JP2020111722A - Thermoplastic resin composition and molded article of the same - Google Patents

Abstract

To provide a thermoplastic resin composition capable of obtaining a molded article having good glossiness and chemical resistance while maintaining excellent impact resistance even when being colored.SOLUTION: A thermoplastic resin composition contains a graft copolymer (A) having a stem polymer composed of a rubbery polymer and a graft chain graft-polymerized with the stem polymer, a specific thermoplastic resin (B) and a specific polyester elastomer (C), in which with respect to 100 pts.mass of the total of the components (A) to (C), a content of the component (A) is 10-45 pts.mass, a content of the component (B) is 89.5 to 40 pts.mass and a content of the component (C) is 0.5-15 pts.mass, particle size distribution of the rubbery polymer is bimodel particle size distribution of a first peak derived from a rubbery polymer (a1) having a mass average particle diameter of 0.20 μm or more and less than 0.50 μm and a second peak derived from a rubbery polymer (a2) having a mass average particle diameter of 0.10 μm or more and less than 0.20 μm.SELECTED DRAWING: Figure 2

Description

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

Styrene-based resins, particularly acrylonitrile-butadiene-styrene copolymers (hereinafter also referred to as “ABS resins”) are excellent in mechanical properties such as impact resistance and rigidity and processing properties, and thus have been conventionally used in automobiles, It is used in various applications such as housing materials, household appliances, and cosmetic containers. In recent years, for the purpose of further increasing the commercial value, a resin composition having a good surface gloss in addition to performance such as impact resistance has been demanded.
However, in general, when a rubbery polymer is contained in a resin composition for the purpose of enhancing properties such as impact resistance, when the particle size of the rubbery polymer is reduced, surface gloss becomes good but impact resistance is improved. On the contrary, when the particle size of the rubbery polymer is increased, the impact resistance is improved but the gloss is decreased.

As a method for solving the above-mentioned problems, conventionally, by obtaining a styrene-based resin composition in which two kinds of rubbery polymers having a specific average particle size and a specific particle size distribution are used in combination, excellent impact resistance and good impact resistance are obtained. A method of obtaining gloss has been proposed (see, for example, Patent Documents 1 and 2).

On the other hand, it is known that ABS resin causes dissolution or swelling, cracking or breakage due to permeation or absorption when it comes into contact with a chemical solution.
In particular, the occurrence of cracks or breakage due to an attack reagent is a major problem for resin materials, and is called environmental stress fracture (ESC). Since this environmental stress fracture occurs due to the strain during molding that remains inside the molded product, it can occur even when no external force is applied to the molded product of the resin material, which greatly limits the application of ABS resin. ing.

In recent years, sunscreen cosmetics have been used for the purpose of protecting the skin exposed to the sun during outdoor work or leisure from sunburn, cancer and photoaging.
Since the sunscreen cosmetic has a high attack property (attack property) to the resin material, when the sunscreen cosmetic comes into contact with a molded product using the ABS resin, for example, a cosmetic container, cracking may occur and the commercial value may be impaired. For this reason, molded articles using ABS resin are required to have high chemical resistance.

As a method of improving the chemical resistance of a molded article using an ABS resin, a method of increasing the amount of an acrylonitrile (AN) component of the ABS resin is disclosed (for example, refer to Patent Document 3).

Further, as another method for improving the chemical resistance of a molded article using an ABS resin, a method of adding a polyester having excellent chemical resistance to the ABS resin is known. For example, a method of adding 0.1 to 50% by mass of a saturated polyester resin to a resin composition containing a copolymer component having a predetermined intrinsic viscosity is disclosed (see, for example, Patent Document 4). A method of adding 5 to 55 mass% of terephthalate is disclosed (for example, refer to Patent Document 5).

Also, a method of replacing the diene rubber component of the ABS resin with an acrylate ester rubber component (acrylic rubber) is disclosed (for example, see Patent Document 6).

Japanese Unexamined Patent Publication No. 9-310002 JP, 9-310003, A Japanese Examined Patent Publication No. 60-28311 JP-A-59-219362 Japanese Patent Laid-Open No. 02-294347 JP-A-07-331024 Japanese Patent Laid-Open No. 9-157470

However, the technique described in Patent Document 3 has insufficient chemical resistance for sunscreen cosmetics, which has a high effect on ABS resins.
Further, in the methods described in Patent Documents 4 and 5, when the amount of polyester is large, the appearance of a molded product or the appearance after coating is significantly deteriorated, and mechanical properties such as heat resistance and rigidity are deteriorated. If the amount of polyester is small, satisfactory results cannot be obtained in the effect of improving chemical resistance.
Further, in the method described in Patent Document 6, the elastic modulus of the acrylic rubber is lower than that of the diene rubber, elastic recovery is slow, and plastic deformation is likely to occur. Therefore, a resin composition containing an acrylic rubber component is used as a molding material. When a molded product is manufactured by the injection molding method, the flow deformation and orientation of the particles of the acrylic rubber component are remarkable, and the surface of the molded product exhibits a pearly luster, flow marks and color separation, and the appearance is remarkable. It may get worse.

Furthermore, as described above, chemical resistance can be enhanced by adding a chemical resistance aid such as polyester or acrylate rubber (acrylic rubber) to the ABS resin. There is a risk that the external appearance originally possessed by the above may be impaired or the mechanical properties may deteriorate.

Furthermore, Patent Document 7 discloses that chemical resistance and impact resistance can be improved by adding a small amount of polyester elastomer to ABS resin. However, regarding impact resistance and gloss during coloring, Is not stated.

In the conventional resin composition as described above, when a colorant is added for the purpose of imparting a design property, the impact resistance is deteriorated, and even if the resin composition is colored, excellent impact resistance is maintained and a good gloss is obtained. Molded product with high resistance and chemical resistance cannot be obtained.

Therefore, in the present invention, to provide a molded article having good gloss and chemical resistance while maintaining excellent impact resistance even if colored, and a thermoplastic resin composition from which the molded article can be obtained. With the goal.

As a result of earnestly researching the above-mentioned problems, the present inventors have found that a graft copolymer (A) and a thermoplastic resin (B) containing a polymer containing a vinyl cyanide monomer unit are used. A thermoplastic resin composition containing a predetermined amount of a polyester elastomer (C) having a predetermined hard segment and a predetermined soft segment, wherein the graft copolymer (A) is a trunk made of a rubbery polymer. A polymer and a rubber polymer (a1) having a graft chain graft-polymerized on the trunk polymer and having a particle size distribution of the rubber polymer, the mass average particle size of which is 0.20 μm or more and less than 0.50 μm. To have a bimodal particle size distribution of the first peak derived from the first peak and the second peak derived from the rubbery polymer (a2) having a mass average particle size of 0.10 μm or more and less than 0.20 μm. As a result, they have found that the above-mentioned problems of the prior art can be solved, and have completed the present invention.
That is, the present invention is as follows.

[1]
A trunk polymer composed of a rubbery polymer, and a graft copolymer (A) having a graft chain graft-polymerized on the trunk polymer;
A thermoplastic resin (B) containing a polymer containing vinyl cyanide-based monomer units;
A polyester elastomer (C) in which the hard segment is an aromatic polyester and the soft segment is an aliphatic polyether and/or an aliphatic polyester,
The content of the graft copolymer (A) is 10 to 45 parts by mass with respect to 100 parts by mass of the total amount of the graft copolymer (A), the thermoplastic resin (B) and the polyester elastomer (C), The content of the thermoplastic resin (B) is 89.5 to 40 parts by mass, the content of the polyester elastomer (C) is 0.5 to 15 parts by mass,
The particle size distribution of the rubber-like polymer has a mass-average particle size of 0.10 μm and a first peak derived from the rubber-like polymer (a1) having a mass-average particle size of 0.20 μm or more and less than 0.50 μm. A thermoplastic resin composition having a bimodal particle size distribution with a second peak derived from the rubber-like polymer (a2) of 0.20 μm or more.
[2]
The temperature-loss tangent (tan δ) curve in the graft copolymer (A) has two or more peaks, and at least one of the two or more peaks is −73° C. or higher −64. Peak I having a peak top in the range of less than °C,
The thermoplastic resin composition according to the above [1], wherein the “half width/peak height” of the peak I is 40 or more and less than 60.
[3]
The graft copolymer (A) contains a vinyl cyanide-based monomer unit,
In the graft copolymer (A), the content ratio (D) of vinyl cyanide-based monomer units in all monomer units (100% by mass) other than the rubbery polymer is 15 to 50% by mass. The thermoplastic resin composition according to the above [1] or [2].
[4]
The content ratio (E) of vinyl cyanide-based monomer units in all the monomer units (100% by mass) in the thermoplastic resin (B) is 15 to 55% by mass, [1] to [3] ] The thermoplastic resin composition as described in any one of these.
[5]
In the particle size distribution of the rubber polymer (a1), the SD value represented by the following formula (1) is 0.01 μm or more and less than 0.07 μm,
Any one of [1] to [4] above, wherein the SD value represented by the following formula (1) in the particle size distribution of the rubber polymer (a2) is 0.01 μm or more and less than 0.07 μm. The thermoplastic resin composition according to.
SD=(d84%-d16%)/2 (1)
(In the formula (1), d16% represents the particle size (μm) at the point where the cumulative curve becomes 16% in the particle size distribution, and d84% represents the particle at the point where the cumulative curve becomes 84% in the particle size distribution. Indicates the diameter (μm).)
[6]
The difference between the mass average particle size of the rubbery polymer (a1) and the mass average particle size of the rubbery polymer (a2) is 0.10 μm or more and less than 0.25 μm, [1] to [5] ] The thermoplastic resin composition as described in any one of these.
[7]
The thermoplastic resin composition according to any one of [1] to [6], wherein the polyester elastomer (C) has a Shore hardness D of 20 to 80.
[8]
The rubbery polymer constituting the graft copolymer (A) is polybutadiene, styrene-butadiene copolymer, styrene-butadiene block copolymer, acrylonitrile-butadiene copolymer, and acrylonitrile-styrene-butadiene copolymer. The thermoplastic resin composition according to any one of the above [1] to [7], which is at least one selected from the group consisting of coalescence.
[9]
A molded product of the thermoplastic resin composition according to any one of [1] to [8].
[10]
The molded article according to the above [9], which is a cosmetic container.

According to the present invention, a molded article having good gloss while maintaining excellent impact resistance even after being colored and having excellent chemical resistance, and a thermoplastic resin composition from which the molded article can be obtained are provided. can do.

1 is an example of a temperature-loss tangent (tan δ) curve of a graft copolymer. It is a figure which shows the peak top of peak I, the peak height, and the half value width in an example of the temperature-loss tangent (tan(delta)) curve 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, but the present invention is limited to the following embodiments. However, the present invention can be implemented by variously modifying within the scope of the gist. Further, in the present specification, “(meth)acrylic” means “acrylic” and its corresponding “methacrylic”, and “(meth)acrylate” means “acrylate” and its corresponding “methacrylate”.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present embodiment is a graft polymer (A) having a trunk polymer composed of a rubbery polymer and a graft chain graft-polymerized to the trunk polymer (hereinafter, referred to as a component (A)). And a thermoplastic resin (B) containing a polymer containing a vinyl cyanide monomer unit (hereinafter sometimes referred to as a thermoplastic resin (B) or a component (B)). , A polyester elastomer (C) in which the hard segment is an aromatic polyester and the soft segment is an aliphatic polyether and/or an aliphatic polyester.

In the thermoplastic resin composition of the present embodiment, the graft copolymer (A) is added to 100 parts by mass of the total amount of the graft copolymer (A), the thermoplastic resin (B) and the polyester elastomer (C). 10 to 45 parts by mass, the content of the thermoplastic resin (B) is 89.5 to 40 parts by mass, and the content of the polyester elastomer (C) is 0.5 to 15 parts by mass.
In addition, the particle size distribution of the rubber-like polymer is such that the mass average particle size is from 0.20 μm to less than 0.50 μm and the first peak is derived from the rubber-like polymer (a1), and the mass average particle size is 0. 10 is a bimodal particle size distribution with a second peak derived from the rubbery polymer (a2) of 10 μm or more and less than 0.20 μm.
The thermoplastic resin composition of the present embodiment having the above-mentioned constitution can maintain a high impact resistance even if it is colored, have a good luster, and obtain a molded article excellent in chemical resistance.

(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. Furthermore, regarding the particle size distribution of the rubber-like polymer, the first peak derived from the rubber-like polymer (a1) having a mass average particle size of 0.20 μm or more and less than 0.50 μm and a mass average particle size of 0. It is a bimodal particle size distribution with the second peak derived from the rubbery polymer (a2) of 10 μm or more and less than 0.20 μm.

In the present embodiment, the bimodal particle size distribution has two peaks (peaks) in the particle size distribution with the particle size as the horizontal axis and the frequency (%) as the vertical axis. It is a particle size distribution. Each of the two mountain-like peaks has one maximum particle size. The maximum particle size at each peak (peak) is the particle size at which the frequency is maximum at each peak (peak).

Further, in the present embodiment, the mass average particle size means, for example, 100 rubbery polymers in an arbitrary range (15 μm×15 μm) of an ultrathin section photographed by a transmission electron microscope (TEM) described later. Is a value calculated by measuring the circle-converted particle size of and using the following formula.
Mass average particle size=(Σn _i D _i ⁴ )/(Σn _i D _i ³ )
(N _i in the formula represents the number of rubber-like polymers having a circle-converted particle diameter D _i (μm)).

Further, the content of (a1) is preferably 20 to 80 mass% with respect to the total amount of the rubber-like polymer (a1) and the rubber-like polymer (a2). The content is preferably 80 to 20% by mass.
The SD value “(d84%−d16%)/2” in the particle size distribution of the rubber polymer (a1) is preferably 0.01 μm or more and less than 0.07 μm, and 0.03 μm or more and 0.02 μm or more. More preferably, it is not more than 06 μm. The SD value “(d84%−d16%)/2” in the particle size distribution of the rubber polymer (a2) is preferably 0.01 μm or more and less than 0.07 μm, and 0.03 μm or more and 0.06 μm or less. Is more preferable.
The difference between the mass average particle size of the rubber polymer (a1) and the mass average particle size of the rubber polymer (a2) is preferably 0.10 μm or more and less than 0.25 μm, It is more preferably 12 μm or more and 0.23 μm or less.

The thermoplastic resin composition of the present embodiment has the above-described constitution of the graft copolymer (A), and thus has excellent impact resistance and gloss even when colored, and various chemicals including sunscreen cosmetics. It has excellent chemical resistance to, and in particular, it is used extensively in more severe operating environments where chemicals adhere to the surface and dry without being washed away, and chemicals with a high concentration remain adhered for a long time. A molded product that can be obtained is obtained.

Examples of the rubbery polymer that constitutes the graft copolymer (A) include, but are not limited to, diene rubber, acrylic rubber, and ethylene rubber.
Specifically, but not limited to, for example, polybutadiene, styrene-butadiene copolymer, styrene-butadiene block copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-styrene-butadiene copolymer , Butyl acrylate-butadiene copolymer, polyisoprene, butadiene-methyl methacrylate copolymer, butyl acrylate-methyl methacrylate copolymer, butadiene-ethyl acrylate copolymer, ethylene-propylene copolymer, ethylene -Propylene-diene copolymers, ethylene-isoprene copolymers and ethylene-methyl acrylate copolymers may be mentioned.
These may be used alone or in combination of two or more.
Among these, at least one rubber substance selected from the group consisting of polybutadiene, styrene-butadiene copolymer, styrene-butadiene block copolymer, acrylonitrile-butadiene copolymer and acrylonitrile-styrene-butadiene copolymer. Polymers are preferred from the viewpoint of impact resistance.

When the rubbery polymer is a copolymer, the composition (distribution) of each structural unit in the rubbery polymer may be uniform or may be different, or continuously. It may have a different composition. The composition of each structural unit of the rubbery polymer can be confirmed by a Fourier transform infrared spectrophotometer (FT-IR). The rubbery polymer constitutes the trunk polymer. The rubbery polymer in the graft copolymer (A) is in the form of a dispersed phase (island) dispersed in the continuous phase (sea) of the thermoplastic resin (B), and the thermoplastic resin composition of the present embodiment. The thing has a sea-island form. The shape of the dispersed phase of the dispersed rubbery polymer is not particularly limited, and examples thereof include an amorphous shape, a rod shape, a flat plate shape, and a particle shape. Of these, the particulate form is preferable from the viewpoint of impact resistance. The dispersed phase may be dispersed individually in the continuous phase of the thermoplastic resin (B), or may be dispersed in the state of an aggregate in which several dispersed phases are aggregated. From the viewpoint of impact resistance, it is preferable that the particles are dispersed independently.

In the thermoplastic resin composition of the present embodiment, the particle size distribution of the rubber-like polymer is different from that of the rubber-like polymer (a1) having different mass average particle size ranges from the viewpoint of gloss and impact resistance retention at the time of coloring. 2 is a bimodal particle size distribution (two peak distribution) of the first peak derived from (1) and the second peak derived from the rubbery polymer (a2).
The size of the rubbery polymer is such that, when the shape of the rubbery polymer is particulate, the mass average particle diameter of the rubbery polymer (a1) is from the viewpoint of gloss and retention of impact resistance during coloring. 0.20 μm or more and less than 0.50 μm, preferably 0.25 μm or more and 0.40 μm or less, more preferably 0.30 μm or more and 0.40 μm or less, further preferably 0.30 μm or more and 0.35 μm or less is there. On the other hand, the mass average particle diameter of the rubbery polymer (a2) is 0.10 μm or more and less than 0.20 μm, preferably 0.12 μm or more and less than 0.20 μm from the viewpoint of impact resistance and impact resistance retention rate during coloring. It is less than 20 μm, more preferably 0.14 μm or more and less than 0.20 μm, and further preferably 0.16 μm or more and less than 0.20 μm.

Here, an example of a method for controlling the mass average particle diameter of the rubber polymer will be described below.
For example, when producing a rubbery polymer by emulsion polymerization, as a method of controlling the mass average particle diameter of the rubbery polymer, adjusting the concentration of the emulsifier, the ratio of the monomer charged before the start of polymerization and deionized water And the like.
When adjusting the ratio of the monomer to deionized water, in the polymerization of the rubbery polymer (a1), the preferable ratio of the monomer to deionized water is (monomer/deionized water)=1.20 to 1.80. Is more preferable, 1.30 to 1.70 is more preferable, and 1.40 to 1.60 is further preferable.
On the other hand, in the polymerization of the rubbery polymer (a2), the preferable ratio of the monomer to the deionized water is (monomer/deionized water)=0.95 to 1.20, more preferably 1.00 to 1 0.15, and more preferably 1.05 to 1.10.
The ratio of the monomer to the deionized water is a mass ratio, and is specifically defined as “monomer (parts by mass)/deionized water (parts by mass)”.
By setting the ratio of the monomer to deionized water within the above range, it becomes possible to control the mass average particle diameters of the rubbery polymers (a1) and (a2) within a preferable range.

The content ratio of the rubber-like polymer (a1) in the rubber-like polymer ((a1)+(a2)=100% by mass) is preferably 20 to 80 from the viewpoint of gloss and impact resistance retention at the time of coloring. %, more preferably 30 to 70% by mass, further preferably 40 to 60% by mass, and even more preferably 45 to 55% by mass. On the other hand, the content ratio of the rubbery polymer (a2) in the rubbery polymer ((a1)+(a2)=100% by mass) is preferably from the viewpoint of impact resistance and impact resistance retention rate during coloring. Is 20% by mass or more and 80% by mass or less, more preferably 30 to 70% by mass, further preferably 40 to 60% by mass, and still more preferably 45 to 55% by mass.
The ratio of the rubber-like polymer (a1) and the rubber-like polymer (a2) can be adjusted by preparing each rubber-like polymer separately from the viewpoint of controlling the particle size, and then blending them at an arbitrary ratio. It can be controlled within the above numerical range.

As an index of the particle size distribution of the rubbery polymer, it is preferable to use the SD value represented by the following formula (1).
SD=(d84%-d16%)/2 (1)
(In the formula, d16% represents the particle size (μm) at the point where the cumulative curve becomes 16% in the particle size distribution, and d84% represents the particle size (μm at the point where the cumulative curve becomes 84% in the particle size distribution. ).)
The smaller the SD value, the narrower the particle size distribution.
In the thermoplastic resin composition of the present embodiment, the SD value “(d84%−d16%)/2” in the particle size distribution of the rubbery polymer (a1) is gloss and retention of impact resistance during coloring. From the viewpoint of, it is preferably 0.01 μm or more and less than 0.07 μm, more preferably 0.02 μm or more and less than 0.07 μm, still more preferably 0.03 μm or more and less than 0.07 μm, and still more preferably 0.03 μm or more 0. It is 0.06 μm or less.
On the other hand, the SD value “(d84%−d16%)/2” in the particle size distribution of the rubbery polymer (a2) is preferably 0. 0 from the viewpoint of impact resistance and impact resistance retention rate during coloring. It is at least 01 μm and less than 0.07 μm, more preferably at least 0.02 μm and less than 0.07 μm, even more preferably at least 0.03 μm and less than 0.07 μm, and even more preferably at least 0.03 μm and less than 0.06 μm. "(D84%-d16%)/2" in the particle size distribution of the rubbery polymer (a1) and the SD value "(d84%-d16%)/2" in the particle size distribution of the rubbery polymer (a2) are By adjusting the emulsifier concentration during the polymerization of the rubbery polymer, it is possible to control within the above-mentioned numerical range.

The difference between the mass average particle size of the rubber polymer (a1) and the mass average particle size of the rubber polymer (a2) is preferably 0.10 μm from the viewpoint of the impact resistance retention rate during coloring. Or more and less than 0.25 μm, more preferably 0.12 or more and 0.23 μm or less, still more preferably 0.14 or more and 0.23 μm or less, still more preferably 0.16 or more and 0.20 μm or less.

The mass average particle diameters of the rubber-like polymer (a1) and the rubber-like polymer (a2) are determined by a known method. For example, it is calculated as follows. First, an ultrathin section is prepared from a molded article of the thermoplastic resin composition of the present embodiment, and the ultrathin section is dyed with a dyeing agent such as osmium tetroxide and ruthenium tetroxide. Thereafter, the stained ultrathin section is photographed by a transmission electron microscope (TEM), and the image is analyzed in an arbitrary range (15 μm×15 μm) of the ultrathin section. The image can be analyzed using, for example, image analysis software "A image-kun" (manufactured by Asahi Kasei Engineering Co., Ltd.).

The content ratio of the rubbery polymer (a1) and the rubbery polymer (a2) in the rubbery polymer ((a1)+(a2)=100% by mass) is as described above. ) And the mass average particle diameter of the rubber polymer (a2), and the measured mass average particle diameter of the rubber polymer (a1) is 0.20 μm or more and less than 0.50 μm, and the mass average particle. It can be obtained by calculating the content ratio of the rubbery polymer (a2) having a diameter of 0.10 μm or more and less than 0.20 μm to the total amount thereof.

The rubber-like polymer (a1) contained in the thermoplastic resin composition of the present embodiment has a particle size distribution of the rubber-like polymer. It is an aggregate of individual rubber-like polymers having a particle size included in the peak (peak). In addition, the rubber-like polymer (a2) contained in the thermoplastic resin composition of the present embodiment has a smaller particle size side of the two peaks (peaks) present in the particle size distribution of the rubber-like polymer. It is an aggregate of individual rubber-like polymers having a particle size included in the peak (peak).

The SD value “(d84%−d16%)/2” in the particle size distribution of the rubbery polymer (a1) and the rubbery polymer (a2) is as described above. The image obtained by the same method as the method for measuring the mass average particle diameter of the polymer (a2) and taken by a transmission electron microscope (TEM) was analyzed, and d84%: the cumulative curve in the particle diameter distribution was 84%. The particle diameter (μm) at the point where d is 16%, and the particle diameter (μm) at the point where the cumulative curve is 16% in the particle diameter distribution: 16% are obtained and are applied to the above formula (1).

The reduced specific viscosity (ηsp/c) of the component derived from the graft chain of the graft copolymer (A) contained in the thermoplastic resin composition of the present embodiment is 0.20 to 0.80 dL from the viewpoint of impact resistance. It is preferably in the range of /g. The reduced specific viscosity is more preferably 0.30 to 0.75 dL/g, further preferably 0.40 to 0.70 dL/g, and still more preferably 0.5 to 0.65 dL/g. is there. By setting the reduced specific viscosity of the component derived from the graft chain to 0.20 dL/g or more, it is possible to further suppress the decrease in impact resistance and strength, and to set the reduced specific viscosity to 0.80 dL/g or less. Thus, it is possible to obtain more sufficient fluidity. The reduced specific viscosity of the component derived from the graft chain can be determined by measuring the viscosity of a solution of 0.25 g of a measurement sample dissolved in 50 mL of 2-butanone using a Cannon-Fenske type capillary tube at 30°C.
The reduced specific viscosity (ηsp/c) of the component derived from the graft chain of the graft copolymer (A) is controlled within the above numerical range by adjusting the addition amount of the initiator and the chain transfer agent during the graft polymerization. be able to.

The component derived from the graft chain of the graft copolymer (A) is obtained through oxidative decomposition of the graft copolymer (A). As the method of oxidative decomposition, for example, ozone decomposition, osmic acid decomposition and the like can be used. More specifically, the method described in Kobunshi Kobunshi (Fumio Ide et al., vol. 32, No. 7, P. 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.

The temperature-loss tangent (tan δ) curve derived from the graft copolymer (A) preferably has two or more peaks.
When the temperature-loss tangent (tan δ) curve derived from the graft copolymer (A) has two or more peaks, at least one peak of the two or more peaks is −73° C. or higher and lower than −64° C. It is preferable that the peak has a peak top within the range (hereinafter, referred to as “peak I”).
Further, at least one of the two or more peaks is preferably a peak having a peak top in the range of 0° C. or higher and lower than 150° C. (hereinafter, referred to as “peak II”). ..
From the viewpoint of impact resistance and impact resistance retention during coloring, the peak top position of peak I is more preferably within the range of -73°C or higher and lower than -64°C, and -73°C or higher and lower than -68°C. Is more preferably within the range of -71°C or more and less than -69°C.
From the viewpoint of impact resistance and color tone, the peak top position of peak II is preferably in the range of 90°C or higher and lower than 150°C, more preferably in the range of 100°C or higher and lower than 140°C. More preferably, it is in the range of 110°C or higher and lower than 130°C.

In the temperature-loss tangent (tan δ) curve derived from the graft copolymer (A), the “half-value width/peak height” of peak I is 40 or more from the viewpoint of impact resistance and impact resistance retention rate during coloring. Is more preferable, 42 or more is more preferable, and 44 or more is still more preferable. In addition, the “half-value width/peak height” of peak I is preferably less than 60, more preferably 58 or less, still more preferably 56 or less, from the viewpoint of gloss and impact resistance retention during coloring. .. In the temperature-loss tangent (tan δ) curve derived from the graft copolymer (A), the half value width/peak height of peak I can be controlled within the above numerical range by a method described later.

Further, in the temperature-loss tangent (tan δ) curve derived from the graft copolymer (A), the peak top position of the peak I can be controlled within the above numerical range by the method described later.

In the temperature-loss tangent (tan δ) curve derived from the graft copolymer (A), when there are two or more peaks in the range of −73° C. or higher and lower than −64° C., that is, when there are two or more peaks I. It is preferable that all peaks I satisfy the above range.

Here, an example of a method for controlling the “half-value width/peak height” and the peak top position of the peak I in the temperature-loss tangent (tan δ) curve derived from the graft copolymer (A) will be described.

As a method for controlling the “half-width/peak height” of the peak I in the temperature-loss tangent (tan δ) curve derived from the graft copolymer (A) within a desired numerical range, (1) the graft copolymer ( Examples of the method include the method of adjusting the graft ratio of A) and the method of adjusting the degree of crosslinking of the rubber polymer (2), and the methods (1) and (2) may be used alone or in combination. It is possible.
In the case of the above method (1), the graft ratio of the graft copolymer (A) can be controlled by adjusting the addition amounts of the polymerization initiator and the chain transfer agent in the graft polymerization. By setting the graft ratio of the graft copolymer (A) to 10% or more and 200% or less, which is the numerical range described below, the peak I "in the temperature-loss tangent (tan δ) curve derived from the graft copolymer (A). It is possible to control the “half-value width/peak height” within a preferable range.
In the case of the method (2), the swelling index can be used as an index showing the degree of crosslinking of the rubbery polymer when adjusting the degree of crosslinking of the rubbery polymer.
The swelling index of the rubbery polymer is preferably 10 to 50%, more preferably 15 to 40%, and further preferably 20 to 30%.
By adjusting the swelling index of the rubbery polymer within the above range, the “half width/peak height” of peak I in the temperature-loss tangent (tan δ) curve derived from the graft copolymer (A) is controlled within a preferable range. It becomes possible to do.
Control of the swelling index of the rubber polymer, for example, when producing a rubber polymer by emulsion polymerization, increase the addition amount of the chain transfer agent, increase the polymerization temperature, increase the polymerization conversion rate at the end of the polymerization, It is possible to employ a method in which the monomer/polymer ratio during the polymerization is reduced to perform the polymerization, etc. By doing so, the swelling index of the rubbery polymer becomes small and the degree of crosslinking can be increased. Further, the swelling index can be reduced by copolymerizing and using a crosslinkable monomer such as divinylbenzene.

As a method for controlling the peak top position of the peak I in the temperature-loss tangent (tan δ) curve derived from the graft copolymer (A) so as to fall within a desired temperature range, a diene in each constitutional unit of the rubbery polymer is used. The method of adjusting the content rate of a system monomer is mentioned.
For example, when the rubbery polymer is a styrene-butadiene copolymer, the preferable butadiene content is 50 to 99% by mass, more preferably 80 to 97% by mass, and further preferably 90 to 95% by mass. .. By adjusting the butadiene content within this range, it becomes possible to control the peak top position of the peak I in the temperature-loss tangent (tan δ) curve derived from the graft copolymer (A) within a preferable range.

FIG. 1 is an example of a temperature-loss tangent (tan δ) curve of the graft copolymer, and FIG. 2 is a peak top and peak height of peak I in the example of the temperature-loss tangent (tan δ) curve of the graft copolymer. It is a figure which shows S and the half value width.
1 and 2, the horizontal axis represents temperature and the vertical axis represents tan δ.
As shown in FIG. 2, a point P is an intersection of a baseline of the peak I (broken line in FIG. 2) and a vertical line from the peak top of the peak I.
The peak height of the peak I is obtained from the difference between tan δ at the peak top of the peak I and tan δ at the point P, and the “half-value width/peak height” of the peak I is further obtained.
For example, when the peak height is 0.5 and the half width is 20° C., “half width/peak height”=20/0.5=50 can be calculated.

The temperature-loss tangent (tan δ) curve derived from the graft copolymer (A) can be measured as follows.

A thermoplastic resin composition containing the graft copolymer (A) or a molded article containing the graft copolymer (A) is molded into a sheet having a thickness of 0.1 to 0.3 mm by heat pressing at a preset temperature of 240°C. A length of 30 mm and a width of 10 mm are cut out to prepare a measurement sample.
Using a dynamic viscoelasticity measuring device, 5 mm portions on both ends of the long side of the sample are fixed with a tension jig, and the measurement is performed under the following conditions.
Measuring device: Dynamic viscoelasticity measuring device (Iplexer 500N GABO)
Mode: Tension Frequency: 8Hz
Temperature rising rate: 3°C/min Measuring temperature: -100 to 150°C

In the present embodiment, the graft copolymer (A) is obtained by adding a vinyl cyanide-based monomer and one or more copolymerizable vinyl cyanide-based monomers to a rubber-like polymer as a trunk polymer. It is preferably a graft copolymer obtained by graft-polymerizing a mixture of monomers containing a monomer.
The graft ratio in the graft copolymer (A) is preferably 10% or more and 200% or less. The graft ratio in the graft copolymer (A) is more preferably 20% or more and less than 150%, further preferably 30% or more and 100% or less, and still more preferably 40% or more and 70% or less. By setting the graft ratio in the graft copolymer (A) in this range, the “half-width/peak height” of the peak I in the temperature-loss tangent (tan δ) curve derived from the graft copolymer (A) is in a preferable range. Can be controlled.

The graft ratio is defined as 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 centrifugal separator. At this time, the component insoluble in acetone is a trunk polymer made of a rubbery polymer and a graft chain graft-polymerized on the trunk polymer. The graft copolymer (A) in the thermoplastic resin composition of the present embodiment is It includes. The acetone-soluble component contains the thermoplastic resin (B). A component insoluble in acetone is analyzed by a Fourier transform infrared spectrophotometer (FT-IR) to obtain the constitutional ratio of the trunk polymer and the graft chain in the graft copolymer (A), and based on the result, Then, the graft ratio of the graft copolymer (A) can be obtained.

In the thermoplastic resin composition of the present embodiment, a graft copolymer (A), a thermoplastic resin (B) containing a polymer containing a vinyl cyanide monomer unit, and a polyester elastomer (C) When the total amount is 100 parts by mass, the content ratio of the graft copolymer (A) is 10 to 45 parts by mass, preferably 15 to 43 parts by mass, more preferably 20 to 40 parts by mass, More preferably, it is 22 to 38 parts by mass. From the viewpoint of impact resistance, it is preferable to set the content ratio of the graft copolymer (A) to 10 parts by mass or more based on 100 parts by mass of the total of the components (A) to (C). On the other hand, it is preferable from the viewpoint of fluidity that the content ratio of the graft copolymer (A) is 45 parts by mass or less based on 100 parts by mass of the components (A) to (C) in total.
Further, the composition of the constitutional units other than the rubbery polymer in the graft copolymer (A) (the kind and the proportion of the constitutional units, the same applies hereinafter) and the polymer containing the vinyl cyanide monomer unit are contained. When the compatibility is enhanced by controlling the composition of the thermoplastic resin (B) to be used, the dispersed state of the rubber-like polymer is further improved, and the impact resistance and appearance of the molded article can be further improved in balance. .. In order to improve the compatibility, for example, a thermoplastic resin containing a polymer containing a vinyl cyanide monomer unit and the type of constitutional unit other than the rubbery polymer in the graft copolymer (A) ( Examples of the method include making the types of the structural units of B) the same, or making the content ratios of the respective structural units close to each other, preferably the same.

In the graft copolymer (A), the vinyl cyanide-based monomer that is preferable as the monomer to be graft-polymerized with the rubber-like polymer is not limited to the following, and examples thereof include acrylonitrile and methacrylonitrile. Are listed. At least a part of the vinyl cyanide-based monomer unit may be copolymerized with one or more kinds of monomer units copolymerizable therewith. The monomer that can be copolymerized with the vinyl cyanide-based monomer is not limited to the following. For example, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, ethylstyrene, Aromatic vinyl monomers such as pt-butyl styrene and vinyl naphthalene; (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate and butyl (meth)acrylate; ) Acrylic acids such as acrylic acid; N-substituted maleimide-based monomers such as N-phenylmaleimide and N-methylmaleimide; and glycidyl group-containing monomers such as glycidyl (meth)acrylate. They may be used alone or in combination of two or more. Among these, preferable monomers are styrene, α-methylstyrene, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, N-phenylmaleimide, and glycidyl methacrylate from the viewpoint of strength and heat resistance. From the viewpoint of strength, styrene is particularly preferable.

When the graft copolymer (A) contains a vinyl cyanide-based monomer unit, the content of the vinyl cyanide-based monomer unit in all the monomer units (100% by mass) other than the rubbery polymer The ratio (D) is preferably 15% by mass or more from the viewpoint of impact resistance and the impact resistance retention rate during coloring, and is preferably 50% by mass or less from the viewpoint of color tone, more preferably 20 to 45% by mass. %, more preferably 25-40% by mass, even more preferably 30-38% by mass, even more preferably 32-36% by mass.

(Thermoplastic resin (B) containing a polymer containing vinyl cyanide-based 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). The vinyl cyanide-based monomer constituting the polymer containing the vinyl cyanide-based monomer unit contained in the thermoplastic resin (B) is not limited to the following, but for example, Examples thereof include acrylonitrile and methacrylonitrile. The vinyl cyanide-based monomer unit may be copolymerized with one or more monomer units copolymerizable therewith. The copolymerizable monomer with a vinyl cyanide-based monomer is not limited to the following, and examples thereof include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, ethylstyrene, Aromatic vinyl monomers such as pt-butyl styrene and vinyl naphthalene; (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; ) Acrylic acids such as acrylic acid; N-substituted maleimide-based monomers such as N-phenylmaleimide and N-methylmaleimide; and glycidyl group-containing monomers such as glycidyl (meth)acrylate. These may be used alone or in combination of two or more. Among these, preferable monomers are styrene, α-methylstyrene, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, N-phenylmaleimide, and glycidyl methacrylate from the viewpoint of strength and heat resistance. From the viewpoint of strength, styrene is particularly preferable.

The thermoplastic resin composition of the present embodiment may further contain a thermoplastic resin other than the polymer containing the vinyl cyanide monomer unit in the thermoplastic resin (B).
The thermoplastic resin other than the polymer containing the vinyl cyanide-based monomer unit (may be referred to as other thermoplastic resin) may be a resin that can be injection-molded, and may be used as an injection-molded product. It may be one that can impart strength, hardness, and heat resistance required for practical use.
As the other thermoplastic resin, an amorphous thermoplastic resin is preferable from the viewpoint of miscibility with the graft copolymer (A).
Furthermore, since the other thermoplastic resin has a glass transition temperature (Tg) of 90 to 300° C., an injection-molded article having strength, hardness, and heat resistance necessary for practical use can be obtained more effectively and reliably. be able to.
Examples of such other thermoplastic resins include, but are not limited to, polystyrene, acrylonitrile-styrene resin, methacrylic resin, methylmethacrylate-styrene resin, polycarbonate resin, aromatic polyether resin, and amorphous. Included is a volatile 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 (E) of vinyl cyanide-based monomer units in all the monomer units (100% by mass) in the thermoplastic resin (B) is from the viewpoint of impact resistance and impact resistance retention rate during coloring. Is preferably 15% by mass or more, and from the viewpoint of color tone, it is preferably 55% by mass or less. The content ratio (E) is more preferably 20 to 50% by mass, further preferably 25 to 45% by mass, even more preferably 30 to 42% by mass, and still more preferably 35 to 42% by mass.

The content ratio of the rubbery polymer in the graft copolymer (A), the content ratio (D) of the vinyl cyanide-based monomer units in all the monomer units other than the rubbery polymer, the thermoplastic resin ( The content ratio (E) of vinyl cyanide-based monomer units in all the monomer units in B) can be determined by a Fourier transform infrared spectrophotometer (FT-IR). For example, the content ratio (D) of vinyl cyanide-based monomer units in all the monomer units other than the rubber-like polymer in the graft copolymer (A) is calculated in advance as follows. The content ratio (composition ratio) of each monomer unit in the composition is determined, and then the content ratio (composition ratio) of each monomer unit in all the monomer units in the graft copolymer (A) is calculated by FT-IR. It can be determined by considering the content ratio of the rubbery polymer in the graft copolymer (A) and the graft chain graft-polymerized to the rubbery polymer.
Content ratio of the rubbery polymer in the graft copolymer (A), content ratio (D) of the vinyl cyanide-based monomer units in all monomer units other than the rubbery polymer, thermoplastic resin (B) The content ratio (E) of the vinyl cyanide-based monomer units in all the monomer units in the above is the vinyl cyanide-based monomer in the polymerization step of the graft copolymer (A) and the thermoplastic resin (B). It can be controlled by adjusting the polymerization conditions such as the addition amount and polymerization time.

The reduced specific viscosity (ηsp/c) of the thermoplastic resin (B) used in the thermoplastic resin composition of the present embodiment is preferably in the range of 0.20 to 1.50 dL/g from the viewpoint of impact resistance. .. The reduced specific viscosity of the thermoplastic resin (B) is more preferably 0.30 to 0.80 dL/g, still more preferably 0.40 to 0.75 dL/g, and even more preferably 0.50. ~0.65 dL/g. By setting the reduced specific viscosity of the thermoplastic resin (B) to 0.20 dL/g or more, it is possible to further suppress the decrease in impact resistance and strength, and the reduced specific viscosity of the thermoplastic resin (B) is 1. By setting it to 50 dL/g or less, more sufficient moldability can be obtained.

In the thermoplastic resin composition of the present embodiment, a graft copolymer (A), a thermoplastic resin (B) containing a polymer containing a vinyl cyanide monomer unit, and a polyester elastomer (C) When the total amount is 100 parts by mass, the content ratio of the thermoplastic resin (B) is 89.5 to 40 parts by mass, preferably 84 to 47 parts by mass, more preferably 78.5 to 54 parts by mass. And more preferably 76 to 58.3 parts by mass. It is preferable that the content ratio of the thermoplastic resin (B) is 89.5 parts by mass or less from the viewpoint of impact resistance. On the other hand, it is preferable that the content ratio of the thermoplastic resin (B) is 40 parts by mass or more from the viewpoint of fluidity.

(Polyester elastomer (C))
In the polyester elastomer (C) contained in the thermoplastic resin composition of the present embodiment, the hard segment is an aromatic polyester and the soft segment is an aliphatic polyether and/or an aliphatic polyester.

The aromatic polyester is not particularly limited, but examples thereof include polybutylene terephthalate and polyethylene terephthalate. Of these, polybutylene terephthalate is preferred.
The aliphatic polyether is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polypentamethylene glycol, polyhexamethylene glycol, and the like, and one kind or a mixture of two or more kinds thereof is used. be able to. Moreover, these copolymers can also be used.
The aliphatic polyester is not particularly limited, and examples thereof include polyesters of adipic acid and alkylene glycol such as polycaprolactone, polyenanthlactone, polycaprylolactone, polyethylene adipate, and polybutylene adipate; and succinic acid such as polyethylene succinate. Polyesters with alkylene glycols; polyesters with sebacic acid such as polybutylene sebacate and alkylene glycols; polyesters with dicarboxylic acids such as polycyclohexane dimethylene succinate and cyclohexane dimethylene glycol, and the like, or one or two of them. The above mixture can be used. Moreover, these copolymers can also be used.
Aliphatic polyethers are preferred as the soft segment of the polyester elastomer (C).

The composition ratio of the hard segment and the soft segment in the polyester elastomer (C) is preferably 20 to 70 mass% for the hard segment, more preferably 30 to 60 mass%, and preferably 30 to 80 mass% for the soft segment, and It is preferably in the range of 40 to 70% by mass.
The composition ratio of the hard segment is preferably 20% by mass or more from the viewpoint of chemical resistance, and is preferably 70% by mass or less from the viewpoint of impact resistance.

The Shore hardness D of the polyester elastomer (C) is preferably 20 to 80, more preferably 30 to 70, and further preferably 35 to 55.
The Shore hardness D of the polyester elastomer (C) is preferably 20 or more from the viewpoint of chemical resistance, and is preferably 80 or less from the viewpoint of impact resistance.
The Shore hardness D of the polyester elastomer (C) can be controlled in the above range by the ratio of the hard segment and the soft segment, and pellets dried with hot air at 90° C. for 3 hours or more using an injection molding machine, A 120 mm×75 mm×2 mm thick square plate can be molded under molding conditions of a predetermined cylinder temperature and mold temperature, and the measurement can be performed according to JIS K7215.

The polyester elastomer (C) is not limited to the following, but includes, for example, polycondensation of a dicarboxylic acid compound and a dihydroxy compound, polycondensation of an oxycarboxylic acid compound, ring-opening polycondensation of a lactone compound, or each of these components. Examples thereof include polyesters obtained by polycondensation of a mixture, and may be homopolyesters or copolyesters.

The dicarboxylic acid compound constituting the polyester elastomer (C) is not limited to the following, and examples thereof include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl. Aromatic dicarboxylic acids such as -4,4-dicarboxylic acid, diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate; 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4-dicarboxylic acid Aliphatic dicarboxylic acids such as acids; diphenyl ether dicarboxylic acids, diphenylethane dicarboxylic acids, succinic acid, oxalic acid, adipic acid, sebacic acid, dodecane dicarboxylic acids and other aliphatic dicarboxylic acids; and mixtures of these dicarboxylic acids. Also included are these alkyl, alkoxy, or halogen substitutions. Also, these dicarboxylic acid compounds can be used in the form of a derivative capable of forming an ester, for example, a lower alcohol ester such as dimethyl ester. In this embodiment, these dicarboxylic acid compounds may be used alone or in combination of two or more. Among these, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, adipic acid and dodecanedicarboxylic acid are preferable.

Examples of the dihydroxy compound constituting the polyester elastomer include, but are not limited to, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, butenediol, hydroquinone, resorcin, dihydroxydiphenyl ether, cyclohexanediol, and 2,2-bis. Examples thereof include (4-hydroxyphenyl)propane, which may be polyoxyalkylene glycols thereof and alkyl, alkoxy or halogen-substituted products thereof.
These dihydroxy compounds can be used alone or in combination of two or more.

Examples of the oxycarboxylic acid compound constituting the polyester elastomer include, but are not limited to, oxybenzoic acid, oxynaphthoic acid, and diphenyleneoxycarboxylic acid, and their alkyl, alkoxy, and halogen-substituted compounds. Good.
These oxycarboxylic acid compounds may be used alone or in combination of two or more.
Lactone compounds such as ε-caprolactone may be used for the production of polyester elastomers.

In the thermoplastic resin composition of the present embodiment, a graft copolymer (A), a thermoplastic resin (B) containing a polymer containing a vinyl cyanide monomer unit, and a polyester elastomer (C) When the total amount is 100 parts by mass, the content ratio of the polyester elastomer (C) is 0.5 to 15 parts by mass, preferably 1 to 15 parts by mass, more preferably 1.5 to 10 parts by mass. %, more preferably 1.5 to 6 parts by mass, and most preferably 1.8 to 3.7 parts by mass. It is preferable that the content of the polyester elastomer (C) is 0.5% by mass or more from the viewpoint of chemical resistance. On the other hand, it is preferable that the content ratio of the polyester elastomer (C) is 15 parts by mass or less from the viewpoint of heat resistance and prevention of phase separation.

(Other ingredients)
The thermoplastic resin composition of the present embodiment comprises a graft copolymer (A), a thermoplastic resin (B) containing a polymer containing vinyl cyanide monomer units, and a polyester elastomer (C). In addition, if necessary, one or more other optional components such as a lubricant may be included.

Examples of the lubricant include, but are not limited to, fatty acid metal salts, polyolefins, and polyamide elastomers.
When these lubricants are blended, the preferable amount thereof is 0.01 parts by mass or more and 10 parts by mass or less, when 100 parts by mass of the thermoplastic resin composition of the present embodiment is used. If it is 0.01 parts by mass or more, it is preferable from the viewpoint of fluidity and releasability, and if it is 10 parts by mass or less, it is preferable from the viewpoint of mechanical properties such as impact resistance and rigidity.

Examples of the fatty acid metal salt include, but are not limited to, salts of a metal and a fatty acid containing at least one selected from sodium, magnesium, calcium, aluminum, and zinc.
Examples of the fatty acid metal salt include, but are not limited to, sodium stearate, magnesium stearate, calcium stearate, aluminum stearate (mono, di, tri), zinc stearate, sodium montanate, calcium montanate, and ricinol. Calcium acid and calcium laurate are mentioned. Among these, stearic acid-based metal salts such as sodium stearate, magnesium stearate, calcium stearate, and zinc stearate are preferable.
Among the stearic acid-based metal salts, calcium stearate is more preferable from the viewpoint of suppressing silver stroke during molding.

Examples of the above-mentioned polyolefins include, but are not limited to, polymers produced from at least one kind of ethylene, propylene, α-olefin, and the like, and these also include polymers derived from the polymers.
Specific examples thereof include, but are not limited to, polypropylene, ethylene-propylene copolymer, polyethylene (high density, low density, linear low density), oxidized polyolefin, and graft-polymerized polyolefin.
Among these, oxidized polyolefin wax and polyolefin grafted with styrene resin are preferable, and polypropylene wax, polyethylene wax, oxidized polypropylene wax, oxidized polyethylene wax, acrylonitrile-styrene copolymer grafted polypropylene, acrylonitrile-styrene copolymer are preferred. Grafted polyethylene, styrene polymer-grafted polypropylene, and styrene polymer-grafted polyethylene are more preferable.

The polyamide elastomer as a lubricant is not limited to the following, and examples thereof include aminocarboxylic acids or lactams having 6 or more carbon atoms, and nylon mn salt having m+n of 12 or more. The hard segment (X) is not limited to the following. However, aminocarboxylic acids such as ω-aminocaproic acid, ω-aminoenoic acid, ω-aminocaprylic acid, ω-aminobergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid; caprolactam , Lactams such as laurolactam, nylon 6,6, nylon 6,10, nylon 6,12, nylon 11,6, nylon 11,10, nylon 12,6, nylon 11,12, nylon 12,10, nylon 12 , 12 and the like nylon salts.
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, and ethylene oxide. Examples thereof include block or random copolymers of propylene oxide and block or random copolymers 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 , and more preferably 2.5×10 ^{2 to} 4.0×10 ³ . The above number average molecular weight can be measured as a polystyrene reduced molecular weight by comparison with standard polystyrene by gel permeation chromatography (GPC).
Both ends of poly(alkylene oxide) glycol may be aminated or carboxylated before use.

When a lubricant is added to the thermoplastic resin composition of the present embodiment, an acid-modified or epoxy-modified modified resin may be further mixed in order to improve the compatibility.

[Method for producing thermoplastic resin composition]
(Method for producing graft copolymer (A))
The graft copolymer (A) is obtained by graft-polymerizing a predetermined vinyl monomer onto the rubber-like polymer contained in the graft copolymer (A). The method for producing the rubbery polymer contained in the graft copolymer (A) is not particularly limited, and examples thereof include bulk polymerization method, solution polymerization method, suspension polymerization method, bulk suspension polymerization method, and emulsion polymerization. Method can be used. Among these, the emulsion polymerization method, the suspension polymerization method, and the bulk suspension polymerization method are preferably used because a rubber component (dispersed phase) in the form of particles can be obtained and the particle diameter can be easily controlled. 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 method in which a rubbery polymer separately obtained by emulsion polymerization is used and a vinyl monomer is graft-polymerized may be used. The graft chain obtained here is preferably one compatible with the thermoplastic resin (B) from the viewpoint of impact resistance. In addition, after the particulate rubbery polymer is produced, the above graft polymerization may be continuously carried out in the same reactor, or the rubber particles may be once isolated as a latex and then graft polymerized again. ..

Specifically, one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers and acrylic monomers are radically added to the polybutadiene latex obtained by emulsion polymerization. The method of obtaining a graft copolymer by polymerizing is mentioned. Examples of the one or more monomers include, but are not limited to, styrene and acrylonitrile; styrene and methyl methacrylate; styrene; methyl methacrylate; and acrylonitrile.

(Method for producing thermoplastic resin (B) containing polymer containing vinyl cyanide monomer unit)
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, producing a copolymer by radical polymerization using two or more kinds of 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 a vinyl cyanide-based monomer unit and, if necessary, a thermoplastic resin other than the above can be produced. Further, the thermoplastic resin (B) may be produced together with the production of the graft copolymer (A). For example, the thermoplastic resin (B) may be formed by polymerizing the monomer itself added for graft-polymerizing the rubbery polymer when the graft copolymer (A) is produced.

(Method for producing polyester elastomer (C))
The polyester elastomer (C) can be produced by a known polymerization method. Usually, it can be produced by a two-step melt transesterification of an aromatic dicarboxylic acid, a low molecular weight polyalkylene glycol ether and a low molecular diol, and the production method is preferably a continuous or batch process.

(Method for producing thermoplastic resin composition)
The thermoplastic resin composition of this embodiment is obtained by mixing the graft copolymer (A), the thermoplastic resin (B), the polyester elastomer (C) and any other material. The method for mixing (kneading) the graft copolymer (A), the thermoplastic resin (B), and the polyester elastomer (C) is not particularly limited, and examples thereof include open roll, intensive mixer, internal mixer, coder, Examples thereof include a melt-kneading method using a kneader such as a continuous kneader with a twin-screw rotor or an extruder. As the extruder, either a single screw extruder or a twin screw extruder can be used. Regarding the method of supplying the graft copolymer (A), the thermoplastic resin (B), and the polyester elastomer (C) to the melt-kneader, all of them may be supplied to the same supply port at a time, and they may be respectively supplied. You may supply from a different supply port. For example, using an extruder having two charging ports, the graft copolymer (A) is supplied from the main charging port installed on the screw base side, and the auxiliary charging port is installed between the main charging port and the tip of the extruder. Alternatively, the thermoplastic resin (B) and the polyester elastomer (C) may be supplied and melt-kneaded.

When the graft copolymer (A), the thermoplastic resin (B) and the polyester elastomer (C) are supplied from the same supply port, they may be mixed in advance and then charged into an extruder hopper, Alternatively, they may be separately kneaded and then kneaded.

A preferable melt-kneading temperature varies depending on the type of the thermoplastic resin (B) and is not particularly limited. For example, when melt-kneading an acrylonitrile-styrene resin, it is preferable that the cylinder set temperature is about 180 to 270°C. By setting the melt-kneading temperature in such a range, the rubbery polymer can be dispersed well, and the impact resistance and appearance of the molded article can be improved in balance.

When an extruder is used, the temperature of the supply zone is preferably 30 to 200° C. of the cylinder temperature, and the temperature of the kneading zone in which melt kneading is performed is the melting point of crystalline resin +30 to 100. C., and in the case of an amorphous resin, it is preferable to set the Tg+60 to 150.degree. By thus setting the temperature in two stages, the graft copolymer (A), the thermoplastic resin (B) and the polyester elastomer (C) can be kneaded more smoothly, and a molded product, particularly an injection molded product. The surface smoothness is improved and the appearance is further improved. Further, by setting the cylinder temperature within the above range, more excellent appearance 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.

Further, when the thermoplastic resin composition of the present embodiment is produced by an extruder and a molded article 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. Is preferred. By setting the volatile content in such a range, more excellent appearance can be obtained. In order to make the volatile content in such a range, for example, the volatile content is sucked at a pressure reduction degree of −100 to −800 hPa from a vent hole provided between the center of the cylinder of the twin-screw extruder and the tip of the extruder. Preferably.

When the thermoplastic resin composition of the present embodiment is produced by an extruder, the extruded thermoplastic resin composition is directly cut into pellets, or formed into a strand and then cut with a pelletizer to be pelletized. be able to. The shape of the pellet is not particularly limited, and may be a general shape such as a cylinder, a prism, or a sphere, but a cylinder is preferable.

〔Molding〕
The molded product of the present embodiment is a molded product containing the above-mentioned thermoplastic resin composition and is obtained by molding a material containing the thermoplastic resin composition. For molding the material containing the thermoplastic resin composition, for example, injection molding, injection compression molding, extrusion molding, blow molding, inflation molding, vacuum molding, press molding and the like can be used.

In particular, examples of the injection molding method include injection compression molding, gas-assisted molding using nitrogen gas or carbon dioxide gas, and high-speed heat cycle molding for increasing the mold temperature. 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, the “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 and the like, a method of injecting a pressurized gas into a molded article after injecting a thermoplastic resin composition into a mold cavity, Japanese Patent No. 3819972, etc. As described, after injecting the thermoplastic resin composition into the mold cavity, a method of pressurizing a pressurized gas into the cavity corresponding to one side of the molded article, as described in Japanese Patent No. 3349070, Examples thereof include a method in which the plastic resin composition is filled with gas in advance and molded. Of these, the method of pressurizing the pressurized gas into the cavity corresponding to one surface of the molded product is preferable.

In the present embodiment, the holding pressure for preventing sink marks and warpage is preferably 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 mold temperature can be further suppressed and the holding pressure required to prevent sink and warp. The time can be shortened.

Using an injection molding machine from the pellets produced by kneading the kneaded product of the graft copolymer (A), the thermoplastic resin (B), the polyester elastomer (C), and other optional components as described above. An injection-molded product can be manufactured by. As a 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 appearance, the arithmetic mean surface roughness Ra of the mold is preferably 0.02 μm or less, more preferably 0.01 μm or less.

There is no particular limitation on the method for setting the arithmetic average surface roughness Ra of the mold within the above range, and for example, a diamond file, a grindstone, a ceramic grindstone, a ruby grindstone, a GC grindstone, or the like is used as an ultrasonic grinder or manual work. It can be raised by polishing. Further, the steel material of the die 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 that has been polished as described above may be used.

The mold temperature in the injection molding is set near the Vicat softening point of the kneaded product containing the graft copolymer (A), the thermoplastic resin (B) and the polyester elastomer (C) from the viewpoint of appearance, and molding is performed. It is preferable to carry out. Specifically, it is preferably −25 to +20° C., more preferably −15 to +5° C., with respect to the Vicat softening point according to ISO306. When the mold temperature is within such a range, the transferability to the cavity surface is further improved, and an injection-molded article having more excellent appearance can be obtained.

Generally, if the temperature of the mold (cavity surface) is increased, the time until cooling becomes longer, which causes 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 appearance and productivity. The surface of the molded product is preferably cooled at 1 to 100° C./second from the viewpoint of the appearance of the molded product. The cooling rate of the surface of this molded product is more preferably 30 to 90° C./second, further preferably 40 to 80° C./second.

Further, a molding method in which the mold temperature is raised or lowered by using a mold having steam piping or a heating wire built therein, and a molding method using supercritical CO ₂ can also be preferably used.

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

In the manufacturing process of the injection-molded article of the thermoplastic resin composition of the present embodiment, the injection speed is preferably 1 to 50 mm/s, more preferably 5 to 30 mm/s, from the viewpoint of appearance. ..

The molded article of the present embodiment is a phosphite-based, hindered phenol-based, benzotriazole-based, benzophenone-based, benzoae-based, and cyanoacrylate-based ultraviolet absorber and antioxidant within a range capable of achieving the object of the present invention; Fatty acids, acid ester-based and acid amide-based lubricants and plasticizers such as higher alcohols; montanic acid and its salts, esters thereof, half esters thereof, stearyl alcohol, release agents such as stellaamide and ethylene wax; phosphorous acid Anti-coloring agents such as salts and hypophosphite salts; nucleating agents, amine-based, sulfonic acid-based, polyether-based antistatic agents; 1,3-phenylene bis(2,6-dimethylphenyl-phosphate), tetra Phosphorus flame retardants such as phenyl-m-phenylene bisphosphate, phenoxyphosphoryl and phenoxyphosphazene; and one or more optional additives such as halogen flame retardants may be contained. From the viewpoint of weather resistance, the amount of each of these added is preferably 0.01 to 3% by mass, and more preferably 0.05 to 1% by mass.

For the purpose of imparting appearance, the molded product may include, for example, an inorganic pigment, an organic pigment, a metallic pigment, and a dye, although not limited thereto. Among the colorants, those which make the color of the molded product white, black or red can give a particularly outstanding high-class appearance to the molded product and are preferably used.

Examples of the inorganic pigment include, but are not limited to, titanium oxide, carbon black, titanium yellow, iron oxide pigment, ultramarine blue, cobalt blue, chromium oxide, spinel green, lead chromate pigment, and cadmium pigment. Examples include pigments.

Examples of the organic pigment include, but are not limited to, for example, azo lake pigments, benzimidazolone pigments, dialide pigments, azo pigments such as condensed azo pigments, phthalocyanine blue, phthalocyanine pigments such as phthalocyanine green, and isoindo Examples thereof include condensed polycyclic pigments such as linone pigments, quinophthalone pigments, quinacridone pigments, perylene pigments, anthraquinone pigments, perinone pigments and dioxazine violet.

Examples of the metallic pigment include, but are not limited to, for example, scaly aluminum metallic pigments, spherical aluminum pigments used to improve the weld appearance, and mica powder for pearly metallic pigments. Other examples include polyhedral particles of inorganic substances such as glass coated with a metal by plating or sputtering.

Examples of the dye include, but are not limited to, nitroso dye, nitro dye, azo dye, stilbene azo dye, ketoimine dye, triphenylmethane dye, xanthene dye, acridine dye, quinoline dye, methine/polymethine dye. , Thiazole dyes, indamine/indophenol dyes, azine dyes, oxazine dyes, thiazine dyes, sulfur dyes, aminoketone/oxyketone dyes, anthraquinone dyes, indigoid dyes, and phthalocyanine dyes.

These colorants may be used alone or in combination of two or more. From the viewpoint of color tone, the amount of these added is preferably 0.05 to 2% by mass, and more preferably based on the total mass of the graft copolymer (A), the thermoplastic resin (B), and the polyester elastomer (C). It is 0.1 to 1.5 mass %.

The molded product of this embodiment may be a combination of any of the above items.
[Cosmetic container]
The molded article of the present embodiment is particularly preferable for use as a cosmetic container, while maintaining excellent impact resistance even when colored, having good gloss, and exerting an excellent chemical resistance effect, which is preferable. ..
In particular, it is more preferably used as a cosmetic container having excellent chemical resistance to sunscreen cosmetics.

According to the present embodiment, it is possible to provide a molded article having good gloss and chemical resistance while maintaining excellent impact resistance even when colored, and a thermoplastic resin composition from which the molded article can be obtained. ..

Hereinafter, the present embodiment will be described in detail with reference to specific examples and comparative examples, but the present embodiment is not limited to the following examples. The evaluation methods and the physical property measurement methods applied to the examples and comparative examples are as follows.

Charpy impact strength with notch (kJ/m ² ) was used for evaluation of impact resistance.

((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 of length 8 cm×width 1 cm, thickness 4 mm is cut out. It was Then, the Charpy impact strength with notch was measured for the obtained test piece according to ISO179. If the Charpy impact strength with notch is 24 kJ/m ² or more, it is judged that it can be satisfactorily used without any practical problems in applications such as general equipment and household appliances cosmetic containers, and the impact resistance of the test piece is evaluated as follows. did.
“Not allowed” if the Charpy impact strength with notch is less than 24 kJ/m ^2.
Notched Charpy impact strength of 24 kJ/m ² or more and less than 26 kJ/m ² is “OK”
Notch Charpy impact strength of 26 kJ/m ² or more and less than 28 kJ/m ² is “good”
Notch Charpy impact strength of 28 kJ/m ² or more is “excellent”

((2) Flexural modulus (MPa))
Using the test piece prepared in "(1) Charpy impact strength with notch", the flexural modulus was measured according to ISO178 and evaluated as follows.
"Improper" if the flexural modulus is less than 1800 MPa
Bending elastic modulus of 1800 MPa or more and less than 2400 MPa is “OK”.
Bending elastic modulus of 2400 MPa or more and less than 2500 MPa is “good”.
Bending elastic modulus of 2500 MPa or more and less than 2600 MPa is “excellent”
"Excellent" if the flexural modulus is 2600 MPa or more

((3) Gloss (%))
Using a TOSHIBA MACHINE injection molding machine (product number: EC60N), a flat plate of 5 cm×9 cm and 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. The mold used was one having a No. 10000 file and its surface polished until the surface roughness Ra reached 0.01 μm. After leaving this flat plate for 24 hours in an air atmosphere at a temperature of 23° C. and a relative humidity of 50%, the surface gloss of the flat plate at an incident angle of 60 degrees was measured using a Suga Test Instruments variable angle gloss meter (product number: UGV-5K). Was measured. It was judged that a gloss of 89% or more would facilitate obtaining a high-quality appearance, and the evaluation was made as follows.
"Improper" if the gloss is less than 89%
"OK" when the gloss is 89% or more and less than 92%
"Good" when the gloss is 92% or more and less than 94%
"Excellent" when the gloss is 94% or more and less than 95%
A gloss of 95% or more is "excellent"

((4) Yellowness (YI: Yellow Index))
The flat plate produced by the above-mentioned "(4) Gloss" was left for 24 hours in an air atmosphere having a temperature of 23°C and a relative humidity of 50%, and then a multi-source spectrophotometer (product number: MSC-5N-GV5) manufactured by Suga Test Instruments Co., Ltd. Was used to measure the yellowness index (YI) of the flat plate. The measurement conditions are as follows.
・Spectral 5nm optical reflection ・Light source: C light 2° field of view ・Measurement (d/8) condition excluding specular reflection light ・Observation field of view: diameter 15mm
It was judged that high-quality appearance and color tone were easily obtained by setting the yellowness to less than 25%, and the evaluation was performed as follows.
"No" for yellowness of 25% or more
"OK" if the yellowness is 24% or more and less than 25%
"Good" if the yellowness is 23% or more and less than 24%
"Excellent" if the yellowness is 22% or more and less than 23%
"Excellent" if the yellowness is less than 22%

((5) Liquidity (MVR))
The fluidity of the thermoplastic resin composition was evaluated by melt volume flow rate (MVR) (cm ³ /10 minutes). Using the pellets obtained in each Example and Comparative Example described below, MVR was measured under the conditions of 220° C. and 10 kg load according to ISO1133, and evaluated as follows.
"No" for MVR less than 2
"OK" if the MVR is 2 or more and less than 5
Good with MVR of 5 or more and less than 8
"Excellent" if the MVR is 8 or more

((6) Charpy impact retention during coloring (kJ/m ² ))
Using an injection molding machine manufactured by Toshiba Machine (product number: EC60N), a colored kneaded product containing 100 parts by mass of the thermoplastic resin composition and 1 part by mass of titanium oxide is molded at a cylinder temperature of 250°C and a mold temperature of 60°C. Then, a test piece having a length of 8 cm×a width of 1 cm and a thickness of 4 mm was cut out. Then, the Charpy impact strength of the obtained test piece was measured according to ISO179. From the measurement results, the Charpy impact retention rate when the test piece was colored was calculated and evaluated as follows.
"Not allowed" when the Charpy impact retention rate when coloring is less than 85%
"OK" if the Charpy impact retention rate during coloring is 85% or more and less than 87%
Charpy impact retention rate of 87% or more and less than 89% when colored is “good”
"Excellent" when the Charpy impact retention rate during coloring is 89% or more and less than 91%
"Best" when the Charpy impact retention rate is 91% or more when colored
The Charpy impact retention rate during coloring is defined by the ratio (%) of the Charpy impact strength evaluated by the method described in (6) to the Charpy impact strength evaluated by the method described in (1) above. ..

((7) Resistance to sunscreen cosmetics (cracking of molded products)
A 10 mm long test piece was cut out from a 3 mm thick compression molded product. Then, the obtained test piece was annealed at 80° C. for 24 hours, attached to a bending bar, and applied with a sunscreen cosmetic.
Then, the test piece was allowed to stand in an environment of room temperature of 23° C. and humidity of 50% for 24 hours, the stop position (inch) of the generated crack was measured, and the critical strain (%) was obtained from the following formula.
Critical strain (%) = "test piece thickness (inch)" x √3/[2 x (3 + 2 x "crack stop position (inch)") ^1.5 ]
From the obtained critical strain (%), the resistance (chemical resistance) of the test piece to the sunscreen cosmetics was evaluated according to the following criteria.
"Improper" if the critical strain is less than 0.36%
Those with a critical strain of 0.36% or more and less than 0.40% are “OK”
"Good" when the critical strain is 0.40% or more and less than 0.44%
"Best" with a critical strain of 0.44% or more
As a sunscreen cosmetic, an anesthesia whitening essence facial UV (SPF50+PA++++) manufactured by Shiseido was used.

(Characteristics of Graft Copolymer and Thermoplastic Resin Constituting Thermoplastic Resin Composition)
<Method for measuring mass average particle diameter of rubbery polymer (a1) and rubbery polymer (a2)>
The mass average particle diameters of the rubbery polymer (a1) and the rubbery polymer (a2) were determined by the following method. First, an ultrathin section was prepared from a molded article of the thermoplastic resin composition, and the ultrathin section was dyed with a dyeing agent such as osmium tetroxide and ruthenium tetroxide. Then, the stained ultrathin section was photographed with a transmission electron microscope (TEM), and the image was analyzed for an arbitrary range (15 μm×15 μm) of the ultrathin section. The image was analyzed using image analysis software "A image-kun" (manufactured by Asahi Kasei Engineering Co., Ltd.).

<Ratio of rubbery polymer (a1) and rubbery polymer (a2) in rubbery polymer>
A rubbery polymer having a mass average particle diameter of 0.20 μm or more and less than 0.50 μm, which is measured by <Method for measuring mass average particle diameter of rubbery polymer (a1) and rubbery polymer (a2)>. The content ratios of (a1) and the rubber polymer (a2) having a mass average particle diameter of 0.10 μm or more and less than 0.20 μm with respect to the total amount thereof were calculated.

<SD value “(d84%−d16%)/2” of rubbery polymers (a1) and (a2)>
Particles of the rubber-like polymer (a1) and the rubber-like polymer (a2) were prepared in the same manner as in <Measurement method of mass average particle diameter of rubber-like polymer (a1) and rubber-like polymer (a2)>. The diameter was measured, and the image photographed by a transmission electron microscope (TEM) was analyzed. d84%: particle diameter at the point where the cumulative curve becomes 84% in the particle diameter distribution (μm), and d16%: particle diameter The particle diameter (μm) at the point where the cumulative curve was 16% in the distribution was obtained, and the SD value “(d84%−d16%)/2” of each was calculated.

<“Half width/peak height” and peak top position of peak I>
FIG. 1 is an example of a temperature-loss tangent (tan δ) curve of the graft copolymer (A). The horizontal axis represents temperature and the vertical axis represents tan δ. FIG. 2 is a diagram showing a peak top of peak I, a peak height, and a half width in an example of a temperature-loss tangent (tan δ) curve of the graft copolymer. As shown in FIG. 2, the intersection of the baseline of peak I (broken line in FIG. 2) and the perpendicular from peak top of peak I was designated as point P. The peak height of peak I was determined from the difference between tan δ at the peak top of peak I and tan δ at point P, and the “half-width/peak height” of peak I was determined.

<Graft rate>
The thermoplastic resin composition was dissolved in acetone and separated into an acetone-soluble component and an acetone-insoluble component by a centrifugal separator. At this time, the component insoluble in acetone is a trunk polymer composed of a rubbery polymer and a graft chain graft-polymerized on the trunk polymer, and is a component containing the graft copolymer (A) in the thermoplastic resin composition. ..
The component soluble in acetone is a component containing the thermoplastic resin (B) in the thermoplastic resin composition.
A component insoluble in acetone was analyzed by a Fourier transform infrared spectrophotometer (FT-IR) to obtain the constituent ratio of the trunk polymer and the graft chain, and the graft ratio was calculated based on the result.

<Content ratio (composition ratio) of each monomer unit in all monomer units in the graft copolymer (A)>
Acetone-insoluble components obtained by the same method as in the measurement of <graft ratio> above were analyzed by a Fourier transform infrared spectrophotometer (FT-IR) to obtain all monomers in the graft copolymer (A). The content ratio (composition ratio) of each monomer unit in the monomer unit was calculated.

<Content ratio (D) of vinyl cyanide-based monomer unit in all monomer units other than rubber-like polymer of graft copolymer>
In the graft copolymer (A), the content ratio (D) of vinyl cyanide-based monomer units in all the monomer units other than the rubbery polymer is determined by Fourier transform infrared spectrophotometer (FT-IR). Sought by.
Specifically, the content ratio (D) of vinyl cyanide-based monomer units in all the monomer units other than the rubber-like polymer in the graft copolymer (A) is calculated in advance based on the total monomer amount in the rubber-like polymer. The content ratio (composition ratio) of each monomer unit in the body unit is obtained, and then the content ratio (composition ratio) of each monomer unit in all the monomer units in the graft copolymer (A). Was determined by FT-IR, and the content ratio of the rubbery polymer in the graft copolymer (A) and the graft chain graft-polymerized to the rubbery polymer was taken into consideration.

<Content Ratio (E) of Vinyl Cyanide Monomer Unit in All Monomer Units of Thermoplastic Resin (B)>
The content ratio (E) of vinyl cyanide-based monomer units in all the monomer units in the thermoplastic resin (B) was determined by a Fourier transform infrared spectrophotometer (FT-IR).

<Reduced specific viscosity of component derived from graft chain of graft copolymer (A)>
The reduced specific viscosity (ηsp/c) of the component derived from the graft chain of the graft copolymer (A) was measured by dissolving a solution of 0.25 g of a measurement sample in 50 mL of 2-butanone at 30° C. in a Cannon-Fenske type capillary tube. It was determined by measuring the viscosity using. The component derived from the graft chain of the graft copolymer (A) was obtained through oxidative decomposition of the graft copolymer (A). Ozone decomposition was used as the oxidative decomposition method. Specifically, the method described in Kobunshi Kobunshi (Fumio Ide et al., vol. 32, No. 7, PP. 439-444 (July. 1975)) was used. In this document, the isolated branch polymer corresponds to the component derived from the graft chain.

<Reduced specific viscosity of thermoplastic resin (B)>
The reduced specific viscosity (ηsp/c) of the thermoplastic resin (B) is obtained by measuring a solution of 0.25 g of a measurement sample dissolved in 50 mL of 2-butanone at 30° C. using a Cannon-Fenske type capillary tube. Sought by.

(Production Example 1) [Production of rubber latex (L-1)]
Butadiene 93 parts by mass, acrylonitrile 2 parts by mass, styrene 5 parts by mass, deionized water (iron concentration: less than 0.02 ppm) 67 parts by mass, potassium rosinate 0.54 parts by mass, sodium stearate 0.06 parts by mass, tasha. 0.25 parts by mass of lead decyl mercaptan, 0.15 parts by mass of sodium hydroxide, 0.35 parts by mass of sodium persulfate, and 0.5 parts by mass of sodium bicarbonate were placed in a pressure vessel equipped with a stirrer degassed to vacuum. After being stored, the temperature was raised from room temperature to 65° C. to start polymerization.
After 7 hours from the start of polymerization, 0.72 parts by mass of potassium rosinate and 0.08 parts by mass of sodium stearate are added, and after 4 hours, 0.63 parts by mass of potassium rosinate and 0.07 parts by mass of sodium stearate. Parts, and after further 4 hours, 0.18 parts by mass of potassium rosinate and 0.02 parts by mass of sodium stearate were added, and the system was heated to 80° C., then 0.45 parts by mass of potassium rosinate, 0.05 parts by mass of sodium stearate and 15 parts by mass of deionized water were added. After the lapse of 30 hours from the start of polymerization, the system was cooled to complete the polymerization.
In the obtained polymerization liquid, the solid content was 54.9% by mass, and the mass average particle diameter of the solid content measured by Nikkiso Co., Ltd. Microtrac particle size analyzer (trade name: nanotrac150) was 340 nm. The swelling index measured by the above method was 22%.
Moreover, the composition ratio of the monomer in the rubbery polymer which is the solid content is measured by using a Fourier transform infrared spectrophotometer (FT-IR) (manufactured by JASCO Corporation, product number: FT/IR-7000). As a result of analysis, the butadiene unit was 93.1% by mass, the acrylonitrile unit was 1.8% by mass, and the styrene unit was 5.1% by mass.

(Production Example 2) [Production of rubber latex (L-2)]
Butadiene 93 parts by mass, acrylonitrile 2 parts by mass, styrene 5 parts by mass, deionized water (iron concentration: less than 0.02 ppm) 75 parts by mass, potassium rosinate 0.54 parts by mass, sodium stearate 0.06 parts by mass, tasha. 0.25 parts by mass of lead decyl mercaptan, 0.15 parts by mass of sodium hydroxide, 0.35 parts by mass of sodium persulfate, and 0.5 parts by mass of sodium bicarbonate were placed in a pressure vessel equipped with a stirrer degassed to vacuum. After being stored, the temperature was raised from room temperature to 65° C. to start polymerization.
After 7 hours from the start of polymerization, 0.72 parts by mass of potassium rosinate and 0.08 parts by mass of sodium stearate are added, and after 4 hours, 0.63 parts by mass of potassium rosinate and 0.07 parts by mass of sodium stearate. Parts, and after further 4 hours, 0.18 parts by mass of potassium rosinate and 0.02 parts by mass of sodium stearate were added, and the system was heated to 80° C., then 0.45 parts by mass of potassium rosinate, 0.05 parts by mass of sodium stearate and 15 parts by mass of deionized water were added. After the lapse of 23 hours from the start of the polymerization, the system was cooled to complete the polymerization.
In the obtained polymerization liquid, the solid content was 52.6% by mass, and the mass average particle diameter of the solid content measured by Nikkiso Co., Ltd. Microtrac particle size analyzer (trade name: nanotrac150) was 260 nm. The swelling index measured by the above method was 23%.
Moreover, the composition ratio of the monomer in the rubbery polymer which is the solid content is measured by using a Fourier transform infrared spectrophotometer (FT-IR) (manufactured by JASCO Corporation, product number: FT/IR-7000). As a result of analysis, the butadiene unit was 93.2% by mass, the acrylonitrile unit was 1.8% by mass, and the styrene unit was 5.0% by mass.

(Production Example 3) [Production of rubber latex (L-3)]
83 parts by mass of butadiene, 2 parts by mass of acrylonitrile, 15 parts by mass of styrene, 67 parts by mass of deionized water (iron concentration: less than 0.02 ppm), 0.54 parts by mass of potassium rosinate, 0.06 parts by mass of sodium stearate, tasha 0.25 parts by mass of lead decyl mercaptan, 0.15 parts by mass of sodium hydroxide, 0.35 parts by mass of sodium persulfate, and 0.5 parts by mass of sodium bicarbonate were placed in a pressure vessel equipped with a stirrer degassed to vacuum. After being stored, the temperature was raised from room temperature to 65° C. to start polymerization.
After 7 hours from the start of polymerization, 0.72 parts by mass of potassium rosinate and 0.08 parts by mass of sodium stearate are added, and after 4 hours, 0.63 parts by mass of potassium rosinate and 0.07 parts by mass of sodium stearate. Parts, and after further 4 hours, 0.18 parts by mass of potassium rosinate and 0.02 parts by mass of sodium stearate were added, and the system was heated to 80° C., then 0.45 parts by mass of potassium rosinate, 0.05 parts by mass of sodium stearate and 15 parts by mass of deionized water were added. After the lapse of 30 hours from the start of polymerization, the system was cooled to complete the polymerization.
In the obtained polymerization liquid, the solid content was 54.5% by mass, and the mass average particle diameter of the solid content measured by Nikkiso Co., Ltd. Microtrac particle size analyzer (trade name: nanotrac150) was 335 nm. The swelling index measured by the above method was 21%.
Moreover, the composition ratio of the monomer in the rubbery polymer which is the solid content is measured by using a Fourier transform infrared spectrophotometer (FT-IR) (manufactured by JASCO Corporation, product number: FT/IR-7000). As a result of analysis, the butadiene unit was 83.3 mass %, the acrylonitrile unit was 1.9 mass %, and the styrene unit was 14.8 mass %.

(Production Example 4) [Production of rubber latex (L-4)]
Butadiene 93 parts by mass, acrylonitrile 2 parts by mass, styrene 5 parts by mass, deionized water (iron concentration: less than 0.02 ppm) 67 parts by mass, potassium rosinate 0.54 parts by mass, sodium stearate 0.06 parts by mass, tasha. 0.35 parts by mass of lead decyl mercaptan, 0.15 parts by mass of sodium hydroxide, 0.35 parts by mass of sodium persulfate, and 0.5 parts by mass of sodium bicarbonate were placed in a pressure vessel equipped with a stirrer that was degassed to vacuum. After being stored, the temperature was raised from room temperature to 65° C. to start polymerization.
After 7 hours from the start of polymerization, 0.72 parts by mass of potassium rosinate and 0.08 parts by mass of sodium stearate are added, and after 4 hours, 0.63 parts by mass of potassium rosinate and 0.07 parts by mass of sodium stearate. Parts, and after further 4 hours, 0.18 parts by mass of potassium rosinate and 0.02 parts by mass of sodium stearate were added, and the system was heated to 80° C., then 0.45 parts by mass of potassium rosinate, 0.05 parts by mass of sodium stearate and 15 parts by mass of deionized water were added. After the lapse of 30 hours from the start of polymerization, the system was cooled to complete the polymerization.
In the obtained polymerization liquid, the solid content was 54.0% by mass, and the mass average particle diameter of the solid content measured by Nikkiso Co., Ltd. Microtrac particle size analyzer (trade name: nanotrac150) was 335 nm. The swelling index measured by the above method was 15%.
Moreover, the composition ratio of the monomer in the rubbery polymer which is the solid content is measured by using a Fourier transform infrared spectrophotometer (FT-IR) (manufactured by JASCO Corporation, product number: FT/IR-7000). As a result of analysis, the butadiene unit was 93.1% by mass, the acrylonitrile unit was 1.7% by mass, and the styrene unit was 5.2% by mass.

(Production Example 5) [Production of rubber latex (L-5)]
Butadiene 93 parts by mass, acrylonitrile 2 parts by mass, styrene 5 parts by mass, deionized water (iron concentration: less than 0.02 ppm) 67 parts by mass, potassium rosinate 0.54 parts by mass, sodium stearate 0.06 parts by mass, tasha. 0.15 parts by mass of lead decyl mercaptan, 0.15 parts by mass of sodium hydroxide, 0.35 parts by mass of sodium persulfate, and 0.5 parts by mass of sodium bicarbonate were placed in a pressure vessel equipped with a stirrer that was degassed to vacuum. After being stored, the temperature was raised from room temperature to 65° C. to start polymerization.
After 7 hours from the start of polymerization, 0.72 parts by mass of potassium rosinate and 0.08 parts by mass of sodium stearate are added, and after 4 hours, 0.63 parts by mass of potassium rosinate and 0.07 parts by mass of sodium stearate. Parts, and after further 4 hours, 0.18 parts by mass of potassium rosinate and 0.02 parts by mass of sodium stearate were added, and the system was heated to 80° C., then 0.45 parts by mass of potassium rosinate, 0.05 parts by mass of sodium stearate and 15 parts by mass of deionized water were added. After the lapse of 30 hours from the start of polymerization, the system was cooled to complete the polymerization.
In the obtained polymerization liquid, the solid content was 54.8% by mass, and the mass average particle size of the solid content measured by Nikkiso Co., Ltd. Microtrac particle size analyzer (trade name: nanotrac150) was 340 nm. The swelling index measured by the above method was 35%.
Moreover, the composition ratio of the monomer in the rubbery polymer which is the solid content is measured by using a Fourier transform infrared spectrophotometer (FT-IR) (manufactured by JASCO Corporation, product number: FT/IR-7000). As a result of analysis, the butadiene unit was 93.3 mass %, the acrylonitrile unit was 1.7 mass %, and the styrene unit was 5.0 mass %.

(Production Example 6) [Production of rubber latex (L-6)]
Butadiene 93 parts by mass, acrylonitrile 2 parts by mass, styrene 5 parts by mass, deionized water (iron concentration: less than 0.02 ppm) 67 parts by mass, potassium rosinate 0.27 parts by mass, sodium stearate 0.03 parts by mass, tasha. 0.25 parts by mass of lead decyl mercaptan, 0.15 parts by mass of sodium hydroxide, 0.35 parts by mass of sodium persulfate, and 0.5 parts by mass of sodium bicarbonate were placed in a pressure vessel equipped with a stirrer degassed to vacuum. After being stored, the temperature was raised from room temperature to 65° C. to start polymerization.
After 7 hours from the start of polymerization, 0.72 parts by mass of potassium rosinate and 0.08 parts by mass of sodium stearate are added, and after 4 hours, 0.63 parts by mass of potassium rosinate and 0.07 parts by mass of sodium stearate. Parts, and after further 4 hours, 0.18 parts by mass of potassium rosinate and 0.02 parts by mass of sodium stearate were added, and the system was heated to 80° C., then 0.45 parts by mass of potassium rosinate, 0.05 parts by mass of sodium stearate and 15 parts by mass of deionized water were added. After the lapse of 30 hours from the start of polymerization, the system was cooled to complete the polymerization.
In the obtained polymerization liquid, the solid content was 54.4% by mass, and the mass average particle diameter of the solid content measured by Nikkiso Co., Ltd. Microtrac particle size analyzer (trade name: nanotrac150) was 330 nm. The swelling index measured by the above method was 22%.
Moreover, the composition ratio of the monomer in the rubbery polymer which is the solid content is measured by using a Fourier transform infrared spectrophotometer (FT-IR) (manufactured by JASCO Corporation, product number: FT/IR-7000). As a result of analysis, the butadiene unit was 93.1% by mass, the acrylonitrile unit was 1.8% by mass, and the styrene unit was 5.1% by mass.

(Production Example 7) [Production of rubber latex (L-7)]
Butadiene 93 parts by mass, acrylonitrile 2 parts by mass, styrene 5 parts by mass, deionized water (iron concentration: less than 0.02 ppm) 60 parts by mass, potassium rosinate 0.54 parts by mass, sodium stearate 0.06 parts by mass, tasha. 0.25 parts by mass of lead decyl mercaptan, 0.15 parts by mass of sodium hydroxide, 0.35 parts by mass of sodium persulfate, and 0.5 parts by mass of sodium bicarbonate were placed in a pressure vessel equipped with a stirrer degassed to vacuum. After being stored, the temperature was raised from room temperature to 65° C. to start polymerization.
After 7 hours from the start of polymerization, 0.72 parts by mass of potassium rosinate and 0.08 parts by mass of sodium stearate are added, and after 4 hours, 0.63 parts by mass of potassium rosinate and 0.07 parts by mass of sodium stearate. Parts, and after further 4 hours, 0.18 parts by mass of potassium rosinate and 0.02 parts by mass of sodium stearate were added, and the system was heated to 80° C., then 0.45 parts by mass of potassium rosinate, 0.05 parts by mass of sodium stearate and 15 parts by mass of deionized water were added. After the lapse of 35 hours from the start of the polymerization, the system was cooled to complete the polymerization.
In the obtained polymerization liquid, the solid content was 57.1% by mass, and the mass average particle diameter of the solid content measured by Nikkiso Co., Ltd. Microtrac particle size analyzer (trade name: nanotrac150) was 450 nm. The swelling index measured by the above method was 21%.
Moreover, the composition ratio of the monomer in the rubbery polymer which is the solid content is measured by using a Fourier transform infrared spectrophotometer (FT-IR) (manufactured by JASCO Corporation, product number: FT/IR-7000). As a result of analysis, the butadiene unit was 93.3 mass %, the acrylonitrile unit was 1.6 mass %, and the styrene unit was 5.1 mass %.

(Production Example 8) [Production of rubber latex (L-8)]
Butadiene 93 parts by mass, acrylonitrile 2 parts by mass, styrene 5 parts by mass, deionized water (iron concentration: less than 0.02 ppm) 50 parts by mass, potassium rosinate 0.54 parts by mass, sodium stearate 0.06 parts by mass, tasha 0.25 parts by mass of lead decyl mercaptan, 0.15 parts by mass of sodium hydroxide, 0.35 parts by mass of sodium persulfate, and 0.5 parts by mass of sodium bicarbonate were placed in a pressure vessel equipped with a stirrer degassed to vacuum. After being stored, the temperature was raised from room temperature to 65° C. to start polymerization.
After 7 hours from the start of polymerization, 0.72 parts by mass of potassium rosinate and 0.08 parts by mass of sodium stearate are added, and after 4 hours, 0.63 parts by mass of potassium rosinate and 0.07 parts by mass of sodium stearate. Parts, and after further 4 hours, 0.18 parts by mass of potassium rosinate and 0.02 parts by mass of sodium stearate were added, and the system was heated to 80° C., then 0.45 parts by mass of potassium rosinate, 0.05 parts by mass of sodium stearate and 15 parts by mass of deionized water were added. After 40 hours from the start of the polymerization, the system was cooled to complete the polymerization.
In the obtained polymerization liquid, the solid content was 60.6% by mass, and the mass average particle diameter of the solid content measured by Nikkiso Co., Ltd. Microtrac particle size analyzer (trade name: nanotrac150) was 800 nm. The swelling index measured by the above method was 21%.
Moreover, the composition ratio of the monomer in the rubbery polymer which is the solid content is measured by using a Fourier transform infrared spectrophotometer (FT-IR) (manufactured by JASCO Corporation, product number: FT/IR-7000). As a result of analysis, the butadiene unit was 93.0% by mass, the acrylonitrile unit was 1.9% by mass, and the styrene unit was 5.1% by mass.

(Production Example 9) [Production of rubber latex (L-9)]
Butadiene 93 parts by mass, acrylonitrile 2 parts by mass, styrene 5 parts by mass, deionized water (iron concentration: less than 0.02 ppm) 92 parts by mass, potassium rosinate 0.54 parts by mass, sodium stearate 0.06 parts by mass, tasha. 0.25 parts by mass of lead decyl mercaptan, 0.15 parts by mass of sodium hydroxide, 0.35 parts by mass of sodium persulfate, and 0.5 parts by mass of sodium bicarbonate were placed in a pressure vessel equipped with a stirrer degassed to vacuum. After being stored, the temperature was raised from room temperature to 65° C. to start polymerization.
After 7 hours from the start of polymerization, 0.72 parts by mass of potassium rosinate and 0.08 parts by mass of sodium stearate are added, and after 4 hours, 0.63 parts by mass of potassium rosinate and 0.07 parts by mass of sodium stearate. Parts, and after further 4 hours, 0.18 parts by mass of potassium rosinate and 0.02 parts by mass of sodium stearate were added, and the system was heated to 80° C., then 0.45 parts by mass of potassium rosinate, 0.05 parts by mass of sodium stearate and 15 parts by mass of deionized water were added. After 15 hours had passed from the start of the polymerization, the system was cooled to complete the polymerization.
In the obtained polymerization liquid, the solid content was 48.3 mass%, and the mass average particle diameter of the solid content measured by Nikkiso Co., Ltd. Microtrac particle size analyzer (trade name: nanotrac150) was 180 nm. The swelling index measured by the above method was 22%.
Moreover, the composition ratio of the monomer in the rubbery polymer which is the solid content is measured by using a Fourier transform infrared spectrophotometer (FT-IR) (manufactured by JASCO Corporation, product number: FT/IR-7000). As a result of analysis, the butadiene unit was 93.2% by mass, the acrylonitrile unit was 1.7% by mass, and the styrene unit was 5.1% by mass.

(Production Example 10) [Production of rubber latex (L-10)]
Butadiene 93 parts by mass, acrylonitrile 2 parts by mass, styrene 5 parts by mass, deionized water (iron concentration: less than 0.02 ppm) 92 parts by mass, potassium rosinate 0.27 parts by mass, sodium stearate 0.03 parts by mass, tasha. 0.25 parts by mass of lead decyl mercaptan, 0.15 parts by mass of sodium hydroxide, 0.35 parts by mass of sodium persulfate, and 0.5 parts by mass of sodium bicarbonate were placed in a pressure vessel equipped with a stirrer that was degassed to vacuum. After being stored, the temperature was raised from room temperature to 65° C. to start polymerization.
After 7 hours from the start of polymerization, 0.72 parts by mass of potassium rosinate and 0.08 parts by mass of sodium stearate are added, and after 4 hours, 0.63 parts by mass of potassium rosinate and 0.07 parts by mass of sodium stearate. Parts, and after further 4 hours, 0.18 parts by mass of potassium rosinate and 0.02 parts by mass of sodium stearate were added, and the system was heated to 80° C., then 0.45 parts by mass of potassium rosinate, 0.05 parts by mass of sodium stearate and 15 parts by mass of deionized water were added. After 15 hours had passed from the start of the polymerization, the system was cooled to complete the polymerization.
In the obtained polymerization liquid, the solid content was 48.3% by mass, and the mass average particle diameter of the solid content measured by Nikkiso Co., Ltd. Microtrac particle size analyzer (trade name: nanotrac150) was 180 nm. The swelling index measured by the above method was 23%.
Moreover, the composition ratio of the monomer in the rubbery polymer which is the solid content is measured by using a Fourier transform infrared spectrophotometer (FT-IR) (manufactured by JASCO Corporation, product number: FT/IR-7000). As a result of analysis, the butadiene unit was 93.0 mass %, the acrylonitrile unit was 1.8 mass %, and the styrene unit was 5.2 mass %.

(Production Example 11) [Production of rubber latex (L-11)]
Butadiene 93 parts by mass, acrylonitrile 2 parts by mass, styrene 5 parts by mass, deionized water (iron concentration: less than 0.02 ppm) 100 parts by mass, potassium rosinate 0.54 parts by mass, sodium stearate 0.06 parts by mass, tasha. 0.25 parts by mass of lead decyl mercaptan, 0.15 parts by mass of sodium hydroxide, 0.35 parts by mass of sodium persulfate, and 0.5 parts by mass of sodium bicarbonate were placed in a pressure vessel equipped with a stirrer degassed to vacuum. After being stored, the temperature was raised from room temperature to 65° C. to start polymerization.
After 7 hours from the start of polymerization, 0.72 parts by mass of potassium rosinate and 0.08 parts by mass of sodium stearate are added, and after 4 hours, 0.63 parts by mass of potassium rosinate and 0.07 parts by mass of sodium stearate. Parts, and after further 4 hours, 0.18 parts by mass of potassium rosinate and 0.02 parts by mass of sodium stearate were added, and the system was heated to 80° C., then 0.45 parts by mass of potassium rosinate, 0.05 parts by mass of sodium stearate and 15 parts by mass of deionized water were added. After 13 hours from the start of the polymerization, the system was cooled to complete the polymerization.
In the obtained polymerization liquid, the solid content was 46.5% by mass, and the mass average particle size of the solid content measured by Nikkiso Co., Ltd. Microtrac particle size analyzer (trade name: nanotrac150) was 125 nm. The swelling index measured by the above method was 22%.
Moreover, the composition ratio of the monomer in the rubbery polymer which is the solid content is measured by using a Fourier transform infrared spectrophotometer (FT-IR) (manufactured by JASCO Corporation, product number: FT/IR-7000). As a result of analysis, the butadiene unit was 93.3 mass %, the acrylonitrile unit was 1.9 mass %, and the styrene unit was 4.8 mass %.

(Production Example 12) [Production of rubber latex (L-12)]
Butadiene 93 parts by mass, acrylonitrile 2 parts by mass, styrene 5 parts by mass, deionized water (iron concentration: less than 0.02 ppm) 120 parts by mass, potassium rosinate 0.54 parts by mass, sodium stearate 0.06 parts by mass, tasha. 0.25 parts by mass of lead decyl mercaptan, 0.15 parts by mass of sodium hydroxide, 0.35 parts by mass of sodium persulfate, and 0.5 parts by mass of sodium bicarbonate were placed in a pressure vessel equipped with a stirrer degassed to vacuum. After being stored, the temperature was raised from room temperature to 65° C. to start polymerization.
After 7 hours from the start of polymerization, 0.72 parts by mass of potassium rosinate and 0.08 parts by mass of sodium stearate are added, and after 4 hours, 0.63 parts by mass of potassium rosinate and 0.07 parts by mass of sodium stearate. Parts, and after further 4 hours, 0.18 parts by mass of potassium rosinate and 0.02 parts by mass of sodium stearate were added, and the system was heated to 80° C., then 0.45 parts by mass of potassium rosinate, 0.05 parts by mass of sodium stearate and 15 parts by mass of deionized water were added. After 10 hours had passed from the start of the polymerization, the system was cooled to complete the polymerization.
In the obtained polymerization liquid, the solid content was 42.5% by mass, and the mass average particle diameter of the solid content measured by Nikkiso Co., Ltd. Microtrac particle size analyzer (trade name: nanotrac150) was 30 nm. The swelling index measured by the above method was 21%.
Moreover, the composition ratio of the monomer in the rubbery polymer which is the solid content is measured by using a Fourier transform infrared spectrophotometer (FT-IR) (manufactured by JASCO Corporation, product number: FT/IR-7000). As a result of analysis, the butadiene unit was 93.0% by mass, the acrylonitrile unit was 1.7% by mass, and the styrene unit was 5.3% by mass.

(Production Example 13) [Production of rubber latex (L-13)]
Butadiene 100 parts by mass, deionized water (iron concentration: less than 0.02 ppm) 67 parts by mass, potassium rosinate 0.54 parts by mass, sodium stearate 0.06 parts by mass, tertiary decyl mercaptan 0.25 parts by mass, water 0.15 parts by mass of sodium oxide, 0.35 parts by mass of sodium persulfate, and 0.5 parts by mass of sodium bicarbonate were placed in a pressure vessel equipped with a degassed stirrer, and the temperature was changed from room temperature to 65°C. And the polymerization was started.
After 7 hours from the start of polymerization, 0.72 parts by mass of potassium rosinate and 0.08 parts by mass of sodium stearate are added, and after 4 hours, 0.63 parts by mass of potassium rosinate and 0.07 parts by mass of sodium stearate. Parts, and after further 4 hours, 0.18 parts by mass of potassium rosinate and 0.02 parts by mass of sodium stearate were added, and the system was heated to 80° C., then 0.45 parts by mass of potassium rosinate, 0.05 parts by mass of sodium stearate and 15 parts by mass of deionized water were added. After the lapse of 30 hours from the start of polymerization, the system was cooled to complete the polymerization.
In the obtained polymerization liquid, the solid content was 54.9% by mass, and the mass average particle diameter of the solid content measured by Nikkiso Co., Ltd. Microtrac particle size analyzer (trade name: nanotrac150) was 340 nm. The swelling index measured by the above method was 22%.
Moreover, the composition ratio of the monomer in the rubbery polymer which is the solid content is measured by using a Fourier transform infrared spectrophotometer (FT-IR) (manufactured by JASCO Corporation, product number: FT/IR-7000). As a result of analysis, the butadiene unit was 100.0 mass %.

(Production Example 14) [Production of rubber latex (L-14)]
Butadiene 100 parts by mass, deionized water (iron concentration: less than 0.02 ppm) 92 parts by mass, potassium rosinate 0.54 parts by mass, sodium stearate 0.06 parts by mass, tertiary decyl mercaptan 0.25 parts by mass, water 0.15 parts by mass of sodium oxide, 0.35 parts by mass of sodium persulfate, and 0.5 parts by mass of sodium bicarbonate were placed in a pressure vessel equipped with a degassed stirrer, and the temperature was changed from room temperature to 65°C. And the polymerization was started.
After 7 hours from the start of polymerization, 0.72 parts by mass of potassium rosinate and 0.08 parts by mass of sodium stearate are added, and after 4 hours, 0.63 parts by mass of potassium rosinate and 0.07 parts by mass of sodium stearate. Parts, and after further 4 hours, 0.18 parts by mass of potassium rosinate and 0.02 parts by mass of sodium stearate were added, and the system was heated to 80° C., then 0.45 parts by mass of potassium rosinate, 0.05 parts by mass of sodium stearate and 15 parts by mass of deionized water were added. After 15 hours had passed from the start of the polymerization, the system was cooled to complete the polymerization.
In the obtained polymerization liquid, the solid content was 48.3 mass%, and the mass average particle diameter of the solid content measured by Nikkiso Co., Ltd. Microtrac particle size analyzer (trade name: nanotrac150) was 180 nm. The swelling index measured by the above method was 22%.
Moreover, the composition ratio of the monomer in the rubbery polymer which is the solid content is measured by using a Fourier transform infrared spectrophotometer (FT-IR) (manufactured by JASCO Corporation, product number: FT/IR-7000). As a result of analysis, the butadiene unit was 100.0 mass %.

(Calculation method of swell index)
The swelling index was determined by the following method. After drying the rubber latex, it was immersed in toluene at 25° C. for 48 hours, filtered, and washed with a small amount of toluene. After that, toluene adhering to the surface of the obtained rubbery polymer was wiped off to measure the mass (W1) of the rubbery polymer. Next, it was dried for 30 minutes with a hot air dryer set at 60° C., and then for 14 hours with a vacuum dryer adjusted to 60±2° C. Further, after allowing to cool in the desiccator for 30 minutes, the mass (W2) of the rubber-like polymer was measured. The swelling index (swell index) was calculated from the calculated W1 and W2 by the following formula.
Swelling index (%)=[(W1-W2)/W2]×100
The higher the swelling index, the lower the degree of crosslinking.

(Production Example 15) [Production of Resin Composition (I-1)]
37.5 parts by mass (solid content) of the rubber latex (L-1) obtained in (Production Example 1) and 12.5 parts by mass of the rubber latex (L-9) obtained in (Production Example 9) ( 125 parts by mass of deionized water (iron concentration: less than 0.02 ppm) was added to the solid content, and the gas phase part was replaced with nitrogen. An aqueous solution prepared by dissolving 0.080 parts by mass of sodium formaldehyde sulfoxylate, 0.003 parts by mass of ferrous sulfate, and 0.020 parts by mass of ethylenediaminetetraacetic acid disodium salt in 20 parts by mass of deionized water was added thereto. (The above is "Hatsuzo" in Table 1.) Then, the obtained solution was heated to 70°C. Then, over a period of 5 hours, a monomer mixture solution containing 17.5 parts by mass of acrylonitrile, 32.5 parts by mass of styrene, 0.1 part by mass of cumene hydroperoxide, and 0.4 part by mass of tertiary reed decyl mercaptan, Then, an aqueous solution prepared by dissolving 0.045 parts by mass of sodium formaldehyde sulfoxylate in 15 parts by mass of deionized water was added (the above is "addition" in Table 1). After the addition of them, 0.02 parts by mass of cumene hydroperoxide was further added, and then the polymerization reaction was completed for an additional 1 hour while controlling the reaction vessel at 70° C., and 0.6 parts by mass of potassium rosinate was added thereto. Was added (above, "shot" in Table 1). Thus, ABS rubber latex was obtained.

After adding 0.07 parts by mass of a silicone resin defoaming agent and 0.6 parts by mass of a phenolic antioxidant emulsion to 100 parts by mass of the ABS rubber latex thus obtained, the solid content concentration was 10 parts by mass. %, deionized water was added to adjust the temperature, and after heating to 70° C., an aqueous solution of aluminum sulfate was added to solidify 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). The resin composition (I-1) is composed of a graft copolymer (IA-1) and a thermoplastic resin (IB-1), and has an acetone insoluble content, that is, a graft copolymer (I-). The content ratio of A-1) was 80.5 mass %, and the content ratio of the acetone-soluble component, that is, the thermoplastic resin (IB-1) was 19.5 mass %. The reduced specific viscosity (ηsp/c) of the thermoplastic resin (IB-1) was 0.37 dL/g. The reduced specific viscosity was obtained by measuring the viscosity of a solution prepared by dissolving 0.25 g of the sample in 50 mL of 2-butanone using a Cannon-Fenske type capillary tube at 30°C. The method for measuring the reduced specific viscosity was the same in Production Examples 16 to 31 described later.

(Production Examples 16 to 31) [Production of Resin Compositions (I-2) to (I-17)]
Resin compositions (I-2) to (I-17) were produced in the same manner as in (Production Example 15) except that the formulations shown in Table 1 and Table 2 were used. The materials and charging ratios of the resin compositions of (Production Examples 15 to 31), the content ratios of the acetone-insoluble matter and the acetone-soluble matter, and the reduced specific viscosities of the acetone-soluble matter are shown in Tables 1 and 2 below.

(Production Example 32) [Production of Resin Composition (I-18)]
40 parts by mass of a latex of polybutadiene rubber having an average particle size of 0.3 μm (as solid content) and 100 parts by mass of deionized water were placed in a polymerization tank equipped with a reflux condenser, and the temperature was raised to 70° C. while substituting the gas phase with nitrogen. Warmed. Then, a mixed solution containing 36 parts by mass of styrene, 24 parts by mass of acrylonitrile, 0.7 parts by mass of t-dodecyl mercaptan, and 0.12 parts by mass of cumene hydroperoxide, and 50 parts by mass of deionized water, sodium formaldehyde sulfone. An aqueous solution containing 0.2 parts by mass of xylate, 0.012 parts by mass of ferrous sulfate, and 0.08 parts by mass of disodium salt of ethylenediaminetetraacetic acid was continuously added for 5 hours for reaction. During this period, the polymerization temperature was adjusted to 70° C., and after the additional addition was completed, the state was maintained for an additional 1 hour to complete the polymerization, thereby producing a resin composition (I-18). The polymerization rate was 95%.

(Production Example 33) [Production of thermoplastic resin (II-B-1)]
A monomer mixture consisting of 43.4 parts by mass of acrylonitrile, 32.5 parts by mass of styrene, 24.1 parts by mass of ethylbenzene, 0.3 part by mass of α-methylstyrene dimer, and 0.01 part by mass of t-butylperoxyisopropyl carbonate. 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 stirrer rotation speed of the stirrer was set to 95, and the mixture was thoroughly mixed, and the P/V value was 4.0 kw/m ³ . The average residence time was 1.65 hours.
The polymerization mixture having a polymerization rate of 60% and a polymer concentration of 50% by mass thus obtained was continuously withdrawn from the reactor and transferred to the first separation tank. In the first separation tank, the polymerization mixture was heated to 160° C. in a heat exchanger, devolatilized at a vacuum degree of 60 Torr to adjust the polymer concentration in the polymerization mixture 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 was heated to 260° C. by a heat exchanger and devolatilized at a vacuum degree of 32 Torr to give a volatile component content of 0.7% by mass and a polymer concentration of 99. After being adjusted to 0.4% by mass, it was discharged to obtain a 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 compositional analysis, the acrylonitrile unit content was 40.0 mass% and the styrene unit content was 60.0 mass %. The thermoplastic resin (II-B-1) was soluble in acetone, and the reduced specific viscosity (ηsp/c) was 0.58 dL/g.

(Production Example 34) [Production of thermoplastic resin (II-B-2)]
Acrylonitrile 33.2 parts by mass, styrene 29.9 parts by mass, butyl acrylate 8.1 parts by mass, ethylbenzene 28.8 parts by mass, α-methylstyrene dimer 0.3 parts by mass, t-butylperoxyisopropyl carbonate 0.01. A monomer mixture consisting of parts by weight 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 stirrer rotation speed of the stirrer was set to 95, and the mixture was thoroughly mixed, and the P/V value was 4.0 kw/m ³ . The average residence time was 1.65 hours.
The polymerization mixture having a polymerization rate of 60% and a polymer concentration of 50% by mass thus obtained was continuously withdrawn from the reactor and transferred to the first separation tank. In the first separation tank, the polymerization mixture was heated to 160° C. in a heat exchanger, devolatilized at a vacuum degree of 60 Torr to adjust the polymer concentration in the polymerization mixture 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 was heated to 260° C. by a heat exchanger and devolatilized at a vacuum degree of 32 Torr to give a volatile component content of 0.7% by mass and a polymer concentration of 99. After being adjusted to 0.4% by mass, it was discharged to obtain a pellet-shaped thermoplastic resin (II-B-2).
The composition ratio of each monomer unit in this thermoplastic resin (II-B-2) was 38.6 mass% for acrylonitrile units and 51 for styrene units as a result of composition analysis using a Fourier transform infrared spectrophotometer. It was 0.3% by mass and 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.

(Polyester elastomer (C))
As the polyester elastomer (C), a block copolymer was used in which the hard segment was polybutylene terephthalate, the soft segment was an aliphatic polyether, and the Shore hardness D thereof was as follows.
<Polyester elastomer III-C-1>
Polyester elastomer having Shore hardness D of 30 <Polyester elastomer III-C-2>
Polyester elastomer having Shore hardness D of 40 <Polyester elastomer III-C-3>
Polyester elastomer with Shore hardness of 55

(Example 1)
30 parts by mass of the resin composition (I-1) and 68 parts by mass of the thermoplastic resin (II-B-1), 2 parts by mass of the polyester elastomer (III-C-2), which have been sufficiently dried to remove water. 1 part by mass of ethylene bis-stearamide was mixed. Then, the obtained mixture was put into a hopper, and using a twin-screw extruder (ZSK25MC manufactured by Coperion Co., Ltd.), a cylinder set temperature of 250° C., a screw rotation speed of 250 rpm, and a kneaded product discharge rate of 12 kg/hour. The mixture was kneaded under the conditions to obtain pellets which were a thermoplastic resin composition. Table 3 shows the content ratio of each resin in the obtained thermoplastic resin composition. In Tables 3 to 5, the graft copolymer (IA) and the thermoplastic resin (IB) in the resin composition (I) are referred to as “IAn” and “IB-,” respectively. n” (n is an integer of 1 to 17) is indicated, which corresponds to the resin composition (In) shown in Table 1 and Table 2. That is, for example, the graft copolymer (IA-2) and the thermoplastic resin composition (IB-2) shown in Table 3 used in Example 2 are the resin composition (I -2) refers to the graft copolymer and thermoplastic resin included in

The mass average particle size of the rubbery polymers (a1) and (a2) dispersed in this thermoplastic resin composition was determined according to the above method (dyeing agent: osmium tetroxide). The mass average particle diameter of the polymer (a1) was 0.34 μm, and the mass average particle diameter of the rubbery polymer (a2) was 0.18 μm. Moreover, when the content ratios of the rubbery polymers (a1) and (a2) in the rubbery polymer (100% by mass) were determined according to the above method, the content ratio of the rubbery polymer (a1) was found. Was 75% by mass, and the content ratio of the rubbery polymer (a2) was 25% by mass. In addition, the SD value “(d84%−d16%)/2” in the particle size distribution of the rubbery polymers (a1) and (a2) was determined according to the above method, and the rubbery polymers (a1 The SD value of) was 0.051 μm, and the SD value of the rubbery polymer (a2) was 0.042 μm. The difference between the mass average particle size of the rubber polymer (a1) and the mass average particle size of the rubber polymer (a2) was 0.16 μm.

The half value width/peak height of the peak I in the temperature-loss tangent (tan δ) curve of the graft copolymer (A) in this thermoplastic resin composition was 50 as determined according to the above method. .. Further, the peak top position of peak I was determined according to the above method, and was -70°C.

The composition ratio of the monomers in the graft copolymer (A) in this thermoplastic resin composition was determined by Fourier transform infrared spectrophotometer (FT-IR) (manufactured by JASCO Corporation, product number: FT/IR-7000). ), the butadiene unit is 57.8% by mass, the acrylonitrile unit is 14.5% by mass, and the styrene unit is 27.7% by mass. The content ratio (D) of the vinyl cyanide-based monomer unit was 35.1% by mass, and the graft ratio was 52%. On the other hand, the content ratio (E) of acrylonitrile units in all the monomer units in the thermoplastic resin (B) was 39.6% by mass, and the reduced specific viscosity (ηsp/c) was 0.56 dL/g. .. Table 6 shows these results and the results of each evaluation.

(Examples 2-18, Comparative Examples 1-11)
A thermoplastic resin composition was prepared in the same manner as in Example 1 except that the types and content ratios of the graft copolymer (A), the thermoplastic resin (B) and the polyester elastomer (C) were as shown in Tables 3 to 5. Each product was obtained and the evaluation was performed. The evaluation results are shown in Tables 6 to 8.

In Examples 1 to 18, the results were excellent in impact resistance, chemical resistance, and gloss, and also excellent in impact resistance retention during coloring.

INDUSTRIAL APPLICABILITY The thermoplastic resin composition of the present invention has industrial applicability as a molding material for general appliances, home appliances, cosmetic containers, and the like.

Claims (10)

A trunk polymer composed of a rubbery polymer, and a graft copolymer (A) having a graft chain graft-polymerized on the trunk polymer;
A thermoplastic resin (B) containing a polymer containing vinyl cyanide-based monomer units;
A polyester elastomer (C) in which the hard segment is an aromatic polyester and the soft segment is an aliphatic polyether and/or an aliphatic polyester,
The content of the graft copolymer (A) is 10 to 45 parts by mass with respect to 100 parts by mass of the total amount of the graft copolymer (A), the thermoplastic resin (B) and the polyester elastomer (C), The content of the thermoplastic resin (B) is 89.5 to 40 parts by mass, the content of the polyester elastomer (C) is 0.5 to 15 parts by mass,
The particle size distribution of the rubber-like polymer has a mass-average particle size of 0.10 μm and a first peak derived from the rubber-like polymer (a1) having a mass-average particle size of 0.20 μm or more and less than 0.50 μm. A thermoplastic resin composition having a bimodal particle size distribution with a second peak derived from the rubber-like polymer (a2) of 0.20 μm or more. The temperature-loss tangent (tan δ) curve in the graft copolymer (A) has two or more peaks, and at least one of the two or more peaks is −73° C. or higher −64. Peak I having a peak top in the range of less than °C,
The thermoplastic resin composition according to claim 1, wherein the “half width/peak height” of the peak I is 40 or more and less than 60. The graft copolymer (A) contains a vinyl cyanide-based monomer unit,
In the graft copolymer (A), the content ratio (D) of vinyl cyanide-based monomer units in all monomer units (100% by mass) other than the rubbery polymer is 15 to 50% by mass. The thermoplastic resin composition according to claim 1 or 2. 4. The content ratio (E) of vinyl cyanide-based monomer units in all monomer units (100% by mass) in the thermoplastic resin (B) is 15 to 55% by mass. The thermoplastic resin composition as described in 1 above. In the particle size distribution of the rubber polymer (a1), the SD value represented by the following formula (1) is 0.01 μm or more and less than 0.07 μm,
5. The SD value represented by the following formula (1) in the particle size distribution of the rubber-like polymer (a2) is 0.01 μm or more and less than 0.07 μm. The thermoplastic resin composition.
SD=(d84%-d16%)/2 (1)
(In the formula (1), d16% represents the particle size (μm) at the point where the cumulative curve becomes 16% in the particle size distribution, and d84% represents the particle at the point where the cumulative curve becomes 84% in the particle size distribution. Indicates the diameter (μm).) Any of claims 1 to 5, wherein the difference between the mass average particle size of the rubber polymer (a1) and the mass average particle size of the rubber polymer (a2) is 0.10 μm or more and less than 0.25 μm. The thermoplastic resin composition as described in 1 above. The thermoplastic resin composition according to any one of claims 1 to 6, wherein the polyester elastomer (C) has a Shore hardness D of 20 to 80. The rubber-like polymer constituting the graft copolymer (A) is
At least one selected from the group consisting of polybutadiene, styrene-butadiene copolymer, styrene-butadiene block copolymer, acrylonitrile-butadiene copolymer, and acrylonitrile-styrene-butadiene copolymer,
The thermoplastic resin composition according to any one of claims 1 to 7. A molded article of the thermoplastic resin composition according to any one of claims 1 to 8. The molded article according to claim 9, which is a cosmetic container.