JP2016003309A - Thermoplastic resin composition and molded product of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having excellent impact resistance and transparency.SOLUTION: The thermoplastic resin composition comprises 10 to 60 mass% of a graft copolymer (A) and 90 to 40 mass% of a thermoplastic resin (B) comprising a polymer containing vinyl cyanide monomer units. The (A) comprises a main chain consisting of a rubber-like polymer, and grafted chains, where the grafted chains comprise vinyl cyanide monomer units and monomer units of one or more kinds. In a component derived from the grafted chains, distribution of content of the vinyl cyanide monomer units has two or more peaks, namely a first peak having a peak top in a range of 0 to less than 10 mass% and a second peak having a peak top in a range of 10 to less than 55 mass%. A difference between representative values of the first peak and the second peak is 10 mass% or more. Further, a ratio "half-value width/peak height" of a loss modulus of the (A) is 0.1 to less than 0.25.

Description

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

  Thermoplastic resins imparted with impact resistance are widely used for home appliances, game machines, automobile interior materials, and the like. Conventionally, there are cases where a product is subjected to a full coating process or a partial coating process for the purpose of imparting appearance to a resin product and preventing the product from being damaged. However, these coating treatments are liable to cause a decrease in production yield due to poor coating, and further, there is a problem that it is unfavorable in terms of environment due to the recent trend of suppressing VOC emissions. Therefore, in addition to performance such as impact resistance, a resin that has both excellent appearance and scratch resistance without being subjected to a coating treatment is required for the resin used in the above-described products.

  As a technique for solving this problem, a method of obtaining high definition and scratch resistance by limiting the linear expansion coefficient of a rubber component to a specific range is known (for example, see Patent Document 1). On the other hand, attempts to obtain high color development and scratch resistance by limiting the graft ratio of the graft copolymer to a specific range have been proposed (for example, see Patent Document 2).

International Publication No. 2012/043790 JP 2013-18950 A

However, recently, a resin product having a further high-grade appearance, particularly transparency, is required, and in addition, a resin product excellent in impact resistance is required.
This invention is made | formed in view of the said situation, and it aims at providing the thermoplastic resin composition which can give the molded article which is excellent in transparency and impact resistance, and the molded article.

That is, the present invention is as follows.
[1]
For the total amount of the graft copolymer (A) and the thermoplastic resin (B) containing a polymer containing a vinyl cyanide monomer unit,
10-60% by mass of the graft copolymer (A),
90 to 40% by mass of a thermoplastic resin (B) containing a polymer containing the vinyl cyanide monomer unit,
A thermoplastic resin composition comprising:
The graft copolymer (A) has a trunk polymer made 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 unit in the graft chain-derived component of the graft copolymer (A) has two or more peaks,
Of the two or more peaks, at least one peak is a first peak having a peak top within the content range of 0% by mass or more and less than 10% by mass, and at least one other peak is A second peak having a peak top within the range of the content of 10% by mass or more and less than 55% by mass;
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,
A thermoplastic resin composition, wherein the half-width / peak height of the loss elastic modulus of the graft copolymer (A) is 0.1 or more and less than 0.25.
[2]
The thermoplastic resin composition according to [1], wherein a mass average particle diameter of the rubber polymer in the graft copolymer (A) is 0.10 μm or more and less than 0.80 μm.
[3]
The thermoplastic resin composition according to [1] or [2], wherein a graft ratio in the graft copolymer (A) is 80% or more and less than 240%.
[4]
The thermoplastic resin according to any one of [1] to [3], wherein a mass average particle diameter of the rubbery polymer in the graft copolymer (A) is 0.10 μm or more and less than 0.35 μm. Composition.
[5]
A molded article containing the thermoplastic resin composition according to any one of [1] to [4].
[6]
The molded product according to [5], wherein the molded product is a casing.

  ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin composition which can give the molded article excellent in impact resistance and transparency, and the molded article can be provided.

It is a figure which shows typically 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. It is a figure which shows the loss elastic modulus in each temperature of a graft copolymer.

Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail with reference to the drawings as necessary. However, the present invention is limited to the following embodiment. It is not a thing. The present invention can be variously modified without departing from the gist thereof.
In the present specification, “(meth) acryl” means “acryl” and “methacryl” corresponding thereto, and “(meth) acrylate” means “acrylate” and “methacrylate” corresponding thereto.

[Thermoplastic resin composition]
The thermoplastic composition of the present embodiment is a heat containing a graft copolymer (A) (hereinafter sometimes referred to as component (A)) and a polymer containing a vinyl cyanide monomer unit. Contains a plastic resin (B) (hereinafter may be referred to as a thermoplastic resin (B) or a component (B)).
The thermoplastic resin composition of the present embodiment is
For the total amount of the graft copolymer (A) and the thermoplastic resin (B) containing a polymer containing a vinyl cyanide monomer unit,
10-60% by mass of the graft copolymer (A),
90 to 40% by mass of a thermoplastic resin (B) containing a polymer containing the vinyl cyanide monomer unit,
Is a thermoplastic resin composition.
The graft copolymer (A) has a trunk polymer made 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 unit in the graft chain-derived component of the graft copolymer (A) has two or more peaks,
Of the two or more peaks, at least one peak is a first peak having a peak top within the content range of 0% by mass or more and less than 10% by mass, and at least one other peak is A second peak having a peak top within the range of the content of 10% by mass or more and less than 55% by mass;
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 “half width / peak height” of the loss elastic modulus of the graft copolymer (A) is 0.1 or more and less than 0.25.

(Graft copolymer (A))
The graft copolymer (A) has a trunk polymer made of a rubbery polymer and a graft chain graft-polymerized on the trunk polymer.
Examples of the rubbery polymer constituting the graft copolymer (A) in the present embodiment include diene rubber, acrylic rubber, and ethylene rubber. More specifically, polybutadiene, styrene-butadiene copolymer, styrene-butadiene block copolymer, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, polyisoprene, butadiene-methyl methacrylate copolymer. Polymer, butyl acrylate-methyl methacrylate copolymer, butadiene-ethyl acrylate copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-isoprene copolymer and ethylene-acrylic acid A methyl copolymer is mentioned. These are used singly or in combination of two or more. Among 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. Preferably used.

  When the rubbery polymer is a copolymer, the composition (distribution) of each structural unit in the rubbery polymer may be uniform or different, 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 graft copolymer (A) in this embodiment, the rubbery polymer constitutes a trunk polymer.

The rubbery polymer in the graft copolymer (A) takes the form of a dispersed phase (island) dispersed in the continuous phase (sea) of the thermoplastic resin (B), that is, a sea-island form.
The shape of the dispersed phase of the dispersed rubber 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 a viewpoint of impact resistance.
The dispersed phase may be dispersed independently one by one in the continuous phase of the thermoplastic resin (B), or may be dispersed in an aggregated state in which several dispersed phases are aggregated. From the viewpoint of impact properties, it is preferable that each one is dispersed independently.

  In the thermoplastic resin composition of the present embodiment, the size of the rubbery polymer is 0.10 μm or more from the viewpoint of impact resistance as a mass average particle diameter when the rubbery polymer has a particulate shape. It is preferable that it is less than 0.80 μm from the viewpoint of transparency. The mass average particle diameter is more preferably 0.10 to 0.50 μm, and still more preferably 0.10 to 0.35 μm. The particle size distribution of the rubbery polymer can be monodispersed, polydispersed, or bimodal depending on the intended physical properties.

The mass average particle diameter of the rubber polymer is obtained as follows.
First, an ultrathin section is produced 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 is photographed with a transmission electron microscope (TEM), and an arbitrary range (15 μm × 15 μm) of the ultrathin section is obtained by image analysis. The image can be analyzed using, for example, image analysis software “A Image-kun” (manufactured by Asahi Kasei Engineering Corporation).

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, particularly impact resistance based on the DuPont impact test, that the rubber polymer content is not less than the above lower limit and not more than the above upper limit.

The content of the vinyl cyanide monomer unit in the graft chain-derived component of the graft copolymer (A) (hereinafter referred to as “the content of the vinyl cyanide monomer unit in the component derived from the graft chain”) The distribution of “VCN unit content”) has two or more peaks.
Of the two or more peaks, at least one peak has 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 “peak 1”). And at least one of the two or more peaks is a second peak having a peak top within the range of the VCN unit content of 10% by mass or more and less than 55% by mass (hereinafter referred to as “peak 2”). ").
From the viewpoint of transparency, the peak top of peak 1 is preferably in the range of the VCN unit content of less than 10% by mass, and preferably in the range of the VCN unit content of 5% by mass or less. It is more preferable that the VCN unit content is within a range of not more than%.
The peak top of peak 2 is in the range of the VCN unit content of 10% by mass or more and less than 55% by mass from the viewpoint of scratch resistance and transparency.
The peak top of peak 2 is preferably within the range of the VCN unit content of 15% by mass or more and 50% by mass or less, and more preferably within the range of the VCN unit content of 20% by mass or more and 45% by mass or less. preferable.

From the viewpoint of impact resistance and scratch resistance, the difference between the representative value of the VCN unit content indicated by peak 1 and the representative value (C) of the VCN unit content indicated by peak 2 (| (peak 2) − (Peak 1) |) is 10% by mass or more, preferably 15% by mass or more, more preferably 22% by mass or more, and further preferably 25% by mass or more.
Here, the representative value of the VCN unit content indicated by each of the peak 1 and the peak 2 means a weighted average value obtained from an integrated value of the entire peaks of the peak 1 and the peak 2.

The component derived from the graft chain of the graft copolymer (A) is obtained through oxidative decomposition of the graft copolymer (A).
FIG. 1 is a diagram schematically showing an example of a distribution of VCN unit content in a component derived from a graft chain obtained through oxidative decomposition of a graft copolymer (A).
FIG. 1 shows the case where each of peak 1 and peak 2 is one, the horizontal axis indicates the VCN unit content, and the vertical axis indicates the peak intensity. This peak intensity indicates the presence of a component derived from a graft chain. It is an index indicating the ratio.

  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, when the distribution of the VCN unit content has a plurality of peaks 1 and / or a plurality of peaks 2, the representative value of the VCN unit content indicated by the peak 1 is a weighted average obtained from the integral value of the entire peak 1 The representative value of the VCN unit content indicated by the peak 2 means a weighted average value obtained from the integral value of the entire peak 2. 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.

The reduced specific viscosity (ηsp / c) of the graft chain-derived component is preferably in the range of 0.05 to 1.50 dL / g from the viewpoint of impact resistance.
The reduced specific 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 specific viscosity to 0.05 dL / g or more, it is possible to further suppress a reduction in impact resistance and strength, and by setting the reduced specific viscosity to 1.50 dL / g or less, further sufficient moldability. Can be obtained.

In general, when two or more types of monomers are graft-polymerized to a rubbery polymer, the charging ratio of each monomer is set for the purpose of narrowing the distribution of the content of monomer units in the graft chain. Graft polymerization is carried out at a constant level.
On the other hand, in this embodiment, by changing the charging ratio of each monomer to be grafted continuously or stepwise, each component in the component derived from the graft chain of the graft copolymer (A) The content of units, for example, the distribution of VCN unit content can be controlled.

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 of controlling the distribution of the VCN monomer content, and this method is preferable.
In the distribution of the VCN monomer content, each peak may be either monodispersed or polydispersed.

The distribution of VCN unit content in the graft copolymer (A) is determined by isolating the graft chain-derived component after oxidative decomposition of the graft copolymer (A), and measuring the graft chain-derived component by HPLC. It can obtain | require based on the chromatogram obtained.
As a method of oxidative decomposition, for example, ozonolysis, osmium acid decomposition, or the like can be used. More specifically, for example, a method described in a collection of polymer articles (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 VCN unit content in the graft copolymer (A) is determined as follows.

First, the thermoplastic resin composition of the present embodiment is dissolved in acetone and separated into an acetone-soluble component and an acetone-insoluble component by a centrifuge.
This acetone 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 this to methanol, 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)

  The weight average molecular weight (Mw) of the component derived from peak 1 in the graft copolymer (A) is preferably more than 0 and less than 30000 from the viewpoints of transparency, scratch resistance and fluidity. The weight average molecular weight is more preferably 1000 to 30000, still more preferably 1000 to 28000, and even more preferably 1000 to 25000.

  The weight average molecular weight (Mw) of the component derived from peak 2 in the graft copolymer (A) is preferably from 30,000 to less than 300,000 from the viewpoint of impact resistance and fluidity. The weight average molecular weight is more preferably 30000-250,000, still more preferably 80000-250,000, and still more preferably 100,000-250,000.

For the weight average molecular weight of the component derived from peak 1 in the graft copolymer (A) and the weight average molecular weight of the component derived from peak 2, the components corresponding to peak 1 and peak 2 are fractionated by the above-mentioned HPLC. , Respectively, by measuring with GPC (gel permeation chromatography).
The conditions are as follows.
Measuring instrument: Tosoh High Speed GPC HLC-8220GPC
Processing device: Multi-station GPC-8020
Column: TOSOH TSK-GEL (G6000HXL, G5000HXL, G40000HXL, G3000HXL in series), with guard column Detector: RI (differential refraction detector)
Detection sensitivity: 3000 mV / min
Solvent used: THF (first grade: containing stabilizer)
The weight average molecular weight is determined by a calibration curve method using polystyrene as a standard substance.

The “half width / peak height” of the loss elastic modulus of the graft copolymer (A) is 0.1 or more from the viewpoint of impact resistance, preferably 0.11 or more, more preferably 0.12 or more. .
Further, “half width / peak height” is less than 0.25, preferably 0.22 or less, more preferably 0.2 or less, from the viewpoints of transparency and weather resistance.

The loss elastic modulus of the graft copolymer (A) has two or more peaks.
One or more of the two or more peaks is a peak having a peak top within a range of −100 ° C. or more and less than 0 ° C. (hereinafter referred to as “Peak I”). Another one or more is a peak having a peak top within a range of 0 ° C. or higher and lower than 150 ° C. (hereinafter referred to as “peak II”).
From the viewpoint of impact resistance and transparency, the peak top of peak I is preferably in the range of −100 ° C. or more and less than 0 ° C., more preferably in the range of −95 ° C. or more and less than −20 ° C. More preferably, it is in the range of −90 ° C. or more and less than −40 ° C.
The peak top of peak II is preferably in the range of 0 ° C. or higher and lower than 150 ° C., more preferably in the range of 20 ° C. or higher and lower than 140 ° C., from the viewpoint of impact resistance and transparency. More preferably, it is in the range of 40 ° C. or more and less than 130 ° C.

FIG. 2 is a graph showing the loss elastic modulus at each temperature of the graft copolymer (A).
The horizontal axis represents temperature, and the vertical axis represents loss elastic modulus.
For example, 1.0E + 0.8 means 1.0 × 10 ⁸ .
As shown in FIG. 2, a point P is an intersection of the baseline of peak I (broken line in FIG. 2) and the perpendicular of peak I from the peak top.
The peak height of the peak I is obtained from the difference between the loss elastic modulus at the peak top of the peak I and the loss elastic modulus at the point P, and “half width / peak height” is obtained.
For example, when the peak height is 100 MPa and the half width is 20 ° C., “half width / peak height” = 20/100 = 0.2 can be calculated.

  The loss elastic modulus of the graft copolymer (A) is determined as follows.

The graft copolymer (A) was molded into a sheet having a thickness of 0.05 to 0.5 mm by a heat press at a preset temperature of 240 ° C., and cut into a length of 25 mm × a width of 5 mm to prepare a measurement sample.
Using a dynamic viscoelasticity measuring device, 5 mm portions at both ends of the long side of the sample were fixed with a tension jig, and measurement was performed under the following conditions.
Measuring device: Dynamic viscoelasticity measuring device (Rheogel-E-4000: manufactured by UBM)
Mode: Tensile waveform: Sine wave Frequency: 35Hz
Temperature increase rate: 3 ° C / min

In the present embodiment, the graft copolymer (A) comprises a rubbery polymer as a trunk polymer, a vinyl cyanide monomer, and at least one copolymerizable with the vinyl cyanide monomer. A graft copolymer obtained by graft polymerization of a mixture of monomers including a monomer.
The graft ratio in the graft copolymer (A) is preferably 40% or more and 260% or less from the viewpoints of impact resistance, transparency, and scratch resistance. This graft ratio is more preferably 80% or more and less than 240%, further preferably 100% or more and 220% or less, and still more preferably 120% or more and 200% or less.

  The graft ratio is defined by the ratio of the mass of the graft chain to the mass of the trunk polymer. The method for measuring the graft ratio is as follows.

The thermoplastic resin composition of the present embodiment is dissolved in acetone and separated into an acetone-soluble component and an acetone-insoluble component by a centrifuge. At this time, the components insoluble in acetone are a trunk polymer composed of a rubber polymer and a graft chain graft-polymerized to the trunk polymer, and the graft copolymer (A) in the thermoplastic resin composition of the present embodiment is the same. Is included. The component soluble in acetone contains the thermoplastic resin (B).
By analyzing a component insoluble in acetone with a Fourier transform infrared spectrophotometer (FT-IR), the composition ratio of the trunk polymer and the graft chain can be obtained, and the graft ratio can be determined based on the result. it can.

In the thermoplastic resin composition of the present embodiment, the total amount of the graft copolymer (A) and the thermoplastic resin (B) containing a polymer containing a vinyl cyanide monomer unit is 100% by mass. The content of the graft copolymer (A) is 10 to 60% by mass, preferably 15 to 55% by mass, and more preferably 20 to 50% by mass. It is preferable from the viewpoint of impact resistance that the content of the graft copolymer (A) is 10% by mass or more.
On the other hand, it is preferable that the content ratio of the graft copolymer (A) is 60% by mass or less from the viewpoint that the effect of scratch resistance of the molded product is easily exhibited.
Furthermore, the composition of the structural unit other than the rubbery polymer in the graft copolymer (A) (the type and content of the structural unit; the same shall apply hereinafter) and a polymer containing a vinyl cyanide monomer unit are contained. Controlling the composition of the thermoplastic resin (B) to improve compatibility improves the dispersion state of the rubbery polymer and further improves the balance of impact resistance, transparency, and scratch resistance of the molded product Can be made. In order to enhance the compatibility, for example, a thermoplastic resin containing a polymer containing a vinyl cyanide monomer unit and a type of constituent unit other than the rubbery polymer in the graft copolymer (A) Examples thereof include a method in which the types of the structural units of B) are the same, and the content ratios of the respective structural units are made closer, preferably the same.

In the graft copolymer (A), examples of the vinyl cyanide monomer graft-polymerized to the rubbery polymer 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.
Examples of the monomer copolymerizable with the vinyl cyanide monomer include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, ethylstyrene, pt-butylstyrene, vinylnaphthalene and the like. (Meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate; acrylic acids such as (meth) acrylic acid; N- N-substituted maleimide monomers such as phenylmaleimide and N-methylmaleimide; glycidyl group-containing monomers such as glycidyl (meth) acrylate are used, and these are used singly or in combination of two or more. It is done.
Among these, styrene, α-methylstyrene, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, N-phenylmaleimide, and glycidyl methacrylate are preferred from the viewpoint of strength and heat resistance. From this viewpoint, styrene is particularly preferable.

In the graft copolymer (A), the content ratio (E) of vinyl cyanide monomer units in all monomer units (100% by mass) other than the rubbery polymer is impact resistance and scratch resistance. In view of the above, it is preferably 15% by mass or more, and from the viewpoint of transparency, it is preferably less than 55% by mass, more preferably 20 to 50% by mass, still more preferably 25 to 45% by mass, and even more preferably 30 to 30%. 40% by mass.
Further, the difference (| (C) − (E) |) between the representative value (C) of the VCN unit content indicated by peak 2 and the content (E) is based on the impact resistance, particularly the Charpy impact test. From the viewpoint of impact resistance, the content is preferably less than 35% by mass, more preferably less than 25% by mass, and still more preferably less than 15% by mass. In addition, the minimum of difference (| (C)-(E) |) is not specifically limited, For example, you may exceed 0 mass%.

(Thermoplastic resin (B) containing a polymer containing vinyl cyanide monomer units)
The thermoplastic resin composition of the present embodiment contains a thermoplastic resin (B) containing a polymer containing a vinyl cyanide monomer unit from the viewpoint of compatibility with the graft copolymer (A).
Examples of the vinyl cyanide monomer constituting the polymer containing the vinyl cyanide monomer unit contained in the thermoplastic resin (B) include acrylonitrile and methacrylonitrile.
The vinyl cyanide monomer unit may be copolymerized with one or more monomer units copolymerizable therewith.
Examples of the monomer copolymerizable with the vinyl cyanide monomer include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, ethylstyrene, pt-butylstyrene, vinylnaphthalene and the like. (Meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate; acrylic acids such as (meth) acrylic acid; N- N-substituted maleimide monomers such as phenylmaleimide and N-methylmaleimide; glycidyl group-containing monomers such as glycidyl (meth) acrylate are used, and these are used singly or in combination of two or more. It is done. Among these, styrene, α-methylstyrene, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, N-phenylmaleimide, and glycidyl methacrylate are preferred from the viewpoint of strength and heat resistance. From this viewpoint, styrene is particularly preferable.

The thermoplastic resin composition of the present embodiment may contain a thermoplastic resin other than the polymer containing a vinyl cyanide monomer unit as the (B) thermoplastic resin.
The thermoplastic resin other than the polymer containing the vinyl cyanide monomer unit (may be described as other thermoplastic resin) may be a resin that can be injection-molded. It may be capable of imparting practically required strength, hardness, and heat resistance.
The other thermoplastic resin is preferably an amorphous thermoplastic resin from the viewpoint of miscibility with the graft copolymer (A).
Furthermore, when other thermoplastic resins have a glass transition temperature (Tg) of 90 to 300 ° C., an injection-molded product having practically necessary strength, hardness, and heat resistance can be obtained more effectively and reliably. be able to.
Examples of such other thermoplastic resins include polystyrene, acrylonitrile-styrene resin, methacryl resin, methyl methacrylate-styrene resin, polycarbonate resin, aromatic polyether resin, and amorphous polyester. These may be used alone or in combination of two or more.

The thermoplastic resin (B) contained in the thermoplastic resin composition of the present embodiment contains a polymer containing a vinyl cyanide monomer unit. The content ratio (D) of the vinyl cyanide monomer unit in the monomer unit (100% by mass) is preferably 15% by mass or more from the viewpoint of impact resistance and scratch resistance, and is transparent. From the viewpoint, it is preferably 55% by mass or less.
The content ratio (D) is more preferably 20 to 50% by mass, further preferably 25 to 45% by mass, and still more preferably 30 to 40% by mass.

  The difference (| (C)-(D) |) between the representative value (C) of the VCN monomer content indicated by peak 2 and the content (D) is 30% by mass from the point of abrasion resistance. Is preferably less than 20, more preferably less than 20% by mass, and even more preferably less than 10% by mass. By keeping the difference (| (C) − (D) |) within this range, it is possible to obtain a molded article having further excellent abrasion resistance.

In addition, the content ratio of the rubbery polymer in the graft copolymer (A), the content ratio (E) of the vinyl cyanide monomer unit in all the monomer units other than the rubbery polymer, the thermoplastic resin ( The content ratio (D) of the vinyl cyanide monomer unit in all monomer units in B) can be determined by a Fourier transform infrared spectrophotometer (FT-IR).
For example, the content ratio (E) of vinyl cyanide monomer units in all monomer units other than the rubbery polymer in the graft copolymer (A) is determined in advance by the total monomer units in the rubbery polymer. The content ratio (composition ratio) of each monomer unit is determined, and then the content ratio (composition ratio) of each monomer unit in all monomer units in the graft copolymer (A) is determined as FT-IR. It can obtain | require by considering the content rate of the graft polymer (A) graft-polymerized to the rubber polymer in a graft copolymer (A).

  In the present embodiment, the reduced specific viscosity (ηsp / c) of the thermoplastic resin (B) is preferably in the range of 0.20 to 1.50 dL / g from the viewpoint of impact resistance. The reduced specific viscosity is more preferably 0.30 to 0.80 dL / g, still more preferably 0.40 to 0.70 dL / g, and even more preferably 0.40 to 0.55 dL / g. is there. By setting the reduced specific viscosity to 0.20 dL / g or more, impact resistance and strength reduction can be further suppressed, and by setting the reduced specific viscosity to 1.50 dL / g or less, further sufficient moldability is achieved. Can be obtained.

In addition to the thermoplastic resin (B) containing a graft copolymer (A) and a polymer containing a vinyl cyanide monomer unit, the thermoplastic resin composition of the present embodiment may have other One or more optional components may be included.
Examples of such an optional component include various additives that can be contained in the molded article of the thermoplastic resin of the present embodiment, which will be described later, and those contained in ordinary thermoplastic resin compositions.
The content ratio of the optional component contained in the thermoplastic resin composition is not particularly limited as long as the object of the present invention can be achieved, and may be, for example, 0.05 to 4.00% by mass, 3.50 mass% may be sufficient.

  The thermoplastic resin composition of the present embodiment may be a combination of any of the above items.

[Method for producing thermoplastic resin composition]
(Method for producing graft copolymer (A))
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, a bulk suspension polymerization method, and an emulsion polymerization. The method can be used. Among these, a particle-shaped rubber component (dispersed phase) 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. The graft chain obtained here is preferably compatible with the thermoplastic resin (B) from the viewpoint of impact resistance.
In addition, after producing the particulate rubber polymer, the graft polymerization may be continuously performed in the same reactor, or the rubber particles may be once isolated as a latex and then graft polymerization may be performed again. .

Specifically, for example, one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers and acrylic monomers in polybutadiene latex obtained by emulsion polymerization There is a method of obtaining a graft copolymer by radical polymerization of.
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.

(Method for producing thermoplastic resin (B) containing a polymer containing vinyl cyanide monomer units)
The method for producing the thermoplastic resin (B) 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.
For example, a copolymer is produced by radical polymerization using two or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers and acrylic monomers. Thus, a thermoplastic resin (B) containing a polymer containing vinyl cyanide monomer units and, if necessary, other thermoplastic resins can be produced.
Moreover, a thermoplastic resin (B) may be manufactured together when manufacturing a graft copolymer (A). For example, when the graft copolymer (A) is produced, the monomer itself added for graft polymerization to the rubbery polymer may be polymerized to form the thermoplastic resin (B).

  In the present embodiment, the mixing (kneading) method of the graft copolymer (A) and the thermoplastic resin (B) is not particularly limited, and examples thereof include an open roll, an intact mixer, an internal mixer, a kneader, two Examples thereof include a melt kneading method using a kneader such as a continuous kneader with an axial rotor and an extruder. As the extruder, either a single screw or a twin screw extruder can be used.

(Method for producing thermoplastic resin composition)
The thermoplastic resin composition of the present embodiment can be obtained by mixing the graft copolymer (A), the thermoplastic resin (B), and any other material.
Examples of the mixing method include a melt kneading method.
Regarding the method of supplying the graft copolymer (A) and the thermoplastic resin (B) to the melt-kneader, all of them may be supplied to the same supply port at the same time, and they are supplied from different supply ports. May be. For example, using an extruder having two inlets, the graft copolymer (A) is supplied from the main inlet installed on the screw base side, and the auxiliary inlet installed between the main inlet and the extruder tip. Alternatively, the thermoplastic resin (B) may be supplied and melt kneaded.

  Moreover, when supplying a graft copolymer (A) and a thermoplastic resin (B) from the same supply port, after mixing both beforehand, it can also throw into an extruder hopper and can also knead | mix.

  A preferable melt-kneading temperature varies depending on the type of the thermoplastic resin (B) and is not particularly limited. For example, when acrylonitrile-styrene resin is melt-kneaded, it is preferably about 180 to 270 ° C. at a cylinder setting temperature. By setting the melt-kneading temperature in such a range, the dispersion state of the rubbery polymer becomes good, and the balance of the impact resistance, transparency, and scratch resistance of the molded product can be improved.

Moreover, when using an extruder, it is preferable that the temperature of a supply zone is 30-200 degreeC among cylinder temperatures, and the temperature of the kneading | mixing zone where melt-kneading is performed is melting | fusing point + 30-100 in the case of crystalline resin. In the case of an amorphous resin, the temperature is preferably in the range of Tg + 60 to 150 ° C.
By setting the temperature in two stages in this way, the graft copolymer (A) and the thermoplastic resin (B) are kneaded more smoothly, and the surface smoothness of the molded product, particularly the injection molded product, is improved. In addition, the abrasion resistance is further improved. Further, by setting the cylinder temperature within the above range, more excellent scratch resistance can be obtained.

  The melt kneading time is not particularly limited, but is preferably about 0.5 to 5 minutes from the viewpoint of impact resistance.

  In addition, when the thermoplastic resin composition of the present embodiment is produced by extrusion and a molded product is produced by an injection molding machine, the volatile content in the thermoplastic resin composition is 1500 ppm or less at the stage of supplying to the injection molding machine. Preferably there is. By setting the volatile content within such a range, more excellent scratch resistance can be obtained. In order to make the volatile content in such a range, for example, the volatile content is sucked at a vacuum degree of −100 to −800 hPa from a vent hole installed between the center of the cylinder of the twin screw extruder and the tip of the extruder Is preferred.

When the thermoplastic resin composition of the present embodiment is produced by extrusion, the extruded thermoplastic resin composition is directly cut into pellets, or after forming a strand, the pellets are cut with a pelletizer. Can do.
The shape of the pellet is not particularly limited, and may be a general shape such as a cylinder, a prism, or a sphere, for example, but a columnar shape is preferable.

〔Molding〕
The molded article of this embodiment contains the said thermoplastic resin composition, and is obtained by shape | molding the material containing a thermoplastic resin composition.
For molding the material containing the thermoplastic resin composition, for example, methods such as injection molding, injection compression molding, extrusion molding, blow molding, inflation molding, vacuum molding, and press molding can be used.

  In particular, injection molding methods include, for example, injection compression molding, gas assist molding using nitrogen gas or carbon dioxide gas, and high-speed heat cycle molding in which the mold temperature is increased. These can be used alone or in combination. Among these, gas assist molding, high speed heat cycle molding, and a combination of gas assist molding and high speed heat cycle molding are preferable.

Here, “gas assist molding” is generally known injection molding using nitrogen gas or carbon dioxide gas.
For example, as described in Japanese Patent Publication No. 57-14968, etc., a method of injecting a pressurized gas into a molded body after injecting a thermoplastic resin composition into a mold cavity, described in Japanese Patent No. 3819972, etc. A method of injecting a pressurized gas into a cavity corresponding to one side of a molded body after injecting a thermoplastic resin composition into a mold cavity, as described in Japanese Patent No. 3349070, etc. A method of filling the composition with a gas in advance and molding it may be mentioned. Among these, the method of press-fitting pressurized gas into the cavity corresponding to one side of the molded body is preferable.

  In this embodiment, the holding pressure for preventing sink and warp is preferably a holding pressure by gas assist. The holding pressure by gas assist is relatively low compared to the holding pressure by resin (composition), so that the generation of burrs can be further suppressed and the holding pressure necessary to prevent sink and warpage. Time can be shortened.

  From the pellets produced as described above, a kneaded product of the graft copolymer (A), the thermoplastic resin (B), and other optional components is molded into an injection molded product by using an injection molding machine. be able to. As the mold of the molding machine, a mold finished with a file of preferably # 4000 or more, more preferably # 12000 or more can be used. From the viewpoint of scratch resistance, the arithmetic average surface roughness Ra of the mold is preferably 0.02 μm or less, more preferably 0.01 μm or less.

  The method for setting the arithmetic average surface roughness Ra of the mold to the above range is not particularly limited. Polishing by work. Moreover, the steel material of the metal mold to be used is preferably a quenched and tempered steel of 40 HRC or more, more preferably 50 HRC or more. Instead of polishing the mold, a chrome plated mold may be used, or a chrome plated mold may be used on the polished mold as described above.

  Molding is preferably performed at a mold temperature in injection molding near the Vicat softening point of the kneaded product containing the graft copolymer (A) and the thermoplastic resin (B) from the viewpoint of scratch resistance. Specifically, the temperature is preferably −25 to + 20 ° C., more preferably −15 to + 5 ° C., relative to the Vicat softening point based on ISO306. When the mold temperature is within such a range, the transferability to the cavity surface is further improved, and an injection-molded product having more excellent abrasion resistance can be obtained.

  In general, when the mold (cavity surface) temperature is increased, the time until cooling becomes longer, and therefore there is a problem that the molding cycle becomes longer. Therefore, it is preferable to use a high-speed heat cycle molding method in which the cavity surface is heated and cooled in a short time. This makes it possible to achieve both improved scratch resistance and productivity. The surface of the molded body is preferably cooled at 1 to 100 ° C./second from the point of abrasion resistance of the molded body. The cooling rate of the surface of the molded body is more preferably 30 to 90 ° C / second, and further preferably 40 to 80 ° C / second.

In addition, a molding method in which the mold temperature is raised or lowered using a mold having a steam pipe or a heating wire built therein, or a molding method using supercritical CO ₂ can be preferably used.

  The thermoplastic resin composition (the kneaded product) at the time of injection molding is preferably molded at a temperature suitable for the kneaded product to be molded. For example, when the kneaded material contains an ABS-based resin, rubber-modified polystyrene, and / or methyl methacrylate-based resin, a temperature of 220 to 260 ° C. is preferable, and when it includes a polycarbonate, a temperature of 260 to 300 ° C. is preferable. .

  The injection-molded article of the thermoplastic resin composition of the present embodiment preferably has an injection speed of 1 to 50 mm / s, more preferably 5 to 30 mm / s, from the viewpoint of scratch resistance.

A casing is mentioned as 1 type of the molded article containing the thermoplastic resin composition of this embodiment.
The casing is an exterior (cover) of a device having a certain function such as a machine or electricity, and may be an exterior attached to the device. Examples of devices in which the casing is used include home appliances, OA devices, housing equipment, and vehicle equipment. Specifically, home appliances include vacuum cleaners, washing machines, refrigerators, microwave ovens, rice cookers, electric pots, telephones, coffee makers, TVs such as LCDs and plasmas, visual recorders, audio stereos, mobile phones including smartphones, There are a stationary game machine, a portable game machine, and a remote control. Specific 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. Specific examples of the housing equipment include a system kitchen, a wash basin, and a system bath. Specific examples of vehicle equipment include garnish covers for automobile interiors, such as shift lever indicator covers, door handle frames, power window switch frames, center clusters, car stereos, car navigation frames, and center pillar covers.

  The shape and size of the housing of the present embodiment are not particularly limited, and examples of the shape include a thin shape such as a plate shape to a shape having a three-dimensional thickness, and a corner is provided. It may be an angular polygonal shape or 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.

The molded product containing the thermoplastic resin composition of the present embodiment may contain a sliding aid in addition to the graft copolymer (A) and the thermoplastic resin (B).
The purpose of the sliding aid is to impart lubricity to the surface of the molded product. The addition amount of the sliding aid is preferably 0.05 to 2% by mass with respect to the total mass of the graft copolymer (A) and the thermoplastic resin (B) from the viewpoint of impact resistance. By containing a sliding aid, the fiber friction test is further improved.

  Examples of the sliding aid include lubricants such as aliphatic metal salts, polyolefins, polyester elastomers, polyamide elastomers, and polyols.

  As the lubricant, a fatty acid metal salt and a lubricant having an amide group or an ester group are preferable from the viewpoint of abrasion resistance. The fatty acid metal salt is preferably a salt of one or more metals selected from sodium, magnesium, calcium, aluminum and zinc and a fatty acid. Specifically, the fatty acid metal salt is sodium stearate, magnesium stearate, calcium stearate, aluminum stearate (mono, di, tri), zinc stearate, sodium montanate, calcium montanate, calcium ricinoleate, calcium laurate. Is mentioned. Among these, sodium stearate, magnesium stearate, calcium stearate, and zinc stearate are more preferable. Further, from the viewpoint of scratch resistance, stearic acid-based metal salts are preferable, and specifically, calcium stearate is more preferable.

  Examples of the polyolefin include one or more monomeric polyolefins selected from the group consisting of ethylene, propylene and α-olefins. Polyolefins may contain raw materials and by-products, and may be polymers derived from polyolefins. Specific examples include polypropylene, ethylene-propylene copolymer, polyethylene (high density, low density, linear low density), oxidized polyolefin, and graft-polymerized polyolefin.

  Of the polyolefins, polyolefin waxes, oxidized polyolefin waxes, and polyolefins grafted with styrenic resins are preferable from the viewpoint of scratch resistance, and more preferably polypropylene wax, polyethylene wax, oxidized polypropylene wax, oxidized polyethylene wax, acrylonitrile. -Styrene copolymer grafted polypropylene, acrylonitrile-styrene copolymer grafted polyethylene, styrene polymer grafted polypropylene, and styrene polymer grafted polyethylene.

  Examples of the polyester elastomer include a polyester obtained by polycondensation of a dicarboxylic acid compound and a dihydroxy compound, polycondensation of an oxycarboxylic acid compound, ring-opening polycondensation of a lactone compound, or polycondensation of a mixture of these components. Is mentioned. Either a homopolyester or a copolyester may be used.

  Examples of the dicarboxylic acid compound include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, and diphenoxyethanedicarboxylic acid. , Aromatic dicarboxylic acids such as sodium 3-sulfoisophthalate; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4-dicarboxylic acid; diphenyl ether dicarboxylic acid; Diphenylethane dicarboxylic acids; aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, dodecane dicarboxylic acid; and mixtures of these dicarboxylic acids, which are alkyl, alkoxy or halogen substituted Also good. These dicarboxylic acid compounds can also be used in the form of an ester-forming derivative, for example, a lower alcohol ester such as dimethyl ester. In the present embodiment, one of these dicarboxylic acid compounds can be used alone, or two or more can be used in combination.

  Among these, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, adipic acid and dodecanedicarboxylic acid are preferably used from the viewpoints of polymerizability, color tone and impact resistance.

  Examples of the dihydroxy compound include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, butenediol, hydroquinone, resorcin, dihydroxydiphenyl ether, cyclohexanediol, hydroquinone, resorcin, dihydroxydiphenyl ether, cyclohexanediol, and 2,2-bis ( 4-hydroxyphenyl) propane, and these polyoxyalkylene glycols and their alkyl, alkoxy or halogen-substituted products may be used. These dihydroxy compounds can be used alone or in combination of two or more.

Examples of the oxycarboxylic acid compound include oxybenzoic acid, oxynaphthoic acid, and diphenyleneoxycarboxylic acid, and these alkyl, alkoxy, and halogen-substituted products may be used. These oxycarboxylic acid compounds can be used alone or in combination of two or more.
A lactone compound such as ε-caprolactone can also be used for producing a polyester elastomer.

  Examples of the polyamide elastomer include aminocarboxylic acids or lactams having 6 or more carbon atoms, or nylon mn salts having m + n of 12 or more. Examples of the hard segment (X) of the polyamide elastomer include ω-aminocaproic acid, ω-aminoenanoic acid, ω-aminocaprylic acid, ω-aminobergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecane. Aminocarboxylic acids such as acids; lactams such as caprolactam laurolactam; nylon 6,6, nylon 6,10, nylon 6,12, nylon 11,6, nylon 11,10, nylon 12,6, nylon 11,12, Nylon salts such as nylon 12, 10 and nylon 12, 12 are listed.

Examples of the soft segment (Y) such as polyol include polyethylene glycol, poly (1,2- and 1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, Examples thereof include a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydrofuran. The number average molecular weight of these soft segments (Y) is preferably 2.0 × 10 ^{2 to} 6.0 × 10 ³ , more preferably 2.5 × 10 ^{2 to} 4.0 × 10 ³ . Note that both ends of poly (alkylene oxide) glycol may be aminated or carboxylated.

  Among these sliding aids, a combination of a stearic acid-based metal salt and a wax is preferable from the viewpoint of scratch resistance.

When a sliding aid is added to a molded product, an acid-modified or epoxy-modified modified resin may be mixed into the molded product for the purpose of improving their compatibility.
Moreover, you may acid-modify and / or epoxy-modify a part of graft copolymer (A) and / or thermoplastic resin (B) in the range which does not impair external appearance property. For example, a copolymer of a monomer in which the thermoplastic resin (B) is selected from an aromatic vinyl monomer, a vinyl cyanide monomer, and an acrylic monomer is used. When it contains, what copolymerized the vinyl monomer which has a carboxyl group or a glycidyl group to them is mentioned.
A part of the graft copolymer (A) and / or thermoplastic resin (B) modified with acid and / or epoxy is mixed for the purpose of improving the compatibility of the sliding aid. Therefore, it is not converted to the regulation of the contents of the graft copolymer (A) and the thermoplastic resin (B) in the thermoplastic resin composition of the present embodiment.

  Examples of the vinyl monomer having a carboxyl group include unsaturated compounds containing a free carboxyl group such as acrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid, maleic anhydride, itaconic anhydride, and chloromaleic anhydride. And unsaturated compounds containing an acid anhydride type carboxyl group such as citraconic anhydride. Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferable from the viewpoint of scratch resistance.

  Examples of the vinyl monomer having a glycidyl group include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, methyl glycidyl ether, and methyl glycidyl methacrylate. Among these, glycidyl methacrylate is preferable from the viewpoint of scratch resistance.

  The molded article of the present embodiment is a phosphite-based, hindered phenol-based, benzotriazole-based, benzophenone-based, benzoate-based, and cyanoacrylate-based UV absorber and antioxidant, as long as the object of the present invention can be achieved. Fatty acids, acid esters and acid amides, lubricants and plasticizers such as higher alcohols, montanic acid and salts thereof, esters, half esters thereof, stearyl alcohol, stellar amide and ethylene wax, release agents such as phosphorous acid Anti-coloring agents such as salts and hypophosphites, nucleating agents, anti-static agents such as amines, sulfonic acids, and polyethers, 1,3-phenylenebis (2,6-dimethylphenyl phosphate), tetra Phenyl-m-phenylenebisphosphate, phenoxyphosphoryl, phenoxyphosphate Phosphorus-based flame retardants such emissions may also include one or more optional additives such as a halogen-based flame retardant may be free. These addition amounts are each preferably 0.05 to 1% by mass from the viewpoint of weather resistance.

  For the purpose of imparting appearance, the molded article may contain, for example, an inorganic pigment, an organic pigment, a metallic pigment, and a dye. Among the colorants, those which make the color of the molded product white, black or red are preferably used because they give a particularly high-class feeling to the appearance of the molded product.

  Examples of inorganic pigments include titanium oxide, carbon black, titanium yellow, iron oxide pigments, ultramarine blue, cobalt blue, chromium oxide, spinel green, lead chromate pigments, and cadmium pigments.

  Examples of the organic pigment include azo pigments such as azo lake pigments, benzimidazolone pigments, diarylide pigments, and condensed azo pigments, phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, isoindolinone pigments, quinophthalone pigments, quinacridone pigments, and perylenes. Examples thereof include condensed polycyclic pigments such as pigments, anthraquinone pigments, perinone pigments, and dioxazine violet.

  Examples of metallic pigments include flake-like aluminum metallic pigments, spherical aluminum pigments used to improve weld appearance, mica powder for pearl-like metallic pigments, and other polyhedral particles of inorganic substances such as glass. The thing which coat | covered the metal by plating and sputtering is mentioned.

  Examples of the dye include nitroso dyes, nitro dyes, azo dyes, stilbene azo dyes, ketoimine dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, quinoline dyes, methine / polymethine dyes, thiazole dyes, indamine / indophenol dyes, Examples include azine dyes, oxazine dyes, thiazine dyes, sulfur dyes, aminoketone / oxyketone dyes, anthraquinone dyes, indigoid dyes, and phthalocyanine dyes.

  These colorants can be used alone or in combination of two or more. These addition amounts are preferably 0.05 to 2% by mass, more preferably 0.1 to 1.% by mass with respect to the total mass of the graft copolymer (A) and the thermoplastic resin (B) in terms of color tone. 5% by mass.

  The molded product of this embodiment may be a combination of any of the above items.

  According to the present embodiment, not only excellent impact resistance and transparency, but also a molded article excellent in scratch resistance and weather resistance, and a thermoplastic resin composition capable of providing such a molded article are provided. It is also possible to do.

Hereinafter, the present invention will be described in detail with specific examples, but the present invention is not limited to these examples.
In addition, the evaluation method applied to an Example is as follows.

As the evaluation of impact resistance, notched Charpy impact strength (kJ / m ² ) and DuPont impact strength (cm · kg) were used.

((1) Notched Charpy impact strength (kJ / m ² ))
Using a Toshiba Machine injection molding machine (product number: EC60N), the thermoplastic resin composition is molded at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C., and a test piece having a length of 8 cm × width of 1 cm and a thickness of 4 mm is cut out. Then, it evaluated according to ISO179.
It has a notched Charpy impact strength of 6 kJ / m ² or more, and can be used satisfactorily with no practical problems in home appliances, game machines, automobile interior materials, and the like.
Charpy notched impact strength is impossible those less than 6 kJ / m ^2, variable less than 6 kJ / m ² or more 8 kJ / m ^2, less than 8 kJ / m ² or more 9 kJ / m ² good, as good a 9 kJ / m ² or more evaluated.

((2) DuPont impact strength (cm · kg))
Using a Toshiba Machine injection molding machine (product number: EC60N), a 5 cm × 9 cm, 2.5 mm thick flat plate is molded from a thermoplastic resin composition at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. Evaluation was performed according to -6272.
With a DuPont impact strength of 50 cm · kg or more, it can be used practically without problems in home appliances, game machines, automobile interior materials, and the like.
DuPont impact strength of less than 50 cm · kg is “impossible”, 50 cm · kg or more and less than 90 cm · kg is “possible”, 90 cm · kg or more and less than 110 cm · kg is “good”, 110 cm · kg or more and 120 cm -Less than kg was evaluated as "excellent", and 120 cm · kg or more was evaluated as "excellent".

((3) Transparency)
As a reference for transparency, total light transmittance (%) and Haze (%) were used.
Using a Toshiba Machine injection molding machine (product number: EC60N), a 5 cm × 9 cm flat plate with a thickness of 2.5 mm was molded from the thermoplastic resin composition at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C.
With respect to the obtained flat plate, the total light transmittance (%) was measured according to ISO 13468, and the Haze (%) was measured according to ISO 13468.
When the total light transmittance is 50% or more and the haze is less than 55%, a high-quality appearance is easily obtained.
High-quality appearance means that a high-class feeling can be strongly felt with a deep color tone.
“No” if the total light transmittance is less than 57%, “Yes” if it is 57% or more and less than 58%, “Good” if it is 58% or more and less than 59%, “Good” if it is 59% or more. As evaluated.
“No” if haze is 39% or more, “Yes” if 36% or more and less than 39%, “Good” if 33% or more and less than 36%, “Excellent” if 30% or more and less than 33%. Less than 30% was evaluated as “best”.

((4) Scratch resistance)
The molded product formed by molding the thermoplastic resin composition of the present invention has been realized to be unpainted and have a high appearance, but practically, it has a degree of contamination that is usually performed in daily use. It is necessary that the appearance does not deteriorate due to actions such as cleaning and wiping.
The reason why the appearance is deteriorated by the wiping work is that fine scratches are formed on the surface of the molded product.
Therefore, evaluation by a fiber friction test was used as a measure of appearance retention ability, that is, abrasion resistance.

In the fiber friction test, the surface of a molded product (a flat plate described later) was rubbed with a tissue paper to determine the degree of damage.
Specifically, the evaluation was made based on the lightness difference (ΔL *) of the lightness (L *) before and after wiping.
The cleaning and wiping of the molded product performed on a daily basis was reproduced by evaluation under the conditions of a wiping load of 1000 g, a stroke of 60 mm, a speed of 50 mm / sec, and a reciprocation count of 20 times.

When measuring the brightness L *, first, using a Toshiba Machine injection molding machine (product number: EC60N) at a cylinder temperature of 250 ° C. and an injection speed of 50 mm / s, 100 parts by mass of the thermoplastic resin composition and 1 mass of carbon black. A flat plate having a size of 5 cm × 9 cm and a thickness of 2.5 mm was injection-molded from the kneaded product including the parts.
The mold used was a 10000 count file whose surface was polished to a surface roughness Ra of 0.01 μm. Mold temperature is 120 ° C at the time of injection using a heat cycle molding device (injection molding support device) manufactured by Kaken Genex Co., Ltd. up to 70 ° C at a temperature drop rate of about 10 ° C / 1 second after completion of injection. Cooled down. After leaving this flat plate in an air atmosphere at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours, the lightness (L *) of the flat plate was measured with a multi-light source spectral color meter (product number: MSC-5N-GV5) manufactured by Suga Test Instruments. It was measured. The brightness measurement conditions are as follows.
-Spectral 5 nm optical reflection-Light source: C light 2 ° field of view-Measurement (d / 8) conditions excluding specularly reflected light-Observation field of view: diameter 15 mm

Next, the flat plate is fixed at a predetermined position of a Gakushin abrasion tester (trade name “AB-301 Gakushin Friction Fastness Tester” manufactured by Tester Sangyo Co., Ltd.), and the stage side is moved under the following conditions to reciprocate. The plate was rubbed with tissue paper by moving. For the flat plate after the test, the lightness (L *) was measured under the same conditions as above, and the difference ΔL * before and after the test was determined. In this test, if many scratches are made on the flat plate surface, the difference in brightness (ΔL *) increases, that is, it can be evaluated as a thermoplastic resin composition inferior in scratch resistance. On the other hand, if there are only few scratches on the surface of the flat plate, it can be evaluated as a thermoplastic resin composition having a small difference in brightness (ΔL *), that is, excellent scratch resistance. Therefore, the lightness difference (ΔL *) was used as an evaluation standard for scratch resistance. The smaller the ΔL *, the better the scuff resistance. If the ΔL * is less than 1.0, it can be said that it is practically good in daily use.
ΔL * of 1.0 or more is “impossible”, 0.9 to less than 1.0 is “possible”, 0.8 to less than 0.9 is “good”, 0.6 to 0. Those less than 8 were evaluated as “excellent”, and those less than 0.6 were evaluated as “best”.
・ Tissue paper: Elmore (manufactured by Kami Shoji Co., Ltd.), 3 diffraction patterns (8 sheets stacked)
・ Sliding direction: parallel to the fiber direction of tissue paper (easy to tear) ・ Load: 1000 g
・ Stroke: 60mm
・ Sliding speed: 50mm / sec
・ Number of round trips: 20 round trips

((5) Weather resistance)
A flat plate similar to the injection-molded flat plate produced in the above “(4) Scratch resistance” was produced, and using the flat plate, a sunshine weather meter S80 (manufactured by Suga Test Instruments Co., Ltd.) was used, and the temperature was 63 ° C., 18 minutes / 120. The sample was exposed for 500 hours under conditions with a minute rain, and the color difference (ΔE) with the unexposed material piece was measured with a multi-light source spectroscopic color meter (product number: MSC-5N-GV5) manufactured by Suga Test Instruments.
ΔE of 1.0 or more is “impossible”, 0.9 to less than 1.0 is “possible”, 0.8 to less than 0.9 is “good”, 0.6 to 0.7 Those less than 0.6 were evaluated as “excellent” and those less than 0.6 were evaluated as “best”.
The measurement conditions are as follows.
-Spectral 5 nm optical reflection-Light source: C light 2 ° field of view-Measurement (d / 8) conditions excluding specularly reflected light-Observation field of view: diameter 15 mm

(Characteristics of graft copolymer and thermoplastic resin constituting thermoplastic resin composition)
<Number of peaks>
It measured using HPLC (high performance liquid chromatography).
Further, in the distribution of the VCN unit content, whether or not it is a peak was determined using an HPLC detector (Ultraviolet-visible light detector manufactured by Shimadzu Corporation, trade name “SPD-20A”).
<Representative value of VCN unit content indicated by peaks 1 and 2>
The representative value of the VCN unit content indicated by the peaks 1 and 2 was obtained from the weighted average value obtained from the integrated values of the peaks 1 and 2 as a whole.
<"Half-width / peak height" of the loss modulus peak>
The figure which shows the loss elastic modulus in each temperature of a graft copolymer as shown in FIG. 2 was created, and "half-value width / peak height" was calculated | required.
<Graft ratio>
The thermoplastic resin composition was dissolved in acetone and separated into an acetone-soluble component and an acetone-insoluble component by a centrifuge.
At this time, the components insoluble in acetone 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 the thermoplastic resin composition.
A component insoluble in acetone was analyzed by a Fourier transform infrared spectrophotometer (FT-IR) to determine the composition ratio of the trunk polymer and the graft chain, and the graft ratio was calculated based on the result.
<Mass average particle diameter of rubbery polymer>
The mass average particle diameter of the rubber polymer was measured as follows.
First, an ultrathin section was prepared from a molded article of the thermoplastic resin composition, and the ultrathin section was dyed with a staining agent such as osmium tetroxide or ruthenium tetroxide.
Thereafter, the stained ultrathin section was photographed with a transmission electron microscope (TEM), and an arbitrary range (15 μm × 15 μm) of the ultrathin section was determined by image analysis.
The images were analyzed using, for example, image analysis software “A Image-kun” (manufactured by Asahi Kasei Engineering Corporation).
<Weight average molecular weight derived from peaks 1 and 2>
The weight-average molecular weight of the components derived from peaks 1 and 2 in the graft copolymer is measured by GPC (gel permeation chromatography) by fractionating the components corresponding to peak 1 and peak 2 by the aforementioned HPLC. Was obtained.
The conditions are as follows.
Measuring instrument: Tosoh High Speed GPC HLC-8220GPC
Processing device: Multi-station GPC-8020
Column: TOSOH TSK-GEL (G6000HXL, G5000HXL, G40000HXL, G3000HXL in series), with guard column Detector: RI (differential refraction detector)
Detection sensitivity: 3000 mV / min
Solvent used: THF (first grade: containing stabilizer)
The weight average molecular weight was determined by a calibration curve method using polystyrene as a standard substance.
<Composition ratio of monomer>
The thermoplastic resin composition was dissolved in acetone and separated into an acetone-soluble component and an acetone-insoluble component by a centrifuge.
At this time, the components insoluble in acetone are a trunk polymer made of a rubbery polymer and a graft chain graft-polymerized to the trunk polymer.
Components insoluble in acetone were analyzed by a Fourier transform infrared spectrophotometer (FT-IR), and the composition ratio of the monomers was calculated.
<The content ratio (E) of vinyl cyanide monomer units in all monomer units other than the rubbery polymer of the graft copolymer, cyanation in all monomer units of the thermoplastic resin (B) Content ratio of vinyl monomer unit (D)>
Content ratio (E) of vinyl cyanide monomer unit in all monomer units other than rubbery polymer in graft copolymer, vinyl cyanide in all monomer units of thermoplastic resin (B) The content ratio (D) of the system monomer unit was determined by a Fourier transform infrared spectrophotometer (FT-IR).
<Reduced specific viscosity of thermoplastic resin (B)>
The thermoplastic resin composition was dissolved in acetone and separated into an acetone-soluble component and an acetone-insoluble component by a centrifuge. The component soluble in acetone contains the thermoplastic resin (B).
A solution obtained by dissolving 0.25 g of a measurement sample in 50 mL of 2-butanone was obtained by measuring the viscosity using a Cannon-Fenske type capillary at 30 ° C.

(Production Example 1)
[Production of rubber latex (L-1)]
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.
In the obtained polymerization solution, the solid content was 41.8% by mass, and the mass average particle size of the solid content measured by a Nikkiso Co., Ltd. Microtrac particle size analyzer (trade name: nanotrac 150) was 165 nm.

(Production Example 2)
[Production of rubber latex (L-2)]
95 parts by mass of butadiene, 5 parts by mass of styrene, 135 parts by mass of deionized water (iron concentration: less than 0.02 ppm), 3.0 parts by mass of potassium oleate, 0.3 parts by mass of potassium persulfate, 0.03 parts by weight of tertiary decyl mercaptan 2 parts by mass and 0.18 parts by mass of potassium hydroxide were placed in a pressure-resistant vessel equipped with a stirrer degassed in a vacuum, the temperature was raised from room temperature to 70 ° C., and polymerization was started.
After 15 hours from the start of polymerization, the reaction was cooled to complete the polymerization. In the obtained polymerization liquid, the solid content was 40% by mass, and the mass average particle diameter of the solid content was 80 nm.

(Production Example 3)
[Production of rubber latex (L-3)]
0.1 parts by weight of an emulsifier represented by the following formula (1) is added to 100 parts by weight (solid content) of the rubber latex (L-2) obtained in Reference Example 2, and after stirring for 5 minutes, acetic acid is added thereto. 0.65 part by mass was added. Next, 0.65 parts by mass of potassium hydroxide was added to obtain a rubber latex (L-3). The rubber polymer (L-3) had a mass average particle diameter of 360 nm, and the rubber latex (L-3) did not form a coagulum and was a high-concentration agglomerated latex having a solid content of 37% by mass. It was. Moreover, in the rubber latex (L-3), the mass fraction of solids having a particle diameter of 600 nm or more was 8% by mass.

(Production Example 4)
[Production of Resin Composition (I-1)]
95 parts by mass of deionized water (iron concentration: less than 0.02 ppm) is added to 30 parts by mass (solid content) of the rubber latex (L-1) obtained in the above (Production Example 1), and the gas phase part is nitrogen. Substituted, dissolved in 20 parts by mass of deionized water were 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. An aqueous solution was added (the “first addition” in Table 1 above).
Thereafter, the temperature was raised to 70 ° C.
Subsequently, over 3 hours, a monomer mixture composed of 21 parts by mass of styrene and 0.14 parts by mass of cumene hydroperoxide, and 10.5 parts by mass of deionized water were added with 0.0392 of sodium formaldehyde sulfoxylate. An aqueous solution in which parts by mass were dissolved was added (“1st stage addition” in Table 1).
Subsequently, over 3.5 hours, 17.15 parts by mass of acrylonitrile, 31.85 parts by mass of styrene and 0.04 parts by mass of cumene hydroperoxide, and 24.5 deionized water An aqueous solution obtained by dissolving 0.0914 parts by mass of sodium formaldehyde sulfoxylate was added to parts by mass (hereinafter, “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 another hour while controlling the reaction vessel at 70 ° C., and 0.5 parts by mass of potassium rosinate was added there. (“Shot” in Table 1). In this way, ABS rubber latex was obtained.

After adding 0.07 part by mass of a silicone resin defoamer and 0.6 part by mass of a phenolic antioxidant emulsion to 100 parts by mass of the ABS rubber latex thus obtained, the solid content concentration is 10 parts by mass. % Was adjusted by adding deionized water and heated to 70 ° C., then solidified by adding an aqueous aluminum sulfate solution, 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) comprises a graft copolymer (IA-1) and a thermoplastic resin (IB-1), and is insoluble in acetone, that is, the graft copolymer (I- The content ratio of A-1) was 78.9% by mass, and the content of acetone-soluble matter, that is, the thermoplastic resin (IB-1) was 21.1% by mass.
Further, the reduced specific viscosity (ηsp / c) of the thermoplastic resin (IB-1) was 0.53 dL / g.
The reduced specific viscosity was determined by measuring the viscosity of a solution obtained by dissolving 0.25 g of a sample in 50 mL of 2-butanone using a Cannon-Fenske capillary at 30 ° C. (the same applies hereinafter).

(Production Examples 5 to 15)
[Production of Resin Compositions (I-2) to (I-12)]
Resin compositions (I-2) to (I-12) were produced in the same manner as in (Production Example 4) except that the formulations shown in Table 1 were used.
Table 1 below shows the materials and preparation ratios of the resin compositions of (Production Examples 4 to 15), the acetone-insoluble content, the content of acetone-soluble components, and the reduced specific viscosity of acetone-soluble components.

(Production Example 16)
[Production of thermoplastic resin (II-B-1)]
Peroxide 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 (2) (10-hour half-life: 63.5 ° C.) A monomer mixture consisting of 1.05 parts by mass was prepared without contact with air, and continuously supplied to a reactor equipped with a stirrer.
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 thus obtained was continuously extracted 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, the polymer concentration in the polymerization mixture is adjusted to 65% by mass, and then discharged from the first separation 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 99. After adjusting to 4 mass%, it discharged and obtained the pellet-shaped thermoplastic resin (II-B-1).
The composition ratio of each monomer unit in this thermoplastic resin (II-B-1) 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 the composition analysis using), the acrylonitrile unit was 39.5% by mass and the styrene unit was 60.5% by mass.
The thermoplastic resin (II-B-1) was soluble in acetone, and the reduced specific viscosity (ηsp / c) was 0.49 dL / g.

(Production Example 17)
[Production of thermoplastic resin (II-B-2)]
Acrylonitrile 33.2 parts by weight, styrene 29.9 parts by weight, butyl acrylate 8.1 parts by weight, ethylbenzene 28.8 parts by weight, α-methylstyrene dimer 0.3 parts by weight, t-butyl peroxyisopropyl carbonate 0.01 A monomer mixture consisting of parts by mass was prepared without contact with air and continuously fed to a reactor equipped with a stirrer.
The polymerization temperature was adjusted to 142 ° 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 1.65 hours.
The polymerization mixture liquid having a polymerization rate of 60% and a polymer concentration of 50% by mass thus obtained was continuously extracted 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, the polymer concentration in the polymerization mixture is adjusted to 65% by mass, and then discharged from the first separation 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 99. After adjusting to 4 mass%, it discharged and obtained the pellet-shaped thermoplastic resin (II-B-2).
As a result of composition analysis using a Fourier transform infrared spectrophotometer, the composition ratio of each monomer unit in the thermoplastic resin (II-B-2) was 38.6% by mass for the acrylonitrile unit and 51 for the styrene unit. The butyl acrylate unit was 10.1% by mass.
The thermoplastic resin (II-B-2) was soluble in acetone, and the reduced specific viscosity (ηsp / c) was 0.42 dL / g.

(Example 1)
45 parts by mass of resin composition (I-1) and 55 parts by mass of thermoplastic resin (II-B-1) after sufficiently drying and removing moisture, 1 part by mass of ethylene bisstearamide, carbon black # 2600 (Mitsubishi Chemical Co., Ltd., average particle diameter 13 nm, nitrogen adsorption specific surface area 370 m ² / g, volatile content 1.8%) After mixing 1.0 part by mass, the mixture was put into a hopper and a twin screw extruder (Product No .: PCM-30, L / D = 28, manufactured by Ikekai Tekko Co., Ltd.) and kneaded under conditions of a cylinder set temperature of 250 ° C., a screw rotation speed of 200 rpm, and a kneaded product discharge speed of 15 kg / hour. The pellet which is a plastic resin composition was obtained.
Table 2 shows the content of each resin in the obtained thermoplastic resin composition.
In Table 2, the graft copolymer (IA) and the thermoplastic resin (IB) in the resin composition (I) are respectively represented by “IAn”, “IBn” ( n is an integer of 1 to 13, and this corresponds to the resin composition (In) shown in Table 1. That is, for example, the graft copolymer (IA-2) and the thermoplastic resin composition (IB-2) shown in Table 2 used in Example 2 are the same as the resin composition (I -2) refers to the graft copolymer and thermoplastic resin.

When the distribution of the VCN unit content in the graft copolymer (A) was determined according to the above method, two or more peaks were present, and the representative value of the VCN unit content indicated by peak 1 was 0. The representative value (C) of the VCN unit content indicated by 3% by mass and peak 2 was 34.2% by mass. Further, the mass average particle diameter of the rubber polymer dispersed in the thermoplastic resin composition was determined according to the above method (staining agent: osmium tetroxide) and found to be 0.21 μm.
It was 0.156 when the half value width / peak height of the loss elastic modulus peak I in the graft copolymer (A) was determined according to the above method.
It was 15000 when the weight average molecular weight derived from the peak 1 was calculated | required based on the said method.
It was 150,000 when the weight average molecular weight derived from the peak 2 was calculated | required based on the said method.

As a result of analyzing the composition ratio of the monomer in the graft copolymer (A) using a Fourier transform infrared spectrophotometer (FT-IR) (manufactured by JASCO Corporation, product number: FT / IR-7000), The acrylonitrile unit is 14.8% by mass, the styrene unit is 47.1% by mass, the butadiene unit is 38.0% by mass, and the vinyl cyanide monomer unit in all monomer units other than the rubbery polymer. The content ratio (E) was 23.9% by mass, and the graft ratio was 163%.
On the other hand, the content ratio (D) of acrylonitrile units in all monomer units in the thermoplastic resin (B) was 37.2% by mass, and the reduced specific viscosity (ηsp / c) was 0.50 dL / g. . These results and the results of each evaluation are shown in Table 3.

(Examples 2-7, Comparative Examples 1-7)
The content ratios of the graft copolymer (A) and the thermoplastic resin (B) were changed as shown in Table 2. Other conditions were the same as in Example 1, and pellets that were thermoplastic resin compositions were obtained and evaluated.
The evaluation results are shown in Table 3.

In Examples 1-7, it was excellent in impact resistance, and it was the result which was excellent in transparency, abrasion resistance, and weather resistance.
On the other hand, in Comparative Example 1, the “half width / peak height” was outside the range of the present invention, and thus the transparency and weather resistance were insufficient.
In Comparative Example 2, the “half width / peak height” was outside the range of the present invention, and thus the impact resistance was insufficient.
In Comparative Example 3, only peak 2 appears, and the distribution of the VCN unit content is outside the range of the present invention, so that transparency and weather resistance were insufficient.
In Comparative Example 4, only peak 1 appears, and the distribution of the VCN unit content is outside the range of the present invention, so that the impact resistance, transparency, and scratch resistance were insufficient.
In Comparative Example 5, the difference between the representative value of the VCN unit content indicated by the first peak in the above distribution and the representative value of the VCN unit content indicated by the second peak is outside the scope of the present invention. In addition, the impact resistance, transparency, and scratch resistance were insufficient.
In Comparative Example 6, since the content of the graft copolymer (A) was outside the scope of the present invention, transparency, scratch resistance, and weather resistance were insufficient.
In Comparative Example 7, since the content of the graft copolymer (A) was outside the range of the present invention, the impact resistance was insufficient.

By using the thermoplastic resin composition of the present invention, a molded article excellent in impact resistance, transparency (appearance), and scratch resistance can be obtained without application.
Therefore, the thermoplastic resin composition of the present invention can be used as a material for high-end home appliances, game machines, cameras, cases such as mobile phones, decorative frames for televisions, and automobile interior members.
Examples of home appliances include televisions, telephones, printers, computers, vacuum cleaners, speakers, and the like. Examples of automobile interior members include center clusters, switch boards, pillars, and the like. The thermoplastic resin composition of the present invention has industrial applicability in these fields.

Claims (6)

For the total amount of the graft copolymer (A) and the thermoplastic resin (B) containing a polymer containing a vinyl cyanide monomer unit,
10-60% by mass of the graft copolymer (A),
90 to 40% by mass of a thermoplastic resin (B) containing a polymer containing the vinyl cyanide monomer unit,
A thermoplastic resin composition comprising:
The graft copolymer (A) has a trunk polymer made 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 unit in the graft chain-derived component of the graft copolymer (A) has two or more peaks,
Of the two or more peaks, at least one peak is a first peak having a peak top within the content range of 0% by mass or more and less than 10% by mass, and at least one other peak is A second peak having a peak top within the range of the content of 10% by mass or more and less than 55% by mass;
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,
A thermoplastic resin composition, wherein the half-width / peak height of the loss elastic modulus of the graft copolymer (A) is 0.1 or more and less than 0.25.   The thermoplastic resin composition according to claim 1, wherein a mass average particle diameter of the rubbery polymer in the graft copolymer (A) is 0.10 µm or more and less than 0.80 µm.   The thermoplastic resin composition according to claim 1 or 2, wherein a graft ratio in the graft copolymer (A) is 80% or more and less than 240%.   The thermoplastic resin composition according to any one of claims 1 to 3, wherein a mass average particle diameter of the rubbery polymer in the graft copolymer (A) is 0.10 µm or more and less than 0.35 µm. .   The molded article containing the thermoplastic resin composition as described in any one of Claims 1 thru | or 4.   The molded product according to claim 5, wherein the molded product is a casing.

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