned above can be obtained, and the effect of this invention can be acquired reliably.
The thermoplastic resin composition of the present embodiment has the conflicting characteristics of high heat resistance and impact resistance, jet black, weld part appearance, and molding shrinkage ratio 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 using the thermoplastic resin composition described above.
As a method for producing a molded article, known methods such as injection molding, sheet molding, vacuum molding, blow molding, injection blow molding, inflation molding, T-die molding, press molding, extrusion molding, foam molding, molding by casting method, etc. Can be applied.
The thermoplastic resin composition of the present embodiment is characterized in that a molded body having a high-quality appearance can be produced only by molding without painting, and is not a form of the molded body of the present embodiment. Examples include a molded body of paint.
In particular, a molded article having a good appearance can be obtained by an injection molding method.
By using an injection molding machine, for example, the injection molded body has a cylinder temperature = 240 ° C. to 320 ° C., and a general injection molding method or heat and cool molding in which the mold repeats heating / cooling is performed. Although obtained, heat and cool molding is more preferable in order to obtain an injection-molded body having a high appearance.
The molded body of this embodiment is preferably molded at a mold temperature of 100 ° C. or higher during molding. Thereby, a molded article having good appearance characteristics can be obtained. The mold temperature during molding is preferably 100 ° C to 180 ° C, more preferably 120 to 180 ° C, and further preferably 140 to 180 ° C. The mold temperature at the time of heat and cool molding is as described above at the time of heating, and preferably 80 ° C. to 50 ° C. at the time of 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 can be, and the flatness of the rubber polymer on the surface of the molded body can be controlled by adjusting the injection pressure. A high-quality molded article can be obtained.

[Use]
The molded body containing the thermoplastic resin composition of the present embodiment is unpainted, has various types of housing materials that have high heat resistance and impact resistance, high-quality appearance only by molding, and requires design and impact resistance. It is suitable for automobile interior materials, various automobile interior parts, and the like.
A casing, which is a type of molded product containing the thermoplastic resin composition of the present embodiment, is an exterior (cover) of equipment having some function such as machinery or electricity, and is an exterior attached to those equipment. Also good.
Examples of devices in which the casing is used include home appliances, OA devices, housing equipment, and vehicle equipment.
Home appliances include, for example, vacuum cleaners, washing machines, refrigerators, microwave ovens, rice cookers, electric pots, telephones, coffee makers, liquid crystal and plasma televisions, visual recorders, audio stereos, mobile phones including smartphones, stationary types Examples include game machines, portable game machines, and remote controls.
Examples of the OA device include a composite device such as a fax machine and a copy machine, a liquid crystal monitor, a printer, and a personal computer.
Examples of the housing equipment include a system kitchen, a wash basin, and a system bath.
Examples of the vehicle equipment include an interior garnish cover of an automobile, specifically, a shift lever indicator cover, a door handle frame, a power window switch frame, a center cluster, a car stereo, a car navigation frame, and a center pillar cover.
The shape and size of the molded body containing the thermoplastic resin composition of the present embodiment are not particularly limited. For example, the shape has a three-dimensional thickness from a thin shape such as a plate shape. Examples of the shape include a polygonal shape with square corners and a shape with many curved surfaces. The size ranges from a small one included in the range of 10 × 10 × 10 mm to a larger one included in the range of 300 × 100 × 100 mm.

  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]
(Production of Resin Compositions I-1 to I-6)
Resin compositions I-1 to I-6 as raw materials for the thermoplastic resin compositions of Examples and Comparative Examples described below were produced.
Resin compositions I-1 to I-6 were produced using rubber latex produced as follows.
The resin compositions I-1 to I-6 are not grafted with a graft copolymer (A) in which a predetermined monomer unit is graft-polymerized on a rubber latex (rubbery polymer) as described later. The monomer and the polymer which became the continuous phase (B) are included.
<Manufacture of rubber latex to become graft copolymer (A) which is dispersed phase; acrylonitrile / butadiene / styrene copolymer (ABS)>
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.

(Production of Resin Composition I-1)
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. (Hereinafter, “Initial Addition” in Table 1) The temperature was then 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 (hereinafter referred to as “first stage addition” in Table 1).
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 (hereinafter referred to as “second stage addition” in Table 1).
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. (Indicated as “shot” in Table 1). 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 resin composition (I-1).
This resin composition (I-1) has a dispersed phase composed of the graft copolymer (IA-1) and a thermoplastic resin (IB-1) which is a continuous phase, and is a dispersed phase. The content of the graft copolymer (IA-1) was 79.6% by mass, and the content of the thermoplastic resin (IB-1) as a continuous phase was 20.4% by mass.

(Production of Resin Compositions (I-2) to (I-6))
According to the composition shown in Table 1 below, resin conditions (I-2) to (I-6) were produced in the same manner as in the resin composition (I-1) described above.
Table 1 shows the material and charge ratio of the resin composition, the content of chloroform insolubles, the content of chloroform solubles, and the reduced viscosity of chloroform solubles.
In the “third stage addition” in Table 1, each material was added by the same operation as the second stage addition after the second stage addition and before the shot.

The thermoplastic resin (B-7) used as the raw material of the continuous phase of the thermoplastic resin composition of the Example and comparative example which are mentioned later was manufactured as follows.
(Production of thermoplastic resin (B-7) as continuous phase)
Peroxidation having 38.5 parts by weight of acrylonitrile, 31.0 parts by weight of styrene, 30.5 parts by weight of ethylbenzene, 0.3 part by weight of α-methylstyrene dimer, and 7 repeating units represented by the following formula (1) A monomer mixture consisting of 1.05 parts by weight (10-hour half-life: 63.5 ° C.) was prepared in a state where it was not brought into contact with air, and was continuously fed to a reactor equipped with a stirrer and polymerized. .
The polymerization temperature was adjusted to 120 ° C.
The stirring rotation speed of the stirrer was set to 95 rotations and sufficiently mixed, and the P / V value was 4.0 kw / m ³ . The average residence time was 4.0 hours.
The polymerization mixture having a polymerization rate of 55% and a polymer concentration of 50% by mass obtained as described above was continuously withdrawn from the reactor and transferred to the first separation tank.
In the first separation tank, the polymerization mixture is heated to 160 ° C. in a heat exchanger, devolatilized at a degree of vacuum of 60 Torr, and the polymer concentration in the polymerization mixture is adjusted to 65% by mass. The product was discharged from the tank and transferred to the second separation tank.
In the second separation tank, the polymerization mixture is heated to 260 ° C. in a heat exchanger and devolatilized at a degree of vacuum of 32 Torr. The content ratio of volatile components in the polymerization mixture is 0.7 mass%, and the polymer concentration is After adjusting to 99.4 mass%, it discharged | emitted and the pellet-shaped thermoplastic resin (B-7) was obtained.
The composition ratio of each monomer unit in the thermoplastic resin (B-7) is a Fourier transform infrared spectrophotometer (FT-IR, manufactured by JASCO Corporation, product number: FT / IR-7000, the same applies hereinafter). As a result of composition analysis using acrylonitrile, the acrylonitrile unit was 39.5% by mass and the styrene unit was 60.5% by mass.

... (1)

(Thermoplastic resin (B-8) as a continuous phase)
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 having 20 or less carbon atoms Residue 100 mol%) ”manufactured by EASTMAN was used.

(Thermoplastic resin (B-9) that becomes the continuous phase)
Product 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 An 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.

(Thermoplastic resin (B-10) as a continuous phase)
The trade name “WONDERLITE (registered trademark) PC-110 (weight average molecular weight; 42,000)” manufactured by Kimisha Co., Ltd. was used.
The weight average molecular weight was calculated using GPC by dissolving in chloroform and using monodisperse polystyrene as a standard sample.

[Physical property evaluation method]
The evaluation method of physical properties is shown below.
<(1) Measurement of Notched Charpy Impact Strength>
Using the thermoplastic resin compositions of Examples 1 to 7 and Comparative Examples 1 to 5, which will be described later, and using an injection molding machine, the cylinder temperature is 250 ° C. and the mold temperature is 60 ° C. A specimen A type (length 150 mm, narrow portion width 10.0 mm) was molded.
A test piece having a length of 8 cm × width of 1 cm and a thickness of 4 mm was cut out and evaluated.
An average value of 10 measured values was calculated and used as a notched Charpy impact strength.
Notch Charpy impact strength of 35 kJ / m ² or more, and can be used practically without problems in home appliances, game machines, automobile interior materials, etc., notch Charpy impact strength of less than 35 kJ / m ² is not possible, 35 kJ / m ² or more was evaluated as excellent.

<(2) Measurement of deflection temperature under load (DTUL)>
Using the thermoplastic resin compositions of Examples 1 to 7 and Comparative Examples 1 to 5, which will be described later, with an injection molding machine, under conditions of cylinder temperature = 250 ° C. and mold temperature = 60 ° 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 addition average value of the two measured values was calculated and used as the deflection temperature under load.
Since the deflection temperature under load is 90 ° C. or higher and can be used practically without problems in household appliances, game machines, automobile interior materials, etc., those with a deflection temperature under 90 ° C. are not possible, and 90 ° C. or higher is evaluated as excellent.

<(3) 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 7 and Comparative Examples 1 to 5, which will be described later, and then a cylinder was formed 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 temperature = 270 ° C. and a mold temperature = 70 ° 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.
The smaller the value, the lower the brightness and the darker black, meaning that a high-grade appearance was obtained, and because it can hold a high-grade appearance at home appliances, game machines, automobile interior materials, etc. at 3.0 or less, Those whose jet black exceeded 3.0 were evaluated as unacceptable, and those below 3.0 were evaluated as excellent.
Since the judgment value of jet black is such that it can be judged by human eyes even if the difference is 0.1, for example, L * is 3.5 and L * is 2.5. It was possible to judge that this difference of 0.5 is a great effect.

<(4) Measurement of molding shrinkage>
Molding shrinkage was evaluated as an index of dimensional stability.
After mixing 1% by mass of each color (red, yellow, blue, and green) dyes into the thermoplastic resin compositions of Examples 1 to 7 and Comparative Examples 1 to 5, which will be described later, 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 270 ° C. and mold temperature = 70 ° 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.
The vertical and horizontal dimensions of the obtained flat plate were measured, and the molding shrinkage was calculated from the mold dimensions.
The average value of the three measured values was calculated and used as the molding shrinkage rate.
When the molding shrinkage is less than 0.5%, the dimensional stability becomes better.
Mold shrinkage of 0.5% or more was impossible, and less than 0.5% was considered excellent.

<(5) Evaluation of appearance of weld part>
As an index of high-quality appearance, the appearance of the weld portion was evaluated.
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 7 and Comparative Examples 1 to 5, which will be described later, and then a cylinder was formed using an injection molding machine. The temperature is 280 ° C., the mold temperature is 130 ° C. (during heating) / 80 ° C. (during cooling), heat and cool molding is performed, and a box-type thin-walled shape with double-point gates of length mm × width mm × thickness 2 mm. The molded product was injection molded.
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.
The weld part of the obtained molded body was visually observed and judged based on the following criteria.
○: Weld line is not visible.
Δ: Weld line is slightly faintly observed.
X: Weld line is clearly observed.

<(6) (Peak 1)-(Peak 2)>
The thermoplastic resin compositions of Examples 1 to 7 and Comparative Examples 1 to 5, which will be described later, were dissolved in chloroform and separated into a chloroform-soluble component and a chloroform-insoluble component.
8. To this chloroform-insoluble matter (0.5 g), osmium tetroxide (0.0046 g), t-butyl alcohol (10.7 g), organic peroxide (“Perbutyl H-69” (trade name of NOF Corporation) 2g) was added and refluxed for 30 minutes, then concentrated by removing the solvent and dissolved in chloroform.
This was added to methanol to obtain a precipitate, which was separated and dried. This was weighed (0.03 g), dissolved in tetrahydrofuran (10 mL), and used as 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 A calibration curve was created for the relationship.
After the measurement sample was measured by HPLC to obtain a chromatogram, the distribution of VCN unit content was 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)
In the obtained VCN distribution map, the difference between the representative value of the VCN unit content indicated by the first peak and the representative value of the VCN unit content indicated by the second peak = (| (first peak) − ( The second peak) |) was calculated.
Here, the representative value of the VCN unit content indicated by each of the first peak and the second peak is a weighted average obtained from an integrated value of the entire peak of each of the second peak and the second peak. Mean value.

<(7) Glass transition point>
Samples obtained by predrying the thermoplastic resin compositions of Examples 1 to 7 and Comparative Examples 1 to 5, which will be described later, were put into a measurement pan of DSC (Differential Scanning Calorimeter) (DSC8500, manufactured by PerkinElmer), and the following conditions were satisfied. And measured.
The glass transition point was obtained from the obtained 2ndScan chart.
In addition, the glass transition point in the present embodiment indicates an intermediate glass transition temperature.
Temperature increase / decrease rate: 10 ° C / min
Temperature condition: Temperature rise from -120 ° C to 180 ° C (1stScan)
Temperature drop from 180 ° C to -120 ° C (3min hold)
Temperature rise from -120 ° C to 180 ° C (2ndScan)
Atmosphere: In a nitrogen stream (50 ml / min)
Measurement sample: 10 mg

[Example 1]
A thermoplastic resin composition was produced as follows using a twin-screw extruder (“TEM-58SS” manufactured by Toshiba Machine).
The supply port is one on the upstream side, and the resin composition (I-1), the thermoplastic resins (B-7), (B-8), and (B-10) were sufficiently dried to remove moisture. ).
The cylinder temperature of the extruder at that time was set to 250 ° 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.
The types and blending ratios of raw materials at this time are shown in Table 2 below.
Table 2 below shows the results of each evaluation described above using the pellets of the obtained thermoplastic resin composition.

[Examples 2 to 5, Comparative Example 1]
In place of the resin composition (I-1), the material and preparation ratio, and the content of chloroform insolubles, the content of chloroform solubles, the reduced viscosity of chloroform solubles, and the number of additions were changed (I-2) ~ (I-6) was used.
Other conditions were the same as in Example 1 to obtain pellets of a thermoplastic resin composition.
Table 2 below shows the results of the above evaluations using the obtained pellets of the thermoplastic resin composition.

Example 6
(B-7) A pellet was obtained in the same manner as in Example 2 except that the component was not added and the blending ratio was changed.
Table 2 shows the results of the above evaluations using the obtained pellets.

Example 7
The total amount of components (B-7), (B-8), and (B-10) and the charge amount of (I-2) with respect to the thermoplastic resin composition were changed.
Other conditions were the same as in Example 2 to obtain pellets.
Table 2 shows the results of the above evaluations using the obtained pellets.

[Comparative Examples 2 to 5]
The kind and the mixture ratio of continuous phase (B-8), (B-9), (B-10) were changed.
Other conditions were the same as in Example 1 to obtain pellets.
Table 2 shows the types and mixing ratios of the raw materials at this time.
Table 2 shows the results of the above evaluations using the obtained pellets.

The meanings of the words in Table 2 are shown.
In the graft copolymer (IA-1), “graft 75” means that the graft ratio of the component (IA-1) is 75%.
The same applies to the graft copolymers (IA-2) to (IA-6).
“VCN34” in the graft copolymer (IA-1) means the ratio of acrylonitrile in the total amount of styrene and acrylonitrile.
The same applies to the graft copolymers (IA-2) to (IA-6).
The “two peaks” of the graft copolymer (IA-4) means that the second peak has two peak tops.
“VCN24” in (IB-1) is an acrylonitrile / styrene copolymer and means containing 24% by mass of acrylonitrile units.
The same applies to (IB-2) to (IB-6) and (B-7).

  In Examples 1 to 7, a molded product having a good balance of all the characteristics of impact resistance, heat resistance, transparency, dimensional stability (molding shrinkage) and high-quality appearance (jet black, weld part appearance) is obtained. It was.

The thermoplastic resin composition of the present embodiment can be suitably used for various molded articles.
For example, it has industrial applicability as various housing materials and automobile interior parts that require designability, impact resistance, and heat resistance.

Claims (13)

A dispersed phase comprising a graft copolymer (A);
Continuous phase (B);
Including,
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 has a vinyl cyanide monomer unit and one or more monomer units copolymerizable with the vinyl cyanide monomer,
The distribution of the content ratio of the vinyl cyanide monomer unit in the component derived from the graft chain obtained through oxidative decomposition of the graft copolymer (A) has two or more peaks,
One or more of the two or more peaks have a content of the vinyl cyanide monomer unit of 0.
A first peak having a peak top in a range of not less than 10% by mass and less than 10% by mass,
One or more of the peaks different from the first peak is a second peak having a peak top in a range where the content of the vinyl cyanide monomer unit is 10% by mass or more and less than 55% by mass,
When 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 shown by the first peak and the representative value of the content shown by the second peak is 10% by mass or more,
Each having one or more glass transition points at less than 20 ° C and above 20 ° C,
The glass transition point of the 20 ° C. or higher is 100 ° C. or higher, and the thermoplastic resin composition has one or more glass transition points in the range of 120 to 140 ° C. The thermoplastic resin composition is
Each having one or more glass transition points at less than 20 ° C and above 20 ° C,
The glass transition point of 20 ° C. or higher is in the range of 100 ° C. to 150 ° C., and 12
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has one or more glass transition points within a range of 0 to 140 ° C. The thermoplastic resin composition is
Each having one or more glass transition points at less than 20 ° C and above 20 ° C,
The glass transition point of 20 ° C. or higher is two, one in the range of 120 to 140 ° C., 10
The thermoplastic resin composition of Claim 1 or 2 which has one within the range of 0-115 degreeC. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the continuous phase (B) contains an amorphous thermoplastic resin. The continuous phase (B) contains at least a vinyl cyanide monomer.
The thermoplastic resin composition according to any one of the above. The continuous phase (B) contains an aromatic polycarbonate residue and a 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residue. The thermoplastic resin composition according to Item. The graft ratio of the graft copolymer (A) is 150 to 200%.
The thermoplastic resin composition according to any one of the above. Of the content distribution of the component derived from the vinyl cyanide monomer in the component derived from the graft chain obtained through oxidative decomposition of the graft copolymer (A),
The thermoplastic resin according to any one of claims 1 to 7, wherein a peak top of the second peak is within a range of vinyl cyanide monomer unit content of 25% by mass or more and 40% by mass or less. Composition. The thermoplastic resin composition according to any one of claims 1 to 8, further comprising a colorant.   The molded object containing the thermoplastic resin composition as described in any one of Claims 1 thru | or 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 interior material. A method for producing a molded body according to any one of claims 10 to 12,
The manufacturing method of a molded object which has the process of shape | molding the metal mold | die temperature at the time of shaping | molding as 120 degreeC or more.