JP2024008883A - Abs-based resin composition, molding, and coated molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ABS-based resin composition and a molding which have desired bio-based degrees derived from bio-based polyethylene, and do not impair excellent mechanical characteristics and coating properties originally possessed by an ABS-based resin.

SOLUTION: An ABS-based resin composition contains an ABS-based resin (a), bio-based polyethylene (b), and a hydrogenated block copolymer (c), wherein the hydrogenated block copolymer (c) has a polymer block S mainly containing a vinyl aromatic monomer unit and a polymer block B mainly containing a conjugated diene monomer unit, a hydrogenation rate is 50 mol% or more, a mass ratio (a)/(b) is 99/1 to 50/50, a mass ratio (b)/(c) is 90/10 to 50/50, and in dispersion form analysis by a transmission electron microscope, the ABS-based resin (a) forms a continuous phase and the bio-based polyethylene (b) forms a dispersion phase.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to an ABS resin composition, a molded article, and a coated molded article.

In general, vinyl aromatic resins, such as polystyrene resins and ABS resins (acrylonitrile/butadiene/styrene copolymers), have excellent moldability, rigidity, impact resistance, etc., are inexpensive, have low specific gravity, and are economical. Because of its excellent properties, it is used in various fields as a material for injection molded products, sheets and films extruded from T-dies, and round and square tube-shaped extruded products extruded from irregular molds. widely used in

In recent years, with increasing awareness of global environmental issues, there has been a growing momentum to reduce the amount of plastic used and to switch to materials that do not rely on fossil resources, and such efforts are spreading in various fields and applications.

Among the vinyl aromatic resins mentioned above, ABS resin, which has an excellent balance of impact resistance, rigidity, and chemical resistance, is used as a main component of durable consumer goods, mainly injection molded products, such as home appliances, miscellaneous goods, and automobile parts. It is widely used as a material. In these applications, the required level of mechanical properties is high, and at the current technological level, it is difficult to use ABS resins that are widely used in durable consumer goods from fossil raw materials from an economic and industrial perspective. The current situation is that it has not reached the point where it is widely available to the world. Furthermore, in order to produce ABS resin from non-petrified monomer raw materials, there are still many technical issues to be solved, and the reality is that stable industrial production and practical application have not yet been achieved. The shift away from using fossil fuels as raw materials is an immediate issue.

ABS resins currently on the market and used in durable consumer goods are basically fossil resource-based materials that are made from fossil resources, and when they are incinerated as plastic waste after use, they are released into the atmosphere. The new release of carbon dioxide is one of the causes of global warming and the associated abnormal weather. For this reason, the momentum to reduce the consumption of fossil resource-based plastic materials is increasing year by year.

Due to the recent rise in awareness of environmental issues, biopolymers made from plant-derived monomers, such as polyethylene made from plant-derived monomers, are gaining attention as carbon-neutral materials to reduce the amount of fossil resources used. As a result, they are increasingly being adopted for plastic bags, cutlery, etc. (see, for example, Patent Documents 1 and 2).

Patent No. 5453098 Patent No. 5799520

As mentioned above, ABS resin has excellent moldability, rigidity, impact resistance, etc., and is also inexpensive, has a low specific gravity, and is economically superior, so it is widely used in various fields as various molded products. ing. Furthermore, polyethylene using plant-derived monomers has been used for various purposes.
However, ABS resin and polyethylene are completely incompatible systems, and when blended, the mechanical properties such as impact resistance that ABS resin originally has will be greatly impaired, so they cannot be used in practical applications for durable consumer goods. The current state of the art is that no development research of this kind has ever been carried out in industry.

Additionally, painted ABS resin molded bodies are used in many applications and fields as exterior parts. For example, it is still used in many applications as painted molded products, such as automobile exterior parts.
On the other hand, molded bodies of polyolefin resins, typically polyethylene, are generally known to be difficult to paint. The reality is that in order to improve the adhesion of a polyolefin resin molded article to a paint, such as corona discharge treatment or etching treatment, many steps are required, which is time-consuming and costly.
As mentioned above, when a polyolefin resin is blended into an ABS resin molded article that requires good appearance, there are technical issues that need to be solved from the viewpoint of ease of painting.

Therefore, in the present invention, in view of the problems of the prior art described above, we combined ABS resin whose starting monomer is a fossil raw material with bio-based polyethylene whose starting monomer is a bio-based raw material derived from plants. By making them compatible and specifying the dispersion form, we can create an ABS resin composition that has a certain degree of biomass, has excellent balance of mechanical properties, and maintains the excellent paintability that ABS resin originally has. The purpose of this invention is to provide a product and a molded article made from the same.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have discovered that in a combination of acrylonitrile/butadiene/styrene copolymer, so-called ABS resin, and bio-based polyethylene, a hydrogenated block with a specific configuration is further developed. By combining copolymers and specifying the mass ratio and dispersion form of each resin, we are able to develop outstanding mechanical properties that could not be achieved with a resin composition consisting only of ABS resin and bio-based polyethylene. succeeded in maintaining the good paintability originally possessed by ABS resin, and found that the above-mentioned problems of the prior art were solved, leading to the completion of the present invention.
That is, the present invention is as follows.

[1]
An ABS resin composition containing an ABS resin (a), a biobased polyethylene (b), and a hydrogenated block copolymer (c),
The hydrogenated block copolymer (c) has a polymer block S mainly composed of vinyl aromatic monomer units and a polymer block B mainly composed of conjugated diene monomer units,
50 mol% or more of the conjugated diene moiety constituting the hydrogenated block copolymer (c) is hydrogenated,
The mass ratio of the ABS resin (a) and the biobased polyethylene (b) is (a)/(b) = 99/1 to 50/50,
The mass ratio of the bio-based polyethylene (b) and the hydrogenated block copolymer (c) is
(b)/(c)=90/10 to 50/50,
In dispersion morphology analysis using a transmission electron microscope, ABS resin (a) forms a continuous phase and bio-based polyethylene (b) forms a dispersed phase.
ABS resin composition.
[2]
The bio-based polyethylene (b) is
An ethylene homopolymer (b1) and/or a copolymer of ethylene and α-olefin mainly composed of ethylene (b2), which has a biomass degree of 80% or more and 100% or less as defined in ASTM D6866,
The ABS resin composition described in [1] above.
[3]
The hydrogenated block copolymer (c) is
Containing 4 to 70% by mass of vinyl aromatic monomer units and 30 to 96% by mass of conjugated diene monomer units,
The ABS resin composition described in [1] or [2] above.
[4]
A molded article of the ABS resin composition according to any one of [1] to [3] above, which is an injection molded article.
[5]
A molded article of the ABS resin composition according to any one of [1] to [3] above, which is a blow molded article.
[6]
A molded article of the ABS resin composition according to any one of [1] to [3] above, which is an extrusion molded article.
[7]
A coated molded product having the molded product according to any one of [4] to [6] above, and a coating film.
[8]
The apparent melt viscosity ηgpe (Pa s) of the biobased polyethylene (b) relative to the apparent melt viscosity ηabs (Pa s) of the ABS resin (a) in a capillary rheometer under a temperature condition of 220°C. The ratio: ηgpe/ηabs is always 0.3 or more with an apparent shear rate γa (sec ^-1 ) between 12.16 and 1216;
The ABS resin composition described in [2] or [3] above.
[9]
The apparent melt viscosity ηgpe (Pa s) of the biobased polyethylene (b) relative to the apparent melt viscosity ηabs (Pa s) of the ABS resin (a) in a capillary rheometer under a temperature condition of 220°C. The ratio: ηgpe/ηabs is always 1.0 or more with an apparent shear rate γa (sec- ¹ ) between 12.16 and 1216;
The ABS resin composition described in [2] or [3] above.

According to the present invention, in an ABS resin composition composed of an ABS resin, a biobased polyethylene, and a specific hydrogenated block copolymer, the ABS resin composition has a desired degree of biomass derived from the biobased polyethylene, and ABS resin compositions and molded articles that do not impair the excellent mechanical properties and paintability originally possessed by ABS resin compositions and molded articles can be obtained.

The results of analysis of the dispersion form of the ABS resin composition of Example 9 by transmission electron microscopy are shown. The results of analyzing the dispersion form of the ABS resin composition of Comparative Example 7 using a transmission electron microscope are shown. The results of analyzing the dispersion form of the ABS resin composition of Comparative Example 26 using a transmission electron microscope are shown.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail.
The following embodiments are examples for explaining the present invention, and the present invention is not intended to be limited to the following content, and the present invention may be implemented with various modifications within the scope of the gist. Can be done.

[ABS resin composition]
The ABS resin composition of this embodiment is
An ABS resin composition containing an ABS resin (a), a biobased polyethylene (b), and a hydrogenated block copolymer (c),
The hydrogenated block copolymer (c) has a polymer block S mainly composed of vinyl aromatic monomer units and a polymer block B mainly composed of conjugated diene monomer units,
50 mol% or more of the conjugated diene moiety constituting the hydrogenated block copolymer (c) is hydrogenated,
The mass ratio of the ABS resin (a) and the biobased polyethylene (b) is
(a)/(b)=99/1 to 50/50,
The mass ratio of the bio-based polyethylene (b) and the hydrogenated block copolymer (c) is
(b)/(c)=90/10 to 50/50,
This is an ABS resin composition in which the ABS resin (a) forms a continuous phase and the biobased polyethylene (b) forms a dispersed phase in dispersion morphology analysis using a transmission electron microscope.
By having the above structure, the ABS resin composition of the present embodiment has the desired biomass degree derived from biobased polyethylene, while maintaining the mechanical properties and coating properties of the original ABS resin. Depending on the combination, it is possible to obtain an ABS resin composition with excellent balance of mechanical properties, such as exhibiting impact resistance that exceeds that of the original ABS resin without impairing properties.

In addition, in this specification, the expression "consisting mainly" of the proportion occupied by monomer units in a polymer is used, which means that the content of a predetermined monomer unit is 60% by mass or more. It means that. Preferably it is 80% by mass or more, more preferably 90% by mass or more.

(Mass ratio of ABS resin (a) and bio-based polyethylene (b))
In the ABS resin composition of the present embodiment, the mass ratio of the ABS resin (a) to the biobased polyethylene (b) is (a)/(b) = 99/1 to 50/50, preferably , (a)/(b) = 95/5 to 50/50, more preferably (a)/(b) = 90/10 to 50/50, even more preferably (a)/( b)=75/25 to 50/50, even more preferably (a)/(b)=75/25 to 60/40.
Regarding the mass ratio of ABS resin (a) and bio-based polyethylene (b), by setting the mass ratio as described above, the biomass degree can be increased by mixing bio-based polyethylene (b) with ABS resin (a). The best balance can be achieved between the added value and the advantages of the original ABS resin, which has excellent mechanical properties and processability.
When the mass ratio of the bio-based polyethylene (b) is 1 or more, it becomes practical from the viewpoint of the present invention of introducing a degree of biomass into the ABS resin.
In addition, when the mass ratio of bio-based polyethylene (b) is 50 or less, the ABS resin composition has excellent mechanical properties, paintability, and processability.
The ABS resin composition of this embodiment is mainly composed of ABS resin (a), and by combining the ABS resin (a) with biobased polyethylene (b), a desired degree of biomass is introduced. Standing on the idea.

(Mass ratio of bio-based polyethylene (b) and hydrogenated block copolymer (c))
In the ABS resin composition of this embodiment, the mass ratio of biobased polyethylene (b) and hydrogenated block copolymer (c) is (b)/(c) = 90/10 to 50/50. , preferably (b)/(c) = 80/20 to 55/45, more preferably (b)/(c) = 75/25 to 60/40.
Regarding the mass ratio of bio-based polyethylene (b) and hydrogenated block copolymer (c), by setting the mass ratio as described above, a desired biomass degree can be achieved and excellent mechanical properties and processability can be obtained.
When the mass ratio of the biobased polyethylene (b) is 50 or more, it is practical from the viewpoint of the present invention to impart a desired degree of biomass to the ABS resin composition of the present embodiment.
Furthermore, by setting the mass ratio of biobased polyethylene (b) to 90 or less, desired compatibility can be obtained, and excellent mechanical properties and processability can be obtained in the ABS resin composition of this embodiment. .

(Phase composition of ABS resin composition)
In the ABS-based resin composition of the present embodiment, the ABS-based resin (a) forms a continuous phase and the bio-based polyethylene (b) forms a dispersed phase in a dispersion morphology analysis using a transmission electron microscope. ABS resin (a) has particulate butadiene rubber, while polyethylene has crystalline lamella parts, so by dyeing and observing the dispersion form, it is possible to know the dispersion state of each component. .

When analyzing the dispersion morphology of a resin composition using a transmission electron microscope, it is usually possible to observe the resin composition with increased contrast by staining it with heavy metal oxide. As the heavy metal oxide used for this dyeing, osmium tetroxide and ruthenium tetroxide are generally used, but dyeing with ruthenium tetroxide is suitable for the ABS resin composition of this embodiment. By dyeing with ruthenium tetroxide, the hydrogenated block copolymer (c) having a polymer block S mainly composed of vinyl aromatic monomer units was dyed most intensely, followed by the matrix of the ABS resin (a). The bio-based polyethylene (b) is dyed gray, and the butadiene rubber particles contained in the ABS resin (a) are observed as the whitest.

The boundary between the ABS resin (a) and the bio-based polyethylene (b) is dyed somewhat darkly, so the boundary can be clearly identified.
The hydrogenated block copolymer (c) rarely exists in the matrix phase of the ABS resin (a), and the hydrogenated block copolymer (c) is rarely present in the matrix phase of the ABS resin (a) and the boundary between the ABS resin (a) and biobased polyethylene (b) and the biobased polyethylene (b). Because it is included and dispersed within the dispersed phase of the rubber particles, it is clear which phase is the ABS resin (a) and the other is the biobased polyethylene (b) because it is dyed the darkest compared to the undyed rubber particles. It can be easily distinguished from the location where the hydrogenated block copolymer (c) is present.

By adjusting the viscosity of both biobased polyethylene (b) so that the melt viscosity of the biobased polyethylene (b) is the same as that of the ABS resin (a), or the melt viscosity of the biobased polyethylene (b) is higher than that of the ABS resin (a), A dispersed state can be obtained in which the biobased polyethylene (b) forms a dispersed phase in a continuous phase consisting of the resin (a).
These viscosities can be evaluated using melt flow rate or melt viscosity obtained using a capillary rheometer, but the relative viscosity ratio of ABS resin (a) and bio-based polyethylene (b) determines the phase structure. Since the absolute value of viscosity of each component is an important factor in determining the viscosity value, it is not necessary to strictly specify the viscosity value.
However, if the melt flow rate (MFR) of bio-based polyethylene (b) is adjusted to 1 or less under the conditions of 190°C and 2.16 kgf load, what kind of ABS resin (a) can be used as a mating material? Regardless of the selection, the ABS resin (a) generally tends to form a continuous phase and the biobased polyethylene (b) tends to form a dispersed phase. Conversely, if you select an ABS resin (a) with a low melt viscosity or a high melt flow rate value, bio-based polyethylene (b) that can take a dispersed form in the continuous phase of the ABS resin (a) ) will expand the range of melt viscosity or melt flow rate.
By having the dispersed state of the ABS resin composition of this embodiment, excellent mechanical properties and paintability are exhibited. Details will be shown in specific physical property data in Examples below.

(ABS resin (a))
The ABS resin composition of this embodiment contains an ABS (acrylonitrile/butadiene/styrene) resin (a).
The ABS resin (a) includes all so-called ABS resins that have been distributed on the market until now, and any of them can be suitably used regardless of manufacturer or brand.
The ABS resin (a) may be a neat polymer that does not contain functional auxiliary materials such as colorants, lubricants, fillers, and flame retardants, or may be a so-called compound grade containing functional auxiliary materials. Functional ABS resins copolymerized with comonomers such as maleimide to improve heat resistance, ABS resins copolymerized with (meth)acrylic monomers, etc. are also included in ABS resin (a) and are suitable. It can be used for.
In addition, AES resins that use ethylene rubber instead of butadiene rubber for the purpose of improving light resistance, and ASA resins that use acrylate rubber instead of butadiene rubber can also be used in the ABS resin composition of this embodiment. It is included in the ABS resin (a) constituting the product, and such AES resin or ASA resin can be used as the ABS resin (a).
Further, alloy materials with polycarbonate resin and acrylic resin are also included in ABS resin (a).
Moreover, a known manufacturing method can be applied to the manufacturing method of the ABS resin (a). The ABS resin (a) may be an ABS resin manufactured by emulsion polymerization or an ABS resin manufactured by solution polymerization.

Commercially available ABS resins include, for example, "Sevian (registered trademark)" manufactured by Daicel, "Toyolac (registered trademark)" manufactured by Toray, "Clarastic (registered trademark)" manufactured by Nippon A&L, and "Techno ABS (registered trademark)" manufactured by Techno UMG. ``Polylac (registered trademark)'' manufactured by Chimei Industrial Co., Ltd., and ``Teruran (registered trademark)'' manufactured by Ineos.

(Bio-based polyethylene (b))
The ABS resin composition of this embodiment contains bio-based polyethylene (b).
Bio-based polyethylene (b) is polyethylene using monomers derived from plants.
Bio-based polyethylene (b) is an ethylene homopolymer (b1) with a biomass degree of 80% or more and 100% or less as specified in ASTM D6866, and/or a copolymer of ethylene and α-olefin, mainly consisting of ethylene. Combination (b2) is preferred.
The biobased polyethylene (b) may be a single biobased polyethylene or a combination of multiple biobased polyethylenes having different biobased degrees.

The biobased polyethylene (b) preferably has a biomass degree of 80% or more as defined by ASTM D6866. More preferably, it is 85% or more and 100% or less, still more preferably 90% or more and 100% or less, and even more preferably 95% or more and 100% or less.
In general, the technology to produce ethylene monomer from a bio-based source has been established, while for α-olefins, it is currently more advantageous from an economic and industrial point of view to use fossil-based sources. Generally, the biomass content is less than 100%.
In view of the purpose of introducing a biomass degree into the ABS resin composition of this embodiment, it is preferable that the biomass degree of the biobased polyethylene (b) is a relatively high value.

A representative example of bio-based polyethylene is "Green Polyethylene," which is manufactured and sold under the brand "I'm Green" by Braskem of Brazil. The biomass content of each brand of Braskem's green polyethylene is specified in the catalog posted on its website.
As the bio-based polyethylene (b), all types of polyethylene can be suitably used, such as high-density polyethylene (HDPE) type, low-density polyethylene (LDPE) type, and linear low-density polyethylene (LLDPE) type.

Bio-based polyethylene manufactured and sold by Braskem is available in brands for various uses, including those with high MFR values for injection molding, and those with low MFR values such as those for blow molding, spinning, and films. This is possible and can be suitably used in the ABS resin composition of this embodiment.
Regarding bio-based polyethylene (b), if a brand with a low MFR value is used, the mechanical properties and paintability of the resulting ABS resin composition tend to be better, but regarding this experimental fact, Dispersion morphology analysis using a transmission electron microscope revealed that an ABS resin composition in which the ABS resin (a) forms a continuous phase as a matrix and the biobased polyethylene (b) forms a dispersed phase as domains is favorable. It has become clear that this material exhibits excellent mechanical properties and paintability. In the ABS resin composition of this embodiment, the ABS resin (a) forms a continuous phase, and the biobased polyethylene (b) forms a dispersed phase. In other words, it is more preferable to select a brand with a low MFR value for blow molding than a brand with a high MFR value for injection molding from the viewpoint of good mechanical properties and paintability. Specifically, the difference in properties can be verified by comparing examples of ABS resin compositions using bio-based polyethylene with different MFRs in Examples described below.
Since the ABS resin (a) becomes a continuous phase, the included butadiene rubber particles and bio-based polyethylene (b) function as a soft phase capable of absorbing impact, and therefore exhibit good mechanical properties. In addition, generally, polyethylene molded bodies tend to have poor paintability, but the ABS resin composition of this embodiment has ABS resin (a) as a matrix, so that the outermost surface of the molded product is coated with ABS resin. Since the resin (a) matrix is exposed and the bio-based polyethylene (b) is not exposed to the outermost layer, the paintability originally possessed by ABS resin (a) is expressed, and the resin composition exhibits good paintability.

A preferable MFR value of the bio-based polyethylene (b) is 0.1 or more and 30 or less, a more preferable MFR value is 0.1 or more and 10 or less, and an even more preferable MFR value under the conditions of 190° C. and 2.16 kgf load. The value is 0.1 or more and 3 or less, and an even more preferable MFR value is 0.1 or more and 1 or less. By using biobased polyethylene (b) having an MFR value within this range, an ABS resin composition with excellent mechanical properties can be obtained.

The density of the bio-based polyethylene (b) also influences the physical properties of the ABS resin composition.
Specifically, if a low-density type bio-based polyethylene is selected, the stiffness (=flexural modulus) of the resulting ABS resin composition tends to decrease and flexibility is imparted, but the hydrogenated block described below Due in part to the effect of the addition of polymer (c), the impact strength is equivalent to that of the original ABS resin, or depending on the combination, the impact strength is even greater than that of the ABS resin.
On the other hand, if high-density type bio-based polyethylene is selected, the stiffness of the resulting ABS resin composition will be maintained at approximately the same level as the original ABS resin.
As described above, it is preferable to select the density type of bio-based polyethylene (b) from the viewpoint of the physical properties that are important in consideration of the final use.
Generally, the density range of bio-based polyethylene (b) is in the range of 0.91 to 0.97 (g/cm ³ ).

Furthermore, the ABS resin composition of the present embodiment may contain a combination of bio-based polyethylene (b) and petroleum-based polyethylene without departing from the spirit of the present invention. If petroleum-based polyethylene is used in combination, the degree of bio-based content will decrease accordingly, so it is preferable to adjust the amount of petroleum-based polyethylene in consideration of the balance between mechanical properties and economic efficiency.

(Hydrogenated block copolymer (c))
The hydrogenated block copolymer (c) is a block copolymer containing a vinyl aromatic monomer unit and a conjugated diene monomer unit, and 50 mol% or more of the conjugated diene portion is hydrogenated.
The hydrogenated block copolymer (c) has a polymer block mainly composed of vinyl aromatic monomer units and a polymer block mainly composed of conjugated diene monomer units, and any of the polymer blocks Alternatively, it may have two or more of both blocks.

In addition, the hydrogenated block copolymer (c) contains 4 to 70% by mass of vinyl aromatic monomer units, from the viewpoint of the balance between rigidity and impact strength of the molded article of the ABS resin composition of the present embodiment. It is preferable to contain conjugated diene monomer units in an amount of 30 to 96% by mass.
In addition, from the viewpoint of the strength of the molded article of the ABS resin composition of the present embodiment, the hydrogenated block copolymer (c) contains a polymer block S mainly composed of at least one vinyl aromatic monomer unit. shall have.

In the hydrogenated block copolymer (c), 50 mol% or more of the conjugated diene portion is hydrogenated.
By hydrogenating the conjugated diene moiety, it changes to an olefin structure and exhibits compatibility with bio-based polyethylene (b). By setting the hydrogenation rate to 50 mol% or more, the compatibility with the bio-based polyethylene (b) is improved, and even when it is made into a resin composition with the ABS resin (a), the hydrogenated block copolymer ( c) and bio-based polyethylene (b) tend to be more compatible.
The hydrogenation rate can be determined by a known analytical method, and for example, infrared absorption spectroscopy, ¹ H-NMR, etc. can be suitably used.

The hydrogenated block copolymer (c) has a hydrogenation rate of 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and even more preferably is 90 mol% or more.
The upper limit of the hydrogenation rate is not particularly limited, but is preferably 100 mol% or less.
When the hydrogenation rate is 50 mol % or more, compatibility with bio-based polyethylene (b) becomes good, and an ABS resin composition having preferable mechanical properties can be obtained.
The hydrogenation rate of the hydrogenated block copolymer (c) can be controlled within the above numerical range by adjusting the type and amount of the hydrogenation catalyst, the amount of hydrogen supplied in the hydrogenation step, and the hydrogenation step time.

From the viewpoint of the strength of the ABS resin composition of this embodiment, the polymer block S mainly composed of vinyl aromatic monomer units constituting the hydrogenated block copolymer (c) is composed of vinyl aromatic monomer units. A polymer block containing 90% by mass or more of units is preferable.
Further, the polymer block B mainly composed of conjugated diene monomer units constituting the hydrogenated block copolymer (c) may be a conjugated diene polymer block composed of a conjugated diene monomer unit alone, It may also be a copolymer block of a conjugated diene monomer unit and a vinyl aromatic monomer unit. In the case of a copolymer block, various copolymer block structures can be used, such as a uniform random structure and a tapered structure (the composition ratio of monomers changes along the chain).

The hydrogenated block copolymer (c) may be a combination of two or more block copolymers having different average molecular weights, or a copolymerization ratio of vinyl aromatic monomer units and conjugated diene monomer units. Two or more different block copolymers may be combined.
The hydrogenated block copolymer (c) may contain other polymerizable monomer units other than the vinyl aromatic monomer unit and the conjugated diene monomer unit, if necessary.

The vinyl aromatic monomer unit constituting the hydrogenated block copolymer (c) can be formed using a vinyl aromatic compound. The vinyl aromatic compound may be any compound having an aromatic ring and a vinyl group in the molecule. Examples include, but are not limited to, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, 1 , 3-dimethylstyrene, α-methylstyrene, α-methyl-p-methylstyrene, vinylnaphthalene, vinylanthracene, and 1,1-diphenylethylene.
These vinyl aromatic compounds may be used alone or in combination of two or more. Among these, styrene is preferred from the industrial and economical viewpoints.

The conjugated diene monomer unit constituting the hydrogenated block copolymer (c) can be formed using a conjugated diene compound. The conjugated diene compound may be any diolefin having a pair of conjugated double bonds. Examples include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene etc.
These conjugated diene compounds may be used alone or in combination of two or more.
Among these, 1,3-butadiene and isoprene are preferred, and 1,3-butadiene is more preferred, from the viewpoint of industrial and economic efficiency.

In the hydrogenated block copolymer (c), the mass ratio of vinyl aromatic monomer units to conjugated diene monomer units is vinyl aromatic monomer units/conjugated diene monomer units = 4/96. The ratio is preferably 70/30. More preferably, the ratio of vinyl aromatic monomer unit/conjugated diene monomer unit is from 10/90 to 70/30, and even more preferably from 20/80 to 70/30.
When the ratio of each monomer unit is within the above range, the resulting ABS resin composition has a better balance between rigidity and impact strength.

In the range where the mass proportion of the vinyl aromatic monomer unit of the hydrogenated block copolymer (c) is 4% by mass or more and 50% by mass or less, the elastic modulus of the resulting ABS resin composition is somewhat low; They tend to exhibit high impact strength and outperform original ABS resins, that is, ABS resins that do not contain bio-based polyethylene (b) or hydrogenated block copolymers (c). .
On the other hand, in the region where the mass proportion of vinyl aromatic monomer units in the hydrogenated block copolymer (c) is more than 50 mass% and 70 mass% or less, the physical properties are maintained while almost maintaining the elastic modulus of the original ABS resin. It tends to be possible to obtain a well-balanced ABS resin composition.
In this way, like the above-mentioned bio-based polyethylene (b), the hydrogenated block copolymer (c) is also suitable for the vinyl aromatic Preference is given to selecting the mass proportions of the monomer units.

The content of vinyl aromatic monomer units and conjugated diene monomer units in the hydrogenated block copolymer (c) can be determined by the method described in the Examples below.
Further, the content of these monomer units can be controlled by adjusting the amount and ratio of each monomer added in the polymerization step of the hydrogenated block copolymer (c).

The hydrogenated block copolymer (c) is not particularly limited, but includes, for example, block copolymers having block structures shown in the following general formulas (1) to (5).
S-B...(1)
S-(B-S) _n ...(2)
B-(S-B) _n ...(3)
S-(B-S-B) _n ...(4)
(S-B) _n X…(5)
Here, S represents a polymer block mainly composed of vinyl aromatic monomer units, and B represents a polymer block mainly composed of hydrogenated conjugated diene monomer units. Further, n represents any integer from 1 to 6. In (2) to (5), n is independent and may be the same number or different numbers. X represents a coupling agent residue.

The above general formulas (1) to (4) are linear hydrogenated block copolymers, and (5) is a branched (also called star-shaped) hydrogenated block copolymer with B moiety as the bonding center. Both can be suitably used.
In addition, when the ABS resin composition of this embodiment is used for durable consumer goods, from the viewpoint of various required mechanical properties, the hydrogenated block copolymer (c) is a vinyl aromatic monomer. It is preferable to select one having at least two or more polymer blocks S mainly composed of units.
In this specification, a "polymer block mainly composed of vinyl aromatic monomer units" may be referred to as a "polymer block S."

<Peak molecular weight and molecular weight distribution of hydrogenated block copolymer (c)>
The hydrogenated block copolymer (c) has a peak molecular weight within the range of 20,000 to 250,000 in a molecular weight distribution curve measured by gel permeation chromatography (GPC measurement). Preferably there is at least one. This makes the mechanical properties of the ABS resin composition of this embodiment even better.
From the same viewpoint, the hydrogenated block copolymer (c) preferably has a peak molecular weight of 30,000 or more and 150,000 or less, more preferably 35,000 or more and 100,000 or less. More preferably, it exists within. The peak molecular weight of the hydrogenated block copolymer (c) can be measured by the method described in Examples below.

<Molecular weight distribution (Mw/Mn) of hydrogenated block copolymer (c)>
The molecular weight distribution (Mw/Mn) of the hydrogenated block copolymer (c) is not particularly limited. For example, hydrogenated block copolymers (c ) can be obtained.

Furthermore, by adding an appropriate amount of a polymerization initiator during polymerization to initiate polymerization from new polymerization active sites, a hydrogenated block copolymer (c), which is a mixture of polymers with different molecular weights, can be obtained. .
On the other hand, by adding alcohol such as ethanol in a molar equivalent amount smaller than the number of moles of the polymerization initiator into the polymerization system during polymerization to stop the polymerization of some of the polymers, it is possible to create a mixture of polymers with different molecular weights. It is also possible to obtain a hydrogenated block copolymer (c).

<Content and molecular weight of polymer block S of hydrogenated block copolymer (c)>
The content of the polymer block S mainly composed of vinyl aromatic monomer units in the hydrogenated block copolymer (c) is determined by oxidizing the block copolymer with tert-butyl hydroperoxide using osmium tetroxide as a catalyst. A polymer block S component obtained by a decomposition method (method described in I.M. KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)) (however, vinyl having an average degree of polymerization of about 30 or less) (excluding the aromatic hydrocarbon monomer polymer component). Moreover, the molecular weight (Mn and Mv) of the polymer block S can be obtained by measuring the polymer block S component obtained by the above method using gel permeation chromatography (GPC). In this specification, the method is referred to as the "osmium tetroxide method."

The content of the polymer block S in the hydrogenated block copolymer (c) can be determined by a method using a nuclear magnetic resonance apparatus (NMR) using the block copolymer before hydrogenation or the block copolymer after hydrogenation as a sample. (The method described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981)). In this specification, this analytical method is referred to as "NMR method".

In this case, the content of the polymer block S mainly composed of vinyl aromatic monomer units (assumed as Os) measured using the block copolymer before hydrogenation by the osmium tetroxide method and the NMR method. There is a correlation shown in the following formula between the content of the polymer block S mainly composed of vinyl aromatic monomer units (denoted as Ns) measured using the block copolymer after hydrogenation by be.

(Os) = -0.012 (Ns) ² +1.8 (Ns) -13.0... (F)

Therefore, in the present embodiment, when determining the content of the polymer block S of the hydrogenated block copolymer (c) by the NMR method, the value of (Os) determined by the above formula (F) is used in the present embodiment. The content of the polymer block S mainly composed of vinyl aromatic monomer units defined by

<Modification of hydrogenated block copolymer (c)>
The hydrogenated block copolymer (c) may be a modified product having a polar group.
In general, a "polar group" is an atomic group in which there is a bias in charge between covalently bonded atoms, and generally includes an atomic group containing heteroatoms such as oxygen, nitrogen, sulfur, phosphorus, and halogen. Point.

By modifying the hydrogenated block copolymer (c), a graft reaction is caused with the base polymer of the ABS resin (a) or bio-based polyethylene (b) to be modified, thereby forming the ABS resin (a). Compatibility with the bio-based polyethylene (b) can have the effect of reinforcing the interface between the components.
Further, when the ABS resin composition of the present embodiment contains a filler as a compounding material, effects such as promoting dispersion of the filler are exhibited due to a graft reaction with the filler.
However, the compatibility between ABS resin (a) and biobased polyethylene (b) is better when using an unmodified hydrogenated block copolymer than when using a modified hydrogenated block copolymer. In some cases, it is better to modify the hydrogenated block copolymer (c), depending on the characteristics of the ABS resin (a) used and other compounding auxiliary materials, and in other cases, it is better to modify the hydrogenated block copolymer (c). Since there are cases where it is better to select the option, it is preferable to select it each time.

When the hydrogenated block copolymer (c) is used as a modified product, the amount of polar groups added is generally 0.01% by mass to 10% by mass based on 100% by mass of the hydrogenated block copolymer (c). %, preferably 0.01% by mass to 8.0% by mass, more preferably 0.05% to 6.0% by mass, even more preferably 0.05% to 4.0% by mass. %.

Examples of polar groups include, but are not limited to, hydroxyl groups, carboxyl groups, carbonyl groups, thiocarbonyl groups, acid halide groups, acid anhydride groups, carboxylic acid groups, thiocarboxylic acid groups, aldehyde groups, thioaldehyde groups, Carboxylic acid ester group, amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, Examples include isocyanate groups, isothiocyanate groups, silicon halide groups, silanol groups, alkoxy silicon groups, tin halide groups, boronic acid groups, boron-containing groups, boronic acid groups, alkoxytin groups, and phenyltin groups. It may be an atomic group containing at least one functional group.

In particular, an atomic group having at least one functional group selected from the group consisting of an acid anhydride group, a carboxylic acid group, a hydroxyl group, an epoxy group, an amino group, an amide group, a silanol group, and an alkoxysilane group is preferable, and more preferably An atomic group having at least one functional group selected from the group consisting of an acid anhydride group, a carboxylic acid group, a hydroxyl group, an epoxy group, an amino group, and an amide group, and more preferably an acid anhydride group, a carboxylic acid group, and a hydroxyl group. It is an atomic group having at least one kind of functional group selected from the group consisting of.
When an acid anhydride is bonded to a block copolymer in the process of forming polar groups, there is a possibility that the acid anhydride will react with moisture in the air and some of it will become carboxylic acid groups. However, the amount is not particularly limited.

<Method for producing hydrogenated block copolymer (c)>
Known techniques can be used to produce the hydrogenated block copolymer (c).
An example of a typical conventional technique is a method of block copolymerizing a conjugated diene compound and a vinyl aromatic compound using an anionic initiator such as an organolithium compound in a hydrocarbon solvent. For example, in Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17979, Japanese Patent Publication No. 48-2423, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. 57-49567, and Japanese Patent Publication No. 58-11446. It can be manufactured by the method described.

[Polymerization solvent]
The hydrogenated block copolymer (c) is obtained by block copolymerizing a vinyl aromatic compound and a conjugated diene compound in a polymerization solvent.
As the polymerization solvent used for producing the hydrogenated block copolymer (c), conventionally known hydrocarbon solvents can be used. Examples of the hydrocarbon solvent include, but are not limited to, aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; cyclopentane, methylcyclopentane; , alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, cycloheptane, and methylcycloheptane; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.
These hydrocarbon solvents may be used alone or in combination of two or more. Among these, when an organolithium initiator is used, n-hexane and cyclohexane are generally used, and among them, cyclohexane is industrially the most widely used and is preferably used.

[Polymerization initiator]
The polymerization initiator is not particularly limited, but for example, a polymerization initiator that exhibits anionic polymerization activity toward conjugated diene compounds and vinyl aromatic compounds can be suitably used. Examples include alkali metal compounds such as aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, and organic amino alkali metal compounds.

The alkali metal used in the alkali metal compound is not particularly limited, and examples thereof include lithium, sodium, potassium, and the like.
Suitable alkali metal compounds include, but are not limited to, aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms, and compounds containing one lithium in one molecule; Examples include dilithium compounds, trilithium compounds, and tetralithium compounds containing multiple lithium compounds.

Examples of such alkali metal compounds include, but are not limited to, n-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, hexamethylene dilithium, butadienyl dilithium, isoprenyl Examples include dilithium, a reaction product of diisopropenylbenzene and sec-butyllithium, and a reaction product of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene.

Organic alkali metal compounds disclosed in foreign patents such as US Pat. No. 5,708,092, British Patent No. 2,241,239, and US Pat. No. 5,527,753 can also be used. These may be used alone or in combination of two or more. Among these, n-butyllithium is most preferred.

[Polymerization process]
In the polymerization process of the hydrogenated block copolymer (c), the hydrogenated block copolymer (c) finally obtained can be obtained by adjusting the charging ratio of the vinyl aromatic compound and the conjugated diene compound, which are polymerization raw materials. The content of vinyl aromatic monomer units and the content of conjugated diene monomer units can be controlled.

The polymerization process for hydrogenated block copolymer (c) includes, for example, a process in which a polymerization initiator is additionally added during the polymerization, a process in which a polymerization initiator is additionally added during the polymerization, and a process in which a polymerization initiator is partially added by adding a small amount of a polyfunctional monomer having two or more reactive sites. It is also possible to suitably employ a process in which a coupling reaction is carried out, or a process in which alcohol, water, etc. is added in an amount less than the polymerization active site during the polymerization, and then the monomer is supplied again to continue the polymerization. By appropriately selecting such a process, it is possible to produce a hydrogenated block copolymer (c) in which a plurality of types of components having mutually different molecular weights are present.

As a method for producing a copolymer block consisting of a vinyl aromatic monomer unit and a conjugated diene monomer unit, a mixture of a vinyl aromatic compound and a conjugated diene compound is continuously fed into a polymerization system and polymerized. Examples include a method of copolymerizing a vinyl aromatic compound and a conjugated diene compound using a polar compound or a randomizing agent.

Furthermore, the polar compound or randomizing agent also has the effect of increasing the proportion of vinyl bonds in the conjugated diene when the conjugated diene compound is polymerized alone.
The amount of vinyl bonds in the hydrogenated block copolymer (c) can be controlled by using a Lewis base, for example, a compound such as an ether or an amine as a vinylizing agent. The amount of the vinylating agent used can be adjusted depending on the desired amount of vinyl bonding.

Examples of vinylizing agents include, but are not limited to, ether compounds, tertiary amine compounds, and the like.

Examples of the ether compound include, but are not limited to, ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether.
Examples of tertiary amine compounds include, but are not limited to, pyridine, N,N,N',N'-tetramethylethylenediamine, tributylamine, tetramethylpropanediamine, and 1,2-dipiperidiamine. Examples thereof include noethane, bis[2-(N,N-dimethylamino)ethyl]ether, and the like.
These may be used alone or in combination of two or more.
As the tertiary amine compound, a compound having two amines is preferred. Furthermore, among them, those having a structure showing symmetry within the molecule are more preferable, such as N,N,N',N'-tetramethylethylenediamine, bis[2-(N,N-dimethylamino)ethyl]ether, More preferred is 1,2-dipiperidinoethane.

The hydrogenated block copolymer (c) can be produced in the coexistence of an alkali metal alkoxide for the purpose of controlling the amount of vinyl bonds. Alkali metal alkoxide is a compound represented by the general formula: MOR (in the formula, M is an alkali metal and R is an alkyl group), and is a hydrogenated block copolymer (c) having a high vinyl bond content. It becomes possible to obtain.

The alkali metal of the alkali metal alkoxide is preferably sodium or potassium from the viewpoints of high vinyl bond content, narrow molecular weight distribution, high polymerization rate, and high block rate.
Examples of the alkali metal alkoxide include, but are not limited to, sodium alkoxide, lithium alkoxide, and potassium alkoxide having an alkyl group having 2 to 12 carbon atoms, preferably having an alkyl group having 3 to 6 carbon atoms. These include sodium alkoxide and potassium alkoxide, and more preferably sodium t-butoxide, sodium t-pentoxide, potassium t-butoxide, and potassium t-pentoxide. Among these, sodium alkoxides such as sodium t-butoxide and sodium t-pentoxide are more preferred.

In the polymerization step of the hydrogenated block copolymer (c), when polymerization is carried out in the coexistence of a vinylating agent, an organolithium compound, and an alkali metal alkoxide, the molar ratio of the vinylating agent and the organolithium compound (vinylating agent/organolithium compound) and the molar ratio of the alkali metal alkoxide to the organolithium compound (alkali metal alkoxide/organolithium compound) are preferably made to coexist at the following molar ratio.
Vinylating agent/organolithium compound molar ratio: 0.2 to 3.0
Alkali metal alkoxide/organolithium compound molar ratio: 0.01 to 0.3

The molar ratio of vinylating agent/organolithium compound is preferably 0.2 or more from the viewpoint of high vinyl bond content and high polymerization rate, and 3.0 or less from the viewpoint of obtaining narrow molecular weight distribution and high hydrogenation activity. It is preferable that In addition, the molar ratio of alkali metal alkoxide/organolithium compound is preferably 0.01 or more from the viewpoints of high vinyl bond content, high polymerization rate, and high block rate. It is preferable to set it as 0.3 or less from a viewpoint of obtaining. This improves the polymerization rate, increases the amount of vinyl bonds in the desired hydrogenated block copolymer (c), narrows the molecular weight distribution, and tends to improve the block rate.
As a result, it inhibits crystallization originating from the polyethylene structure of the hydrogenated conjugated diene block part, exhibits the characteristics of a flexible elastic body, and at the same time is compatible with various polyolefin resins including bio-based polyethylene (b). It becomes possible to add functions.
By controlling the amount of vinyl bonds in the hydrogenated block copolymer (c), it not only functions as a compatibilizer, but also fulfills various required properties depending on the application, such as impact resistance, flexibility, and transparency. becomes possible.

The optimum polymerization temperature in the polymerization step of the hydrogenated block copolymer (c) varies depending on the polymer structure, but in the case of anionic polymerization using a polymerization initiator, it is generally -10°C to 150°C, preferably The temperature ranges from 10°C to 100°C.
Further, the time required for polymerization is usually within 48 hours, preferably in the range of 0.1 to 10 hours.
Further, the atmosphere of the polymerization system is preferably replaced with an inert gas such as nitrogen gas.
The polymerization pressure is not particularly limited as long as it is within a pressure range sufficient to maintain the monomer and polymerization solvent in a liquid phase within the above polymerization temperature range.
Furthermore, it is preferable to take care not to unintentionally introduce impurities such as water, oxygen, carbon dioxide gas, etc. that would inactivate the polymerization initiator and living polymer into the polymerization system.

When obtaining a hydrogenated block copolymer (c) containing random copolymer blocks, a mixture of a vinyl aromatic compound and a conjugated diene compound is continuously supplied to the polymerization system and polymerized. And/or it is preferable to employ a method such as copolymerizing a vinyl aromatic compound and a conjugated diene compound using a polar compound or a randomizing agent.

When an organic alkali metal is used as a polymerization initiator in the production of hydrogenated block copolymer (c), a coupling reaction in which two or more molecules are combined to terminate the polymerization reaction is preferably used to terminate the polymerization reaction. Can be done.
The coupling reaction can be carried out by adding a coupling agent exemplified below into the polymerization system. In addition, by adjusting the amount of the coupling agent added, it is possible to couple only a part of the polymer in the polymerization system, allowing the uncoupled polymer and the coupled polymer to coexist. A hydrogenated block copolymer (c) having two or more peaks can be produced.

The coupling agent that can be suitably used in the production of the hydrogenated block copolymer (c) is not particularly limited, but includes, for example, any coupling agent having two or more functional groups.
Specifically, tetraglycidyl metaxylene diamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, diglycidyl orthotoluidine, γ-glycidoxy Ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxy Examples include silane compounds containing an amino group such as propyltributoxysilane.
In addition, other coupling agents include, for example, 1-[3-(triethoxysilyl)-propyl]-4-methylpiperazine, 1-[3-(diethoxyethylsilyl)-propyl]-4-methylpiperazine , 1-[3-(trimethoxysilyl)-propyl]-3-methylimidazolidine, 1-[3-(diethoxyethylsilyl)-propyl]-3-ethylimidazolidine, 1-[3-(triethoxysilyl)-propyl]-3-ethylimidazolidine silyl)-propyl]-3-methylhexahydropyrimidine, 1-[3-(dimethoxymethylsilyl)-propyl]-3-methylhexahydropyrimidine, 3-[3-(tributoxysilyl)-propyl]-1- Methyl-1,2,3,4-tetrahydropyrimidine, 3-[3-(dimethoxymethylsilyl)-propyl]-1-ethyl-1,2,3,4-tetrahydropyrimidine, 1-(2-ethoxyethyl) -3-[3-(trimethoxysilyl)-propyl]-imidazolidine, (2-{3-[3-(trimethoxysilyl)-propyl]-tetrahydropyrimidin-1-yl}-ethyl)dimethylamine, etc. Examples include silane compounds containing a silyl group.

Other coupling agents include, for example, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane. , γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxy Propyldimethylmethoxysilane, γ-glycidoxypropyldiethyl ethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropyldimethylphenoxysilane γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropyl Methyldiisopropeneoxysilane, bis(γ-glycidoxypropyl)dimethoxysilane, bis(γ-glycidoxypropyl)diethoxysilane, bis(γ-glycidoxypropyl)dipropoxysilane, bis(γ-glycidoxypropyl)dipropoxysilane, bis(γ-glycidoxypropyl)dipropoxysilane, dibutoxysilane, bis(γ-glycidoxypropyl)diphenoxysilane, bis(γ-glycidoxypropyl)methylmethoxysilane, bis(γ-glycidoxypropyl)methylethoxysilane, bis(γ-glycidoxypropyl)methylethoxysilane, bis(γ-glycidoxypropyl)dibutoxysilane, - Glycidoxy groups such as glycidoxypropyl) methylpropoxysilane, bis(γ-glycidoxypropyl)methylbutoxysilane, bis(γ-glycidoxypropyl)methylphenoxysilane, tris(γ-glycidoxypropyl)methoxysilane, etc. Examples include silane compounds containing .

Other coupling agents include, for example, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-methacryloxyethyltriethoxysilane, bis( Examples include silane compounds containing methacryloxy groups such as γ-methacryloxypropyl) dimethoxysilane and tris(γ-methacryloxypropyl)methoxysilane.

Other coupling agents include, for example, β-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-triethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-triethoxysilane, -Epoxycyclohexyl)ethyl-tripropoxysilane, β-(3,4-epoxycyclohexyl)ethyl-tributoxysilane, β-(3,4-epoxycyclohexyl)ethyl-triphenoxysilane β-(3,4-epoxycyclohexyl) ) Propyl-trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-ethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl -Ethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldipropoxysilane, β-(3,4-epoxycyclohexyl) Ethyl-methyldibutoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldiphenoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylmethoxysilane, β-(3,4-epoxycyclohexyl) Ethyl-diethylethoxysilane β-(3,4-epoxycyclohexyl)ethyl-dimethylethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylpropoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethyl Butoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylphenoxysilane, β-(3,4-epoxycyclohexyl)ethyl-diethylmethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldiisopro Examples include silane compounds containing an epoxycyclohexyl group such as penoxysilane.
Examples of other coupling agents include 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, and N-methylpyrrolidone. .

Note that when the coupling agent is added to the living end of the hydrogenated block copolymer (c), the structure of the living end of the hydrogenated block copolymer (c) is not limited in any way; From the viewpoint of mechanical strength, etc. of the ABS resin composition, it is preferable that the polymer block is a living end of a polymer block mainly composed of vinyl aromatic monomer units.
The amount of the coupling agent used is preferably 0.1 equivalent or more and 10 equivalents or less, and preferably 0.5 equivalent or more and 4 equivalents or less, based on 1 equivalent of the living end of the hydrogenated block copolymer (c). is more preferable.
One type of coupling agent may be used alone, or any two or more types may be used in combination.

[Hydrogenation process]
The hydrogenated block copolymer (c) is produced through a step of hydrogenating some or all of the double bonds in the conjugated diene monomer units of the block copolymer obtained in the polymerization step.
The catalyst used in the hydrogenation reaction is not particularly limited, but examples include supported heterogeneous catalysts in which metals such as Ni, Pt, Pd, and Ru are supported on a carrier such as carbon, silica, alumina, and diatomaceous earth. ; A so-called Ziegler type catalyst using an organic salt such as Ni, Co, Fe, Cr or an acetylacetone salt and a reducing agent such as organic Al; A so-called organic complex catalyst such as an organometallic compound such as Ru or Rh, or reduction to a titanocene compound Examples include homogeneous catalysts using organic Li, organic Al, organic Mg, etc. as agents. Among these, a homogeneous catalyst system using a titanocene compound and organic Li, organic Al, organic Mg, etc. as a reducing agent is preferred from the viewpoint of economy, coloring property of the polymer, or adhesive strength.

The hydrogenation method is not particularly limited, but for example, the method described in Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, and preferably, Japanese Patent Publication No. 63-4841 and Japanese Patent Publication No. 63-5401. For example, the method described in the publication No. Specifically, a hydrogenated block copolymer solution can be obtained by hydrogenating in an inert solvent in the presence of a hydrogenation catalyst.
Although the hydrogenation reaction is not particularly limited, from the viewpoint of developing high hydrogenation activity, it is preferable to carry out the hydrogenation reaction after the step of deactivating the active end of the polymer described above. The hydrogenation step can be performed in either a batch process, a continuous process, or a combination thereof.

In the hydrogenation step, a part of the conjugated bonds of the vinyl aromatic monomer unit may be hydrogenated.
The hydrogenation rate of conjugated bonds in all vinyl aromatic monomer units is preferably 30 mol% or less, more preferably 10 mol% or less, and still more preferably 3 mol% or less.
Considering that mechanical properties are expressed by forming a microphase-separated structure, it is preferable that the vinyl aromatic monomer unit is not hydrogenated and is close to 0 mol %.

[Modification process]
A polar group may be introduced into the hydrogenated block copolymer (c) by carrying out a modification step.
Known methods can be applied to the modification method, and in the polymerization step, a method of modifying by using a compound having a polar group as a polymerization initiator and/or a polymerization terminator (referred to as terminal modification) may be carried out. The hydrogenated block copolymer is modified by adding an unsaturated compound having a polar group using a single-screw or twin-screw extruder, with or without a radical generator. A method (referred to as backbone denaturation) may be performed.

Specific methods for introducing polar groups into the hydrogenated block copolymer (c) include, for example, a melt-kneading method using an extruder or the like, a method of reacting by dissolving and dispersing mixing using a solvent, etc. . This is called a graft reaction or main chain modification. In addition, in the process of polymerizing the hydrogenated block copolymer (c), a method of polymerizing using a monomer having a functional group, and a method of polymerizing using a monomer having a functional group, and a method of polymerizing using a monomer having a functional group instead of alcohols, which are common in the polymerization termination reaction, may be used. A method in which polymerization is terminated by modification with is also applicable. This is called terminal degeneration.

A "polar group" can be formed using a modifier.
Modifiers include, but are not limited to, tetraglycidyl metaxylene diamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ε-caprolactone, δ-valerolactone, 4-methoxybenzophenone, γ-glycidoxy Ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, bis(γ-glycidoxypropyl)methylpropoxysilane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, N-methylpyrrolidone, maleic acid, maleic anhydride, maleic anhydride, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, Examples include glycidyl methacrylate and crotonic acid.

The amount of the modifier added can be measured by a known analytical method.
As a general method, for example, in the case of modification with maleic anhydride, a titration method using sodium methoxide can be exemplified.

(Other additives that can be blended into ABS resin compositions)
The ABS resin composition of the present embodiment may contain any compounding agents or additives within the range of not departing from the spirit of the present invention and not inhibiting the effects of the present invention.
Examples of compounding agents and additives include those commonly used in compounding resins and rubbery polymers, including but not limited to, calcium carbonate, magnesium carbonate, silica, zinc oxide, carbon black, etc. Inorganic fillers; higher alcohols such as stearyl alcohol; higher fatty acids such as palmitic acid, stearic acid, and behenic acid; higher fatty acid metals such as zinc stearate, calcium stearate, magnesium stearate, magnesium behenate, and hydrogenated magnesium ricinoleate. Salts; Lubricants and mold release agents such as fatty acid amides such as erucic acid amide and ethylene bisstearylamide; Paraffin oil, process oil, organic polysiloxanes such as dimethyl silicone and methylphenyl silicone; Softeners and plasticizers such as mineral oil; Hindered phenol-based, phosphorus-based heat stabilizers and antioxidants; hindered amine-based light stabilizers; benzotriazole-based ultraviolet absorbers; halogen-based, phosphorus-based, etc. flame retardants; organic fibers, glass fibers, carbon fibers, metal whiskers reinforcing agents such as; coloring agents such as organic pigments, inorganic pigments, and organic dyes; and the like.

(Method for manufacturing ABS resin composition)
Although the method for producing the ABS resin composition of the present embodiment is not particularly limited, for example, ABS resin (a), bio-based polyethylene (b), and hydrogenated block copolymer (c), After dry blending the pellets at room temperature, they are supplied to a twin-screw extruder hopper, heated and kneaded by the twin-screw extruder, and extruded from a die into a strand shape of the heated and molten ABS resin composition, which is then passed through a cooling bath. An example of this method is to pelletize the resin composition again to obtain a pelletized resin composition.
When heat-melting and kneading, there is no particular restriction as long as it is a kneader for thermoplastic resin that can be heated and melted, such as a kneader, a Banbury mixer, a roll, a ribbon blender, a mixer such as a single-screw extruder or a twin-screw extruder, etc. A kneading machine can be suitably used.
In addition to the strand cutting method using a cooling bath, hot cutting methods and underwater cutting methods can be preferably used depending on the purpose.

In the method for producing an ABS resin composition of the present embodiment, the mass ratio of the ABS resin (a) and the biobased polyethylene (b) is set to (a)/(b) = 99/1 to 50/50. The mass ratio of the bio-based polyethylene (b) and the hydrogenated block copolymer (c) is (b)/(c) = 90/10 to 50/50.
By setting the mass ratio as above, it has a certain degree of bio-based content, has an excellent balance of mechanical properties possessed by the original ABS resin, and can be combined without sacrificing the excellent paintability. An ABS resin composition with excellent balance of mechanical properties, which exhibits impact strength exceeding that of the original ABS resin, can be obtained.

(Preferred physical properties of ABS resin composition)
The ABS resin composition of the present embodiment is characterized in that the biobased polyethylene (b) has a relative melt viscosity ηabs (Pa·s) of the ABS resin (a) in a capillary rheometer under a temperature condition of 220°C. It is preferable that the ratio of the apparent melt viscosity ηgpe (Pa s): ηgpe/ηabs is always 0.3 or more when the apparent shear rate γa (sec ^-1 ) is between 12.16 and 1216, and more preferably Preferably it is 0.5 or more, more preferably 0.8 or more, even more preferably 1.0 or more.
By satisfying these conditions, the ABS resin composition of this embodiment has a good dispersion form. Specifically, when the dispersion form of the ABS resin composition of this embodiment was analyzed using a transmission electron microscope, it was found that the ABS resin (a) forms a continuous phase and the biobased polyethylene (b) forms a dispersed layer. This results in various mechanical properties such as tensile yield strength, tensile elongation at break, bending strength, bending modulus, Charpy impact strength, Rockwell hardness, deflection temperature under load, and softening temperature. The results are excellent, and the paintability of the molded product is also good.

In the ABS resin composition of the present embodiment, the apparent shear rate γa (sec ^-1 ) of the ABS resin (a) is between 12.16 and 1216 at a temperature of 220°C. The ratio of the apparent melt viscosity ηgpe (Pa s) of the biobased polyethylene (b) to the melt viscosity ηabs (Pa s): ηgpe/ηabs is the biomass specified in ASTM D6866 as the biobased polyethylene (b). After using an ethylene homopolymer (b1) and/or a copolymer of ethylene and α-olefin mainly composed of ethylene (b2) having a degree of 80% or more and 100% or less, the ABS resin of this embodiment The mass ratio (a)/(b) of the ABS system (a) and the bio-based polyethylene (b) constituting the composition may be adjusted, or the bio-based polyethylene (b) and the hydrogenated block copolymer ( Control within the above numerical range by adjusting the mass ratio (b)/(c) of c) or appropriately selecting brands of components (a) and (c) based on the melt flow rate value. be able to.

[Molded object, coated film formed object]
Examples of the molded product of the ABS resin composition of the present embodiment include various molded products obtained by various known molding methods, such as injection molded products, blow molded products, and extrusion molded products. There are various uses depending on the various molding methods. Typical examples include housings for home appliances, accessory parts for mobile terminals and devices, indoor wiring covers, automobile interior and exterior parts, stationery, etc. is wide-ranging.
Moreover, the molded object of this embodiment may be a coated molded object having a coating film. In the ABS resin composition of this embodiment, the ABS resin (a) forms a continuous phase and the biobased polyethylene (b) forms a dispersed phase. The molded product has high paint film adhesion and excellent paintability. The coating film can be formed using a conventionally known paint, such as an acrylic paint. Coating film adhesion can be evaluated by the method described in the Examples below.

Hereinafter, the present embodiment will be described in more detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples and comparative examples.

[ABS resin (a), bio-based polyethylene (b), petroleum-based polyethylene (b')]
ABS resins (a)-1 to 3, bio-based polyethylene (b)-1 to 3, and petroleum-based polyethylene (b')-X and Y were obtained from brands sold by various manufacturers and used.
Table 1 below shows the manufacturer, brand name, and representative physical properties of ABS resin (a). Table 2 below shows the manufacturers, brand names, and representative physical properties of bio-based polyethylene (b) and petroleum-based polyethylene (b').

[Hydrogenated block copolymer (c)]
Each of the hydrogenated block copolymers (c) used in Examples and Comparative Examples to be described later was manufactured in the following manner.

(Manufacture of hydrogenation catalyst)
A hydrogenation catalyst was prepared as follows.
Place 1 L of dried and purified cyclohexane in a reaction vessel purged with nitrogen, add 100 mmol of bis(cyclopentadienyl)titanium dichloride, and add an n-hexane solution containing 200 mmol of trimethylaluminum with sufficient stirring. A hydrogenation catalyst was obtained by reacting at room temperature for about 3 days.

(Production of hydrogenated block copolymer)
Hydrogenated block copolymers (c)-1 to 12 were produced according to the following production examples.

<Manufacture example 1>
Using a jacketed tank reactor, a predetermined amount of cyclohexane was charged, and the temperature inside the reactor was adjusted to 75° C. under a nitrogen gas atmosphere.
Next, 0.14 parts by mass of n-butyllithium and 0.33 parts by mass of tetramethylmethylenediamine were added.
Next, a cyclohexane solution containing 15 parts by mass of styrene at a concentration of 20% by mass was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 15 minutes.
Next, a cyclohexane solution containing 70 parts by weight of 1,3-butadiene at a concentration of 20% by weight was supplied to the reactor over about 50 minutes. After the supply, the reaction was continued for 10 minutes while adjusting the temperature inside the reactor to 75°C.
Next, a cyclohexane solution containing 15 parts by mass of styrene at a concentration of 20% by mass was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 15 minutes.

Thereafter, in order to completely stop the polymerization, ethanol was added to the reactor in equal molar proportions to n-butyllithium to stop the polymerization reaction.
Next, the hydrogenation catalyst was added to the obtained polymer solution in an amount of 100 ppm of titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85°C.
After the hydrogenation reaction is completed, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) is added as an antioxidant to 100 parts by mass of the block copolymer. did.
Thereafter, hydrogenated block copolymer (c)-1 was recovered by removing the solvent.

<Production example 2>
Using a jacketed tank reactor, a predetermined amount of cyclohexane was charged, and the temperature inside the reactor was adjusted to 75° C. under a nitrogen gas atmosphere.
Next, 0.17 parts by mass of n-butyllithium and 0.31 parts by mass of tetramethylmethylenediamine were added.
Next, a cyclohexane solution containing 34 parts by mass of styrene at a concentration of 20% by mass was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 15 minutes.
Next, a cyclohexane solution containing 32 parts by weight of 1,3-butadiene at a concentration of 20% by weight was supplied to the reactor over about 30 minutes. After the supply, the reaction was continued for 10 minutes while adjusting the temperature inside the reactor to 75°C.
Next, a cyclohexane solution containing 34 parts by mass of styrene at a concentration of 20% by mass was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 15 minutes.

Thereafter, in order to completely stop the polymerization, ethanol was added into the reactor in an equal molar amount to n-butyllithium to stop the polymerization reaction.
Next, the hydrogenation catalyst was added to the obtained polymer solution in an amount of 100 ppm of titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85°C.
After the hydrogenation reaction is completed, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) is added as an antioxidant to 100 parts by mass of the block copolymer. did.
Thereafter, hydrogenated block copolymer (c)-2 was recovered by removing the solvent.

<Manufacture example 3>
Using a jacketed tank reactor, a predetermined amount of cyclohexane was charged, and the temperature inside the reactor was adjusted to 65° C. under a nitrogen gas atmosphere.
Next, 0.16 parts by mass of n-butyllithium and 0.20 parts by mass of tetramethylmethylenediamine were added.
Next, a cyclohexane solution containing 10 parts by weight of 1,3-butadiene at a concentration of 20% by weight was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 5 minutes.
Next, a cyclohexane solution containing 15 parts by mass of styrene at a concentration of 15% by mass was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 10 minutes.
Next, a cyclohexane solution containing 60 parts by weight of 1,3-butadiene at a concentration of 20% by weight was supplied to the reactor over about 50 minutes. After the supply, the reaction was continued for 10 minutes while adjusting the temperature inside the reactor to 65°C.
Next, a cyclohexane solution containing 15 parts by mass of styrene at a concentration of 20% by mass was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 10 minutes.

Thereafter, in order to completely stop the polymerization, ethanol was added to the reactor in equal molar proportions to n-butyllithium to stop the polymerization reaction.
Next, the hydrogenation catalyst was added to the obtained polymer solution in an amount of 100 ppm of titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85°C.
After the hydrogenation reaction is completed, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) is added as an antioxidant to 100 parts by mass of the block copolymer. did.
Thereafter, hydrogenated block copolymer (c)-3 was recovered by removing the solvent.

<Manufacture example 4>
Using a jacketed tank reactor, a predetermined amount of cyclohexane was charged, and the temperature inside the reactor was adjusted to 65° C. under a nitrogen gas atmosphere.
Next, 0.16 parts by mass of n-butyllithium and 0.20 parts by mass of tetramethylmethylenediamine were added.
Next, a cyclohexane solution containing 5 parts by weight of 1,3-butadiene at a concentration of 20% by weight was supplied to the reactor over about 5 minutes. After the supply, the reaction was continued for 5 minutes.
Next, a cyclohexane solution containing 20 parts by mass of styrene at a concentration of 20% by mass was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 10 minutes.
Next, a cyclohexane solution containing 55 parts by weight of 1,3-butadiene at a concentration of 20% by weight was supplied to the reactor over about 50 minutes. After the supply, the reaction was continued for 10 minutes while adjusting the temperature inside the reactor to 65°C.
Next, a cyclohexane solution containing 20 parts by mass of styrene at a concentration of 20% by mass was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 10 minutes.

Thereafter, in order to completely stop the polymerization, ethanol was added into the reactor in an equal molar amount to n-butyllithium to stop the polymerization reaction.
Next, the hydrogenation catalyst was added to the obtained polymer solution in an amount of 100 ppm of titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85°C.
After the hydrogenation reaction is completed, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) is added as an antioxidant to 100 parts by mass of the block copolymer. did.
Thereafter, hydrogenated block copolymer (c)-4 was recovered by removing the solvent.

<Manufacture example 5>
Using a jacketed tank reactor, a predetermined amount of cyclohexane was charged, and the temperature inside the reactor was adjusted to 60° C. under a nitrogen gas atmosphere.
Next, 0.05 parts by mass of n-butyllithium and 0.05 parts by mass of tetramethylmethylenediamine were added.
Next, a cyclohexane solution containing 10 parts by weight of 1,3-butadiene at a concentration of 20% by weight was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 5 minutes.
Next, after adding 0.004 parts by mass of sodium t-pentoxide, 1.50 parts by mass of tetramethylmethylenediamine was added, and then a cyclohexane solution containing 85 parts by mass of 1,3-butadiene at a concentration of 20% by mass was added. The reactor was fed over approximately 60 minutes. After the supply, the reaction was continued for 10 minutes.
Next, a cyclohexane solution containing 5 parts by mass of styrene at a concentration of 20% by mass was supplied to the reactor over about 5 minutes. After the supply, the reaction was continued for 10 minutes.

Thereafter, in order to completely stop the polymerization, ethanol was added to the reactor in equal molar proportions to n-butyllithium to stop the polymerization reaction.
Next, the hydrogenation catalyst was added to the obtained polymer solution in an amount of 100 ppm of titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85°C.
After the hydrogenation reaction, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) was added as an antioxidant to 100 parts by mass of the hydrogenated block copolymer. Part was added.
Thereafter, hydrogenated block copolymer (c)-5 was recovered by removing the solvent.

<Manufacture example 6>
Using a jacketed tank reactor, a predetermined amount of cyclohexane was charged, and the temperature inside the reactor was adjusted to 50° C. under a nitrogen gas atmosphere.
Next, 0.14 parts by mass of n-butyllithium and 0.27 parts by mass of tetramethylmethylenediamine were added.
Next, a cyclohexane solution containing 15 parts by mass of styrene at a concentration of 20% by mass was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 5 minutes.
Next, a cyclohexane solution containing 85 parts by weight of 1,3-butadiene at a concentration of 20% by weight was supplied to the reactor over about 60 minutes. After the supply, the reaction was continued for 10 minutes.
Next, tetraethoxysilane as a coupling agent was supplied to the reactor in a molar amount of 0.1 times that of n-butyllithium. After the supply, the reaction was continued for 10 minutes.

Thereafter, in order to completely stop the polymerization, ethanol was added to the reactor in a molar amount of 0.9 times n-butyllithium to stop the polymerization reaction.
Next, the hydrogenation catalyst was added to the obtained polymer solution in an amount of 90 ppm of titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85°C. The hydrogenation rate was adjusted by adjusting the amount of hydrogen supplied to the reactor.
After the hydrogenation reaction, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) was added as an antioxidant to 100 parts by mass of the hydrogenated block copolymer. Part was added.
Thereafter, hydrogenated block copolymer (c)-6 was recovered by removing the solvent.

<Manufacture example 7>
Using the hydrogenated block copolymer (c)-1 obtained in Production Example 1, 2 parts by mass of maleic anhydride and 2,5 parts by mass of maleic anhydride as a radical initiator were added to 100 parts by mass of the hydrogenated block copolymer. - 0.15% by mass of dimethyl-2,5-bis(t-butylperoxy)hexane (trade name: Perhexa 25B, manufactured by NOF Corporation) was added, and a twin-screw extruder TEX30α (screw The main chain was modified by a graft reaction on the hydrogenated block copolymer at a cylinder temperature of 220° C. using a cylinder with a diameter of 30 mm, two axes in the same direction, and L/D=42. In this way, a hydrogenated block copolymer (c)-7 modified with maleic anhydride was obtained.

<Manufacture example 8>
Using a jacketed tank reactor, a predetermined amount of cyclohexane was charged, and the temperature inside the reactor was adjusted to 75° C. under a nitrogen gas atmosphere.
Next, 0.14 parts by mass of n-butyllithium and 0.33 parts by mass of tetramethylmethylenediamine were added.
Next, a cyclohexane solution containing 15 parts by mass of styrene at a concentration of 20% by mass was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 15 minutes.
Next, a cyclohexane solution containing 70 parts by weight of 1,3-butadiene at a concentration of 20% by weight was supplied to the reactor over about 50 minutes. After the supply, the reaction was continued for 10 minutes while adjusting the temperature inside the reactor to 75°C.
Next, a cyclohexane solution containing 15 parts by mass of styrene at a concentration of 20% by mass was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 15 minutes.

Thereafter, in order to completely stop the polymerization, ethanol was added into the reactor in an equal molar amount to n-butyllithium to stop the polymerization reaction.
Next, the hydrogenation catalyst was added to the obtained polymer solution in an amount of 100 ppm of titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85°C. The hydrogenation rate was adjusted by adjusting the amount of hydrogen supplied to the reactor.
After the hydrogenation reaction is completed, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) is added as an antioxidant to 100 parts by mass of the block copolymer. did.
Thereafter, hydrogenated block copolymer (c)-8 was recovered by removing the solvent.

<Manufacture example 9>
Using a jacketed tank reactor, a predetermined amount of cyclohexane was charged, and the temperature inside the reactor was adjusted to 75° C. under a nitrogen gas atmosphere.
Next, 0.14 parts by mass of n-butyllithium and 0.33 parts by mass of tetramethylmethylenediamine were added.
Next, a cyclohexane solution containing 15 parts by mass of styrene at a concentration of 20% by mass was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 15 minutes.
Next, a cyclohexane solution containing 70 parts by weight of 1,3-butadiene at a concentration of 20% by weight was supplied to the reactor over about 50 minutes. After the supply, the reaction was continued for 10 minutes while adjusting the temperature inside the reactor to 75°C.
Next, a cyclohexane solution containing 15 parts by mass of styrene at a concentration of 20% by mass was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 15 minutes.

Thereafter, in order to completely stop the polymerization, ethanol was added to the reactor in equal molar proportions to n-butyllithium to stop the polymerization reaction.
Next, the hydrogenation catalyst was added to the obtained polymer solution in an amount of 100 ppm of titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85°C. The hydrogenation rate was adjusted by adjusting the amount of hydrogen supplied to the reactor.
After the hydrogenation reaction is completed, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) is added as an antioxidant to 100 parts by mass of the block copolymer. did.
Thereafter, hydrogenated block copolymer (c)-9 was recovered by removing the solvent.

<Manufacture example 10>
Using a jacketed tank reactor, a predetermined amount of cyclohexane was charged, and the temperature inside the reactor was adjusted to 60° C. under a nitrogen gas atmosphere.
Next, 0.05 parts by mass of n-butyllithium and 0.05 parts by mass of tetramethylmethylenediamine were added.
Next, a cyclohexane solution containing 10 parts by weight of 1,3-butadiene at a concentration of 20% by weight was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 5 minutes.
Next, after adding 0.004 parts by mass of sodium t-pentoxide, 1.50 parts by mass of tetramethylmethylenediamine was added, and then a cyclohexane solution containing 87 parts by mass of 1,3-butadiene at a concentration of 20% by mass was added. The reactor was fed over approximately 60 minutes. After the supply, the reaction was continued for 10 minutes.
Next, a cyclohexane solution containing 3 parts by mass of styrene at a concentration of 20% by mass was supplied to the reactor over about 5 minutes. After the supply, the reaction was continued for 10 minutes.

Thereafter, in order to completely stop the polymerization, ethanol was added into the reactor in an equal molar amount to n-butyllithium to stop the polymerization reaction.
Next, the hydrogenation catalyst was added to the obtained polymer solution in an amount of 100 ppm of titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85°C.
After the hydrogenation reaction, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) was added as an antioxidant to 100 parts by mass of the hydrogenated block copolymer. Part was added.
Thereafter, hydrogenated block copolymer (c)-10 was recovered by removing the solvent.

<Manufacture example 11>
Using a jacketed tank reactor, a predetermined amount of cyclohexane was charged, and the temperature inside the reactor was adjusted to 75° C. under a nitrogen gas atmosphere.
Next, 0.17 parts by mass of n-butyllithium and 0.31 parts by mass of tetramethylmethylenediamine were added.
Next, a cyclohexane solution containing 38 parts by mass of styrene at a concentration of 20% by mass was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 15 minutes.
Next, a cyclohexane solution containing 24 parts by weight of 1,3-butadiene at a concentration of 20% by weight was supplied to the reactor over about 30 minutes. After the supply, the reaction was continued for 10 minutes while adjusting the temperature inside the reactor to 75°C.
Next, a cyclohexane solution containing 38 parts by mass of styrene at a concentration of 20% by mass was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 15 minutes.

Thereafter, in order to completely stop the polymerization, ethanol was added to the reactor in equal molar proportions to n-butyllithium to stop the polymerization reaction.
Next, the hydrogenation catalyst was added to the obtained polymer solution in an amount of 100 ppm of titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85°C.
After the hydrogenation reaction is completed, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) is added as an antioxidant to 100 parts by mass of the block copolymer. did.
Thereafter, hydrogenated block copolymer (c)-11 was recovered by removing the solvent.

<Manufacture example 12>
Using a jacketed tank reactor, a predetermined amount of cyclohexane was charged, and the temperature inside the reactor was adjusted to 65° C. under a nitrogen gas atmosphere.
Next, 0.17 parts by mass of n-butyllithium was added. No tetramethylmethylene diamine was added.
Next, a cyclohexane solution containing 20 parts by mass of styrene at a concentration of 20% by mass was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 10 minutes.
Next, a cyclohexane solution containing 60 parts by weight of 1,3-butadiene at a concentration of 20% by weight was supplied to the reactor over about 50 minutes. After the supply, the reaction was continued for 10 minutes while adjusting the temperature inside the reactor to 65°C.
Next, a cyclohexane solution containing 20 parts by mass of styrene at a concentration of 20% by mass was supplied to the reactor over about 10 minutes. After the supply, the reaction was continued for 10 minutes.

Thereafter, in order to completely stop the polymerization, ethanol was added into the reactor in an equal molar amount to n-butyllithium to stop the polymerization reaction.
Next, the hydrogenation catalyst was added to the obtained polymer solution in an amount of 80 ppm of titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85°C. The hydrogenation rate was adjusted by adjusting the amount of hydrogen supplied to the reactor.
After the hydrogenation reaction, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) was added as an antioxidant to 100 parts by mass of the hydrogenated block copolymer. Part was added.
Thereafter, hydrogenated block copolymer (c)-12 was recovered by removing the solvent.

(Physical properties of hydrogenated block copolymer)
<Content of vinyl aromatic monomer units (styrene units) and hydrogenated conjugated diene monomer units (butadiene units) in each hydrogenated block copolymer (c)-1 to 12>
For each hydrogenated block copolymer obtained in Production Examples 1 to 12 above, the copolymerization ratio of each monomer component, styrene and 1,3-butadiene, was determined by the analysis method shown below to determine the charging ratio during polymerization. We checked to see if there were any differences. An ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation was used as an analytical instrument.

Dissolve approximately 30 mg of each hydrogenated block copolymer (c)-1 to 12 (weighed accurately to the nearest 0.1 mg) in 100 mL of chloroform, fill a quartz cell with the polymer solution, and set it in an ultraviolet-visible spectrophotometer. This was scanned with ultraviolet light having a wavelength of 260 to 290 nm. Utilizing the property that the aromatic ring of styrene exhibits light absorption in this wavelength range, the absorption peak height value obtained by measurement was calculated using a calibration curve created with known samples for each hydrogenated block copolymer ( The styrene composition ratio (mass %) contained in c) was determined. The peak wavelength derived from styrene appears at 269.2 nm.
As a result, it was confirmed that there was no difference between the styrene charge ratio during polymerization and the styrene composition ratio in the hydrogenated block copolymer.
The composition ratio (mass %) of the hydrogenated butadiene portion was determined by subtracting the styrene composition ratio (mass %) from 100.

<Content of polymer block S mainly composed of vinyl aromatic monomer units (styrene units) of each hydrogenated block copolymer (c)-1 to 12>
The polymer solution containing the block copolymers before hydrogenating each of the hydrogenated block copolymers (c)-1 to 12 obtained in the above production example was extracted from the reactor to form each hydrogenated block copolymer. The content (% by mass) of the polymer block S consisting only of vinyl aromatic monomer units was measured.
Here, "polymer block S mainly composed of vinyl aromatic monomer units of a hydrogenated block copolymer" refers to a polymer block S mainly composed of conjugated diene monomer units contained in the hydrogenated block copolymer. It does not include the vinyl aromatic monomer units in the polymer block B, and refers only to the polymer block S mainly composed of vinyl aromatic monomer units.

First, an osmic acid tetroxide solution was prepared.
1 g of osmium tetroxide and 2 kg of "Perbutyl H (chemical name: tert-butyl hydroperoxide, purity 69%)", a commercial product available from NOF Corporation, were dissolved and mixed in 3 L of tert-butyl alcohol. A solution was prepared.

Next, the block copolymer before hydrogenation was dried using a vacuum dryer, and then about 20 mg was accurately weighed.
The weighed block copolymer was placed in a 300 mL Erlenmeyer flask, dissolved in about 10 mL of chloroform, 20 mL of the above osmic acid tetroxide solution was added, and the mixture was boiled at about 90° C. for 30 minutes. As a result, the conjugated diene moiety in the block copolymer was decomposed.
After boiling, the Erlenmeyer flask was cooled with running water, and about 200 mL of methanol was gently poured into the decomposed polymer solution to precipitate components that do not dissolve in the solvent.

This precipitated solid component is a polymer block S consisting only of vinyl aromatic monomer units, and styrene monomers etc. copolymerized in a polymer block B mainly consisting of conjugated diene monomer units. Vinyl aromatic monomer units, styrene monomers that do not form blocks, and styrene with a low degree of polymerization remain dissolved in the methanol/tertiary butyl alcohol/chloroform mixed solution. This precipitate was suction filtered using a glass filter, washed with pure methanol, and vacuum dried to isolate only the polymer block S from the hydrogenated block copolymer (c).
As mentioned above, by isolating the polymer block S and accurately weighing it, it is possible to accurately determine the content of the polymer block S mainly composed of vinyl aromatic monomer units in each hydrogenated block copolymer. It was measured.

<Hydrogenation rate of each hydrogenated block copolymer (c)-1 to 12>
The hydrogenation rate of the unsaturated diene moiety in the conjugated diene in each hydrogenated block copolymer (c) was measured by nuclear magnetic resonance spectroscopy (proton NMR) under the following conditions.

After the hydrogenation reaction was completed, each hydrogenated block copolymer cyclohexane solution before adding the antioxidant was collected in a 10 mL Erlenmeyer flask, and 90 mL of methanol was added thereto to precipitate the hydrogenated block copolymer components. . After suction filtration, it was washed with a sufficient amount of methanol, and after vacuum drying, the hydrogenated block copolymer (c) was recovered and used as a sample for hydrogenation rate measurement.
The hydrogenation rate was calculated by integrating the molar ratio of unhydrogenated conjugated diene parts using a nuclear magnetic resonance apparatus under the following measurement conditions.

[Measurement condition]
Nuclear magnetic resonance apparatus: ECA500 manufactured by JEOL
Solvent: Deuterated chloroform Frequency: 500MHz (1H nucleus)
Reference material: TMS (tetramethylsilane)

<Weight average molecular weight Mw, number average molecular weight Mn, molecular weight distribution Mw/Mn, peak molecular weight, and number of molecular weight peaks of hydrogenated block copolymers (c)-1 to 12>
The weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw/Mn), peak molecular weight, and molecular weight peak number of the hydrogenated block copolymers (c)-1 to 12 are respectively The measurement was performed using an ion chromatography (GPC) device under the following measurement conditions.

[Measurement condition]
GPC device: Tosoh Corporation HLC-8420
Column: 4 TSKgel SuperHZM-N manufactured by Tosoh Corporation connected in series Column temperature: 40°C
Liquid feeding amount: 0.6mL/min Detector: Refractometer (RI)
Solvent: Tetrahydrofuran

A sample for GPC measurement was prepared by dissolving about 10 mg of the polymer whose molecular weight was to be measured in 20 mL of tetrahydrofuran, and filtering to remove insoluble matter.

The measurement method is described below.
First, a calibration curve was created using nine standard polystyrene samples with known molecular weights, each having a different molecular weight. The weight average molecular weight (Mw) of standard polystyrene with the highest molecular weight was 1,090,000, and the standard polystyrene with the lowest molecular weight was 1,050. Subsequently, samples for measurement were prepared in the manner described above using each block polymer whose molecular weight was to be measured.

After confirming that the temperature inside the tank housing the column had become constant, a solution sample was injected and measurement started. After the measurement was completed, the obtained molecular weight distribution curve was statistically processed to calculate the weight average molecular weight (Mw) and number average molecular weight (Mn). The molecular weight distribution (Mw/Mn) was determined by dividing the obtained weight average molecular weight (Mw) by the number average molecular weight (Mn). Moreover, the peak molecular weight and the number of molecular weight peaks were determined from the above molecular weight distribution curve.

<Melt flow rate (MFR) of hydrogenated block copolymer (c)>
The measurement was carried out in accordance with the standard ISO1133 at a temperature of 200° C. and a load of 5 kgf.

Amounts of monomers added during production of hydrogenated block copolymers (c)-1 to 12 obtained in Production Examples 1 to 12, and content of vinyl aromatic monomer units and conjugated diene monomer units Table 3 shows the amount (mass%), the hydrogenation rate of the conjugated diene moiety, the molecular weight information based on the GPC measurement results, and the melt flow rate.

[Manufacture of ABS resin composition]
ABS resins (a)-1 to 3 shown in Table 1, bio-based polyethylene (b)-1 to 3 shown in Table 2, petroleum-based polyethylene (b')-X and Y shown in Table 3, ABS resin compositions were produced using the hydrogenated block copolymers (c)-1 to 12 according to the method described below.

An ABS resin composition was manufactured using the following equipment.
(1) Single screw extruder Manufactured by Tanabe Plastics Machinery Co., Ltd. Single screw extruder VS40-28
Screw diameter 40mm, L/D=28, 2 Dalmage kneading sections (2) Twin-screw extruder Twin-screw extruder TEX-30αII manufactured by Japan Steel Works Co., Ltd.
Screw diameter 30mm, L/D=36
There is a difference in kneading performance between the above-mentioned single-screw extruder and twin-screw extruder, and the single-screw extruder is used for weak kneading, and the twin-screw extruder is used for strong kneading. An ABS resin composition was manufactured on the premise that such a difference existed, and various physical properties were confirmed, but it was found that there was almost no difference in physical properties. Therefore, in the following Examples and Comparative Examples, (1) production was performed using a single screw extruder.

Components (a), (b), and (c) were dry-blended at room temperature in the form of pellets at the composition ratios listed in the table below, and then melt-kneaded using a single-screw extruder. The cylinder temperature was 220°C. Pellets of ABS resin composition were obtained by the strand cutting method.
The resin composition containing the hydrogenated block copolymer (c) was able to draw strands without any problem, but the ABS resin (a) containing no hydrogenated block copolymer (c) and the polyethylene ( All resin compositions mentioned in b), whether the polyethylene resin is bio-based or petroleum-based, cause a surging phenomenon, making it impossible to pull the strands stably, and requiring workers to perform auxiliary work all the time. I needed to.

[Characteristics of ABS resin composition]
The following evaluations were performed regarding various properties of the ABS resin compositions of each Example and Comparative Example.

(Biomass degree)
Measured according to ASTM D6866.

(Melt flow rate (MFR))
The measurement standard was based on ISO1133, and the measurement was carried out at a temperature of 200° C. and a load of 5 kgf. At 220° C. and 10 kgf, which are the general conditions for ABS resins, the fluidity becomes considerably high especially when bio-based polyethylene is blended, making measurement itself difficult, so the above temperature load conditions were adopted.

(mechanical properties, paintability)
<Preparation of various test pieces using an injection molding machine>
Tensile tests, bending tests, Charpy impact strength tests, deflection under load tests, and Vicat softening temperature tests were performed using ISO test piece molds, and Rockwell hardness tests and paint film adhesion tests were performed using flat metal plates of 50 mm x 90 mm x 2 mm. Test pieces were prepared using the following molding machines.
Injection molding machine: FNX110III hybrid type manufactured by Nissei Jushi Kogyo Co., Ltd. Clamping pressure: 110 tons, cylinder temperature: 230°C, mold temperature: 40°C
After each test piece was injection molded, it was cured for 24 hours in a constant temperature room at a temperature of 23° C. and a humidity of 50%, and then various characteristics were evaluated.

<Evaluation standards and conditions for mechanical properties>
Details of the evaluation conditions for each mechanical property are as follows.
The values in the table are the average values for each n number.
Tensile test: Using Minebea's tensile compression tester TG-5kN, it was conducted in accordance with ISO527-1 at a tensile speed of 50 mm/min in a thermostatic chamber at 23° C. with n number 4.
Bending test: Using Minebea's tensile compression tester TG-5kN, it was conducted in accordance with ISO 178 at a compression speed of 2 mm/min in a constant temperature room at 23° C. at n number 4.
Charpy impact test: In accordance with ISO 179, both with and without a notch were conducted in a constant temperature room at 23° C. at n number 10. If the test piece did not break into two or more pieces after the test, it was marked as NB.
Rockwell hardness: Three injection flat plates having a thickness of 2 mm were stacked together, and the test was carried out at ISO 868 in a constant temperature room at 23° C. at a temperature of 6.
Deflection test under load: Using an HDT device manufactured by Toyo Seiki Seisakusho, it was carried out at ISO75-1, tanzak was flatwise, and the number of n was 6.
Vicat Softening Temperature: Using Toyo Seiki Seisakusho HDT equipment and ISO 306, testing was carried out using tanzak cut into about 1/3 as a test piece and n number 6.

<Conditions and evaluation of paint film adhesion test>
Using the injection flat plate of 50 mm x 90 mm x 2 mm, the sample was spray-painted using acrylic paint (Campelacquer A Red, trade name, red paint made by Campe Hapio Co., Ltd.) as a paint, and then the coating film was Adhesion was evaluated.
For evaluation of coating film adhesion, a cross cut (100 squares of 1×1 mm) was made in the center of a flat test piece using a multi-cross cutter, and then a cellophane tape peeling test was performed.
The evaluation was carried out with n number 4, the average value of the number of squares that did not peel off was determined, and the evaluation was made according to the following criteria.
◎: No peeling spots ○: Peeling spots 1 or more, 10 or less ×: Peeling spots 11 or more

(Dispersion morphology analysis using transmission electron microscope)
Each ABS resin composition is heated to 200°C and compression molded to produce a plate with a thickness of about 1 mm, and the plate-shaped ABS resin composition is frozen with liquid nitrogen as needed and then placed using the microtome described below. Ultrathin sections with a thickness of about 70 nm were prepared using the following method.
Next, place the ultra-thin section on a mesh, add 1 mL of water to 0.1 g of ruthenium (III) chloride powder, and then add 5 mL of sodium hypochlorite solution (deer grade 1) to cause a reaction. Staining was performed by exposing the sample to ruthenium tetroxide vapor for 3 minutes. Using an ultrathin section made of the ABS resin composition after staining, observation was performed using a transmission electron microscope described below.
Microtome: Leica UC7
Transmission electron microscope: Hitachi H-600
Vinyl aromatic monomer units with which ruthenium tetroxide easily reacts are observed as dark-colored areas.
The determination of dispersion morphology analysis is as follows.
◎: ABS resin (a) forms a continuous phase, and bio-based polyethylene (b) forms a dispersed phase.
×: ABS resin (a) and (biobased) polyethylene (b) form a co-continuous phase, or ABS resin (a) forms a dispersed phase and (biobased) polyethylene (b) forms a continuous phase.

(Evaluation of melt viscosity of ABS resin (a) and polyethylene (b) using capillary rheometer)
The melt viscosity of ABS resin (a) and polyethylene (b) was measured using the following equipment in accordance with JIS K7199 (Method A).
Capillary rheometer: Capillograph 1D manufactured by Toyo Seiki Seisakusho
Capillary die: inner diameter 1mm, length 10mm
The apparent melt viscosity (ηa (Pa·s)) at each apparent shear rate γa (sec ⁻¹ ) at a test temperature of 220° C. and a piston speed of 1 to 500 mm/min was evaluated.
Furthermore, the apparent melt viscosities of ABS resin (a) and biobased polyethylene (b) were expressed as ηabs (Pa·s) and ηgpe (Pa·s), respectively, and their ratios were calculated.
<Symbols in the table>
・V: Piston speed ・γa: Apparent shear rate ・ηa: Apparent melt viscosity ・Apparent melt viscosity ηabs (Pa・s) of ABS resin (a)
- Apparent melt viscosity of bio-based polyethylene (b) ηgpe (Pa・s)
・These ratios ηgpe/ηabs
The evaluation results are shown in Tables 10 to 13 below.

[Examples 1 to 18, Comparative Examples 1 to 18, Reference Example 1]
The ABS system (a)-1 shown in Table 1 was used, (b)-1 was used as the bio-based polyethylene, and (b')-X and Y were used as the petroleum-based polyethylene. Using the hydrogenated block copolymer (c) shown in (c) or not using it in some comparative examples, various ABS resin compositions were melt-kneaded using the single-screw extruder and under the extrusion conditions described above. Obtained.

Subsequently, various test pieces were molded using the injection molding machine described above. During injection molding, preliminary drying was performed at 90° C. for 2 hours.
The formulation composition and evaluation of physical properties of the ABS resin compositions are shown in Tables 4 to 6 below.

By blending the hydrogenated block copolymer (c) into a composition consisting of ABS resin (a) and bio-based (or petroleum-based) polyethylene (b), tensile elongation at break and Charpy impact strength (without notch) are improved. A remarkable recovery of physical properties was observed.
Although these examples show a slight decrease in the flexural modulus compared to the ABS resin (a)-1 alone, depending on the selection of the hydrogenated block copolymer (c), the original ABS resin alone Some showed higher impact strength.

In addition, hydrogenated block copolymer (c)-5, which has a low styrene ratio and is close to the lower limit, is slightly better than hydrogenated block copolymer (c)-1, 2, 3, etc. from the viewpoint of tensile elongation at break and impact strength. Although the modification effect was slightly inferior in comparison, the modification effect was observed when compared with a system in which the hydrogenated block copolymer (c) was not blended.
On the other hand, the ABS resin composition using hydrogenated block copolymer (c)-2, which has a high styrene ratio close to the upper limit, has high flexural strength and flexural modulus, and has slightly Charpy impact strength (notched). Although it is low, it has become clear that it has the characteristic of being able to exhibit a reforming effect while maintaining rigidity.

Compared to ABS resin (a)-1 alone shown in Reference Example 1, bio-based (or petroleum-based) polyethylene (b) or (b') without blending hydrogenated block copolymer (c) Comparative Examples 1, 3, 5, and 12, which were formulated with It has become clear that there is no advantage in using only this method, and that it cannot be put to practical use.

The modification effect by the hydrogenated block copolymer (c) was not limited to bio-based polyethylene, but also had a similar modification effect on mechanical properties in petroleum-based polyethylene. However, if we take into account that the rigidity is the same or slightly lower than that of ABS resin alone, and the notched Charpy impact strength is also the same or tends to decrease, it is considered that there is no point in blending petroleum-based polyethylene. Although the introduction of bio-based polyethylene can lower the composition ratio derived from fossil raw materials and has the effect of improving physical properties, compositions with petroleum-based polyethylene are outside the scope of the present invention.

Furthermore, all formulations using petroleum-based polyethylene had poor coating adhesion results. This result shows that the melt viscosity of petroleum-based polyethylene was somewhat low, regardless of whether it is petroleum-based or bio-based, so when we checked the dispersion form using an electron microscope, we found that ABS resin (a) and petroleum-based polyethylene (b) were the same. Since the ABS resin (a) forms a continuous phase and the biobased polyethylene (b) forms a dispersed phase, which is a constitutional requirement of the present invention, the coating is not possible. The results of the membrane adhesion test were not good.

[Examples 19-30, Comparative Examples 19-38, Reference Examples 1-3]
Using ABS systems (a)-2 and (a)-3 shown in Table 1, using (b)-1 and (b)-2 as bio-based polyethylene, and hydrogenated blocks shown in Production Examples 2 and 3. Using copolymers (c)-2 and (c)-3, or without using them in some comparative examples, melt-kneading was performed using a single-screw extruder under extrusion conditions to obtain various ABS resin compositions. I got something.

Subsequently, various test pieces were molded using the injection molding machine described above. During injection molding, preliminary drying was performed at 90° C. for 2 hours.
The composition of the ABS resin composition and its physical properties are shown in Tables 7 and 8.

As is clear from these examples, regardless of the brand of ABS resin (a), the hydrogenated block copolymer (c) is blended into a resin composition consisting of this and biobased polyethylene (b). Therefore, in the examples, remarkable physical property recovery was observed in both tensile elongation at break and Charpy impact strength (without notch) compared to the ABS resin (a) alone. Although these examples show a slight decrease in flexural modulus compared to the ABS resin (a) alone, depending on the selection of the hydrogenated block copolymer (c), the elastic modulus is lower than that of the original ABS resin alone. Some showed high impact strength.

In addition, when focusing on Charpy impact strength in particular, the ABS resin composition using bio-based polyethylene (b)-1 is stronger overall than the ABS resin composition using (b)-2. It can be seen that the value is increasing. ABS resin (a) and bio-based polyethylene (b) are originally an incompatible combination, and due to their high viscosity, it is better to disperse domains in the form of particles to make them compatible with the hydrogenated block copolymer (c). It can be assumed that this is because it is easy to remove. In other words, since (b)-1 has a higher viscosity than (b)-2, the surface area of the interface is smaller, and therefore, the compatibilization function by interfacial reinforcement of hydrogenated block copolymer (c) is maximized. It is highly effective in improving mechanical strength by being fully utilized. Visual observation of the fracture surface after the Charpy impact test revealed that the fracture surface of the ABS resin composition using bio-based polyethylene (b)-1 was white, indicating the original ductile fracture of ABS resin (a). However, the ABS resin composition using bio-based polyethylene (b)-2 had a lower degree of whitening of the fracture surface than the one using (b)-1, and showed a tendency for brittle fracture.

In this way, the fact that the ABS resin (a) forms a continuous phase and the bio-based polyethylene (b) forms a dispersed phase greatly improves not only mechanical properties such as impact strength but also paint film adhesion. It is clear that there is an impact.

Furthermore, using (a)-1 as the ABS resin, (b)-3 as the bio-based polyethylene, and (c)-1 as the hydrogenated block copolymer, the composition ratio of the bio-based polyethylene was varied and a series of The physical properties of the material were evaluated.
The composition of the ABS resin composition and its physical properties are shown in Table 9 below.

Bio-based polyethylene (b)-3 has a slightly lower melt viscosity than (b)-1, so ABS resin (a) such as an ABS resin composition using (b)-1 forms a continuous phase. However, since the bio-based polyethylene (b) was slightly out of shape from the ideal dispersion forming a dispersed phase, the coating film adhesion resulted in less than 10 pieces peeling off.

[Results of dispersion morphology analysis using transmission electron microscope]
An example of the results of the above-mentioned (dispersion morphology analysis using a transmission electron microscope) is shown below.
FIG. 1 is a photograph in which the dispersion form of the ABS resin composition of Example 9 was analyzed using a transmission electron microscope.
ABS-based resin, which appears light gray, forms a continuous phase forming a matrix, and bio-based polyethylene, which appears slightly dark gray, forms a dispersed phase.
It can be confirmed that white-looking butadiene rubber particles are dispersed in the ABS resin. The outline around the dispersed phase made of bio-based polyethylene appears black, but this is because a large amount of the hydrogenated block copolymer (c) exists at the interface between the ABS resin and the bio-based polyethylene. Further, black particles can be confirmed inside the bio-based polyethylene dispersed phase, and these are also hydrogenated block copolymer (c).

FIG. 2 is a photograph in which the dispersion form of the ABS resin composition of Comparative Example 7 was analyzed using a transmission electron microscope. Contrast and magnification are the same as in FIG. 1 above.
The petroleum-based polyethylene that forms the dispersed phase has an amorphous shape, and areas containing the ABS-based resin phase can also be confirmed. Petroleum-based polyethylene has a somewhat low viscosity, so it forms such a phase structure. Since the phase boundaries are darkly dyed, it can be seen that the hydrogenated block copolymer is present in large amounts at the phase boundaries.
Since it forms a so-called co-continuous structure, it is difficult to develop coating film adhesion and good paintability cannot be achieved.

FIG. 3 is a photograph of the dispersion form of the ABS resin composition of Comparative Example 26 analyzed using a transmission electron microscope. The magnification is the same as in FIG. 1 above.
In contrast to FIG. 1, it can be seen that the ABS resin, which accounts for 60% by mass, forms the dispersed phase, and the polyethylene, which accounts for 30% by mass, forms the continuous phase. White-looking butadiene rubber particles can be confirmed in the ABS resin phase forming the dispersed phase. Hydrogenated block copolymers are present in large amounts at phase boundaries. Bio-based polyethylene with a low modulus of elasticity forms a continuous phase and becomes a matrix, and ABS resin with a high modulus of elasticity forms a dispersed phase and becomes a domain, making it difficult to develop Charpy impact strength and No film adhesion was developed at all, resulting in poor paintability.

[Results of melt viscosity measurement of ABS resin (a) and polyethylene (b) using a capillary rheometer]
We believe that the difference in relative melt viscosity between ABS resin (a) and (biobased) polyethylene (b) governs the dispersion form, and as mentioned above, we evaluated the melt viscosity using a capillary rheometer at 220°C. The results are shown in Tables 10 to 13 below.
The symbols in Tables 10 to 13 are shown below.
V: Piston speed (mm/min)
γa: Apparent shear rate (sec ^-1 )
ηa: Apparent melt viscosity (Pa・s)

Regarding ABS resin (a) and bio-based polyethylene (b), the apparent melt viscosity of each is expressed as ηabs (Pa・s) and ηgpe (Pa・s), respectively, and the ratio of these (ηgpe/ηabs) is The calculation results are shown in Tables 11 to 13.

As shown in Table 11, when (b)-1 is used, the apparent shear rate is between 12.16 and 1216, and the ratio to the apparent melt viscosity of ABS resins (a)-1 to 3 is All values were 1.0 or more, and in such cases, the dispersion form of the ABS resin composition was evaluated to be good, and excellent physical properties were obtained.
As shown in Table 12, when (b)-2 is used, the apparent shear rate is between 12.16 and 1216, and the ratio to the apparent melt viscosity of ABS resins (a)-1 to 3 is In such a case, the dispersion form of the ABS resin composition could not be evaluated favorably, and the physical property values were also poor.
As shown in Table 13, when (b)-3 is used, the apparent shear rate is between 12.16 and 1216, and the ratio to the apparent melt viscosity of ABS resins (a)-1 to 3 is 0.3 or more and less than 1.0, and in this case, a good evaluation was obtained for the dispersion form of the ABS resin composition, but in terms of physical properties, the ABS resin composition using (b)-1 It was a little inferior compared to the actual product.
As described above, it is clear from these numerical values that the ratio of the respective viscosities of the constituent components is greatly involved in the dispersion form of the ABS resin composition and has a great influence on the development of physical properties.

The bio-based polyethylene (b)-1 used in all Examples has approximately the same or slightly higher melting rate than all ABS resins (a)-1 to 3 over a wide range of shear rates. It showed the viscosity.
On the other hand, for (b)-2,3, (b')-X, Y, which did not give good results in the mechanical properties such as Charpy impact strength or the results of the paint film adhesion test, (b' )-X was found to have a higher value than (b)-2 in the high shear rate range, but the melt viscosity was lower than that of (a)-1 used in the comparative example in Table 6, and overall the ABS It was found that the resins (a)-1 to 3 exhibited low melt viscosity in a wide range of shear rates.

The ABS resin composition blended with the bio-based polyethylene of the present invention tends to have a slightly higher shrinkage rate than ABS resin alone, but the molding conditions and metallurgy should be adjusted in consideration of such shrinkage characteristics. We confirmed that it is possible to design a product for practical use by optimizing the mold design.

The ABS resin composition of the present invention achieves carbon neutrality by utilizing biobased polyethylene, and can reduce carbon dioxide emissions in the process from manufacturing to disposal. It has industrial potential as a material for resin-related molded products.

Claims (9)

An ABS resin composition containing an ABS resin (a), a biobased polyethylene (b), and a hydrogenated block copolymer (c),
The hydrogenated block copolymer (c) has a polymer block S mainly composed of vinyl aromatic monomer units and a polymer block B mainly composed of conjugated diene monomer units,
50 mol% or more of the conjugated diene moiety constituting the hydrogenated block copolymer (c) is hydrogenated,
The mass ratio of the ABS resin (a) and the biobased polyethylene (b) is (a)/(b) = 99/1 to 50/50,
The mass ratio of the bio-based polyethylene (b) and the hydrogenated block copolymer (c) is
(b)/(c)=90/10 to 50/50,
In dispersion morphology analysis using a transmission electron microscope, ABS resin (a) forms a continuous phase and bio-based polyethylene (b) forms a dispersed phase.
ABS resin composition. The bio-based polyethylene (b) is
An ethylene homopolymer (b1) and/or a copolymer of ethylene and α-olefin mainly composed of ethylene (b2), which has a biomass degree of 80% or more and 100% or less as defined in ASTM D6866,
The ABS resin composition according to claim 1. The hydrogenated block copolymer (c) is
Containing 4 to 70% by mass of vinyl aromatic monomer units and 30 to 96% by mass of conjugated diene monomer units,
The ABS resin composition according to claim 1. The molded article of the ABS resin composition according to claim 1, which is an injection molded article. The molded article of the ABS resin composition according to claim 1, which is a blow molded article. The molded article of the ABS resin composition according to claim 1, which is an extrusion molded article. A coated molded product comprising the molded product according to any one of claims 4 to 6 and a coating film. The apparent melt viscosity ηgpe (Pa s) of the biobased polyethylene (b) relative to the apparent melt viscosity ηabs (Pa s) of the ABS resin (a) in a capillary rheometer under a temperature condition of 220°C. The ratio: ηgpe/ηabs is always 0.3 or more with an apparent shear rate γa (sec ^-1 ) between 12.16 and 1216;
The ABS resin composition according to claim 2. The apparent melt viscosity ηgpe (Pa s) of the biobased polyethylene (b) relative to the apparent melt viscosity ηabs (Pa s) of the ABS resin (a) in a capillary rheometer under a temperature condition of 220°C. The ratio: ηgpe/ηabs is always 1.0 or more with an apparent shear rate γa (sec- ¹ ) between 12.16 and 1216;
The ABS resin composition according to claim 2.