JP2024062286A - Styrenic resin composition and molded article - Google Patents

Abstract

[Problem] The object of the present invention is to provide a styrene-based resin composition having excellent dimensional accuracy, fluidity, high rigidity, and molded appearance, and a molded article containing said styrene-based resin composition. [Solution] The present invention is characterized by comprising a styrene-based resin composition containing 45.0 to 99.5 mass % of a styrene-based resin (a) and 0.5 to 55.0 mass % of paramylon (b). [Selected Figure] None

Description

The present invention relates to a styrene-based resin composition and a molded article.

Styrene-based resins are used in a wide range of applications due to their excellent moldability, dimensional stability, and transparency. Biomass materials have also attracted attention from the viewpoint of environmental protection, and composite materials of resin materials and naturally derived organic fillers or biopolymers have been investigated.
For example, algae biomass has been attracting attention as a plant raw material for non-edible components. Algae can be cultivated even on land unsuitable for farming, do not compete with food production, and can be repeatedly cultivated in a cyclical manner using carbon dioxide, nutrients, and sunlight. Therefore, they can be used sustainably as an alternative to fossil resources. Paramylon (β-1,3 glucan) is known as such an algae-derived polysaccharide. Patent Document 1 discloses a thermoplastic resin made from a paramylon derivative.

International Publication No. 2020/013232

However, although Patent Document 1 describes the properties of the paramylon-based resin itself, it does not disclose anything about a resin composition in which the paramylon-based resin is mixed with a styrene-based resin as a composite material, or about the properties of the resin composition.

The object of the present invention is to provide a styrene-based resin composition having excellent dimensional accuracy, flowability, high rigidity, and molded appearance, and a molded article containing the styrene-based resin composition.

In view of the above problems, the inventors conducted extensive research and experimentation, and discovered that the above problems could be solved by using a styrene-based resin composition in which a styrene-based resin (a) and paramylon (b) are mixed in a specific ratio, leading to the completion of the present inventions [1] to [5] below.

[1] A styrene-based resin composition comprising 45.0 to 99.5% by mass of a styrene-based resin (a) and 0.5 to 55.0% by mass of paramylon (b).
[2] The styrene-based resin composition according to [1], wherein the styrene-based resin (a) contains a styrene-based monomer unit and an unsaturated carboxylic acid-based monomer unit.
[3] The styrene-based resin composition according to [1] or [2], further comprising 0.5 to 2.0 parts by mass of a dispersant (c) per 100 parts by mass of the total amount of the styrene-based resin composition.
[4] The styrene-based resin composition according to any one of [1] to [3], wherein the dispersant (c) is one or more compounds selected from the group consisting of phosphinic acid compounds, NOR-type hindered amine compounds, fatty acid ester compounds, polyethylene glycol compounds, terpene compounds, and rosin compounds.
[5] A molded article comprising the styrene-based resin composition according to any one of [1] to [4] above.

The present invention provides a styrene-based resin composition that is excellent in dimensional accuracy, fluidity, high rigidity, and molded appearance, and a molded product that uses the styrene-based resin composition.

The following describes in detail an embodiment of the present invention (hereinafter referred to as the "present embodiment"); however, the present invention is not limited to the following description and can be modified in various ways within the scope of the gist of the present invention.

[Styrene-based resin composition]
The styrene-based resin composition of the present embodiment contains 45.0 to 99.5 mass % of the styrene-based resin (a) and 0.5 to 55.0 mass % of the paramylon (b).
This makes it possible to provide a styrene-based resin composition that has excellent flowability and can form a molded article having excellent dimensional accuracy, high rigidity and molded appearance.

<Styrene-based resin (a) (hereinafter also referred to as component (a))>
In this embodiment, the content of the styrene-based resin (a) is 45.0 to 99.5% by mass, preferably 50.0 to 97.0% by mass, and more preferably 60.0 to 95.0% by mass, based on the entire styrene-based resin composition (100% by mass). By making the content 45.0% by mass or more, it is possible to improve the fluidity and appearance. On the other hand, by making the content 99.5% by mass or less, it is possible to ensure a content at which the effect of paramylon (b) can be exerted, and it is possible to improve dimensional accuracy, rigidity, etc.

The MFR (200°C, 5 kg) of the styrene resin (a) in the present invention is preferably 2 or more. More preferably, it is 5 or more, and even more preferably, it is 8 to 30. If the MFR of the styrene resin (a) is lower than 2, it becomes difficult for the paramylon (b) to disperse in the styrene resin (a), and the dimensional accuracy and appearance are reduced. On the other hand, if the MFR of the styrene resin (a) is 2 or more, the styrene resin (a) is easily impregnated into the aggregates of the paramylon (b), so that the paramylon (b) is uniformly dispersed, and the dimensional accuracy and appearance are improved.
Furthermore, in order to improve dispersibility with paramylon (b), the styrene-based resin (a) preferably contains a styrene-based monomer unit and an unsaturated carboxylic acid-based monomer unit. The content of the unsaturated carboxylic acid-based monomer unit is preferably 2 to 31% by mass, more preferably 4 to 26% by mass, and even more preferably 8 to 23% by mass, based on the total styrene-based resin (a) (100% by mass).
On the other hand, the content of the styrene-based monomer unit is preferably 69% by mass or more and less than 98% by mass, 69% by mass or more and less than 98% by mass, 74% by mass or more and less than 96% by mass, 74% by mass or more and 96% by mass or less, or 77 to 92% by mass, relative to the entire styrene-based resin (a) (100% by mass).
The styrene-based resin (a) used in this embodiment may be one type or a blend of two or more types, and in the case of a blend, the refractive index or MFR is the value of the blend. In this specification, the MFR is a value measured in accordance with ISO 1133.

The styrene-based resin (a) that can be used in this embodiment is preferably a polymer having a styrene-based monomer unit, and more preferably a copolymer having a styrene-based monomer unit and a monomer unit other than the styrene-based monomer unit.More preferably, the styrene-based resin (a) is a styrene-based polymerized resin obtained by polymerizing a styrene-based monomer and one or more monomers selected from other vinyl monomers and rubber polymers that are copolymerizable with the styrene-based monomer.The styrene-based resin (a) in the present invention is not particularly limited, but examples thereof include polystyrene, a styrene-based copolymerized resin having a styrene-based monomer unit, a rubber-modified styrene-based resin in which particles of a rubber-like polymer (A) are dispersed in a polymer matrix having a styrene-based monomer unit, and mixtures thereof.
The polymer matrix may be polystyrene or a styrene-based copolymer resin having a styrene-based monomer unit.

<<Polystyrene>>
In this embodiment, polystyrene is a homopolymer obtained by polymerizing a styrene-based monomer, and generally available ones can be appropriately selected and used. As the styrene-based monomer constituting polystyrene, in addition to styrene, α-methylstyrene, α-methyl-p-methylstyrene, ο-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, ethylstyrene, isobutylstyrene, and t-butylstyrene, or styrene derivatives such as bromostyrene and indene can be mentioned. Styrene is particularly preferable from an industrial viewpoint. One or more of these styrene-based monomers can be used. Although polystyrene may further contain monomer units other than the above-mentioned styrene-based monomer units within a range that does not impair the effects of the present invention, it is typically composed of styrene-based monomer units.

<<Rubber-modified styrene-based resin>>
In the present embodiment, the rubber-modified styrene-based resin is a resin in which particles of a rubber-like polymer (A) (hereinafter, rubber-like polymer particles (A1)) are dispersed in a styrene resin (e.g., polystyrene or a styrene-based copolymer resin having a styrene-based monomer unit) as a polymer matrix having a styrene-based monomer unit, and can be produced by polymerizing a styrene-based monomer in the presence of the rubber-like polymer (A).

In addition to styrene, examples of the styrene monomer constituting the rubber-modified styrene resin of this embodiment include α-methylstyrene, α-methyl-p-methylstyrene, ο-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, ethylstyrene, isobutylstyrene, and t-butylstyrene, or styrene derivatives such as bromostyrene and indene. Styrene is particularly preferred. These styrene monomers can be used alone or in combination.

The rubber-like polymer particles (A1) contained in the rubber-modified styrene-based resin of this embodiment may, for example, contain a styrene monomer unit-containing resin obtained from the above-mentioned styrene-based monomer on the inside and/or may have a styrene monomer unit-containing resin grafted on the outside.

As the rubber-like polymer (A) or rubber-like polymer particles (A1), for example, polybutadiene, polybutadiene containing polystyrene, polyisoprene, natural rubber, polychloroprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, etc. can be used, but polybutadiene or styrene-butadiene copolymer is preferred. As the polybutadiene, both high-cis polybutadiene having a high cis content and low-cis polybutadiene having a low cis content can be used. In addition, as the structure of the styrene-butadiene copolymer, both a random structure and a block structure can be used. These rubber-like polymers (A) or rubber-like polymer particles (A1) can be used alone or in combination. In addition, saturated rubber obtained by hydrogenating butadiene rubber can also be used.
Examples of such rubber-modified styrene-based resins include HIPS (high impact polystyrene), ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), and AES resin (acrylonitrile-ethylene propylene rubber-styrene copolymer).

In the present embodiment, when the rubber-modified styrene-based resin is a HIPS-based resin, the particularly preferred rubber-like polymer (A) is a high-cis polybutadiene having 90 mol % or more of cis-1,4 bonds, preferably having 6 mol % or less of vinyl-1,2 bonds, and more preferably having 3 mol % or less of vinyl-1,2 bonds.
The content of isomers having a cis-1,4, trans-1,4, or vinyl-1,2 structure as a constituent unit of the high-cis polybutadiene can be measured using an infrared spectrophotometer and calculated by processing the data according to the Morello method.
The high-cis polybutadiene can be easily obtained by a known production method, for example, by polymerizing 1,3-butadiene using a catalyst containing an organoaluminum compound and a cobalt or nickel compound.

In this embodiment, the content of the rubber-like polymer (A) contained in the rubber-modified styrene-based resin is preferably 2 to 10 mass% and more preferably 3 to 8 mass% based on 100 mass% of the rubber-modified styrene-based resin. If the content of the rubber-like polymer (A) is less than 2 mass%, the impact resistance of the styrene-based resin may decrease. If the content of the rubber-like polymer (A) is more than 10 mass%, the light transmittance may decrease.
In the present disclosure, the content of the rubber-like polymer (A) contained in the rubber-modified styrene-based resin is a value calculated using pyrolysis gas chromatography.

In this embodiment, the average particle size of the rubber-like polymer particles (A1) contained in the rubber-modified styrene-based resin is preferably 0.5 to 2.5 μm, and more preferably 0.8 to 2.0 μm, from the viewpoint of light transmittance.
In the present disclosure, the average particle size of the rubber-like polymer particles (A1) contained in the rubber-modified styrene-based resin can be measured by the following method.
A 75 nm-thick ultrathin section is prepared from the rubber-modified styrene-based resin stained with osmium tetroxide, and a photograph is taken at a magnification of 10,000 times using an electron microscope. In the photograph, the particles stained black are rubber-like polymer particles (A1). From the photograph, the following formula (N1):
Average particle size = ΣniDri ³ / ΣniDri ² (N1)
(In the above formula (N1), ni is the number of rubber-like polymer particles (A1) having a particle diameter Dri, and the particle diameter Dri is the particle diameter calculated as a circle-equivalent diameter from the area of the particle in the photograph.)
The area average particle diameter is calculated from the above and is regarded as the average particle diameter of the rubber-like polymer particles (A1). In this measurement, a photograph is scanned at a resolution of 200 dpi and the measurement is carried out using particle analysis software of an image analyzer IP-1000 (manufactured by Asahi Kasei Corporation).

In this embodiment, the reduced viscosity of the rubber-modified styrene-based resin (which is an index of the molecular weight of the rubber-modified styrene-based resin) is preferably in the range of 0.50 to 0.85 dL/g, and more preferably in the range of 0.55 to 0.80 dL/g. If it is less than 0.50 dL/g, there is a risk that the impact strength will decrease, and if it exceeds 0.85 dL/g, there is a risk that the moldability will decrease due to a decrease in fluidity.
In this disclosure, the reduced viscosity of the rubber-modified styrene-based resin is a value measured in a toluene solution at 30° C. and a concentration of 0.5 g/dL.

In this embodiment, the method for producing the rubber-modified styrene-based resin is not particularly limited, but it can be produced by bulk polymerization (or solution polymerization) in which a styrene-based monomer (and a solvent) is polymerized in the presence of the rubber-like polymer (A), or bulk-suspension polymerization in which the reaction transitions to suspension polymerization during the reaction, or emulsion graft polymerization in which a styrene-based monomer is polymerized in the presence of the rubber-like polymer (A) latex. In bulk polymerization, the rubber-like polymer (a) can be produced by continuously supplying a mixed solution containing the rubber-like polymer (a) and the styrene-based monomer, and optionally an organic solvent, an organic peroxide, and/or a chain transfer agent, to a polymerization apparatus consisting of a complete mixing reactor or a tank reactor and multiple tank reactors connected in series.

<<Styrene-based copolymer resin>>
In the present embodiment, the styrene-based copolymer resin is preferably a resin containing a styrene-based monomer unit and an unsaturated carboxylic acid-based monomer unit. Therefore, a preferred form of the styrene-based resin (a) may be a styrene-based copolymer resin containing a styrene-based monomer unit and an unsaturated carboxylic acid-based monomer unit.
In this specification, the term "unsaturated carboxylic acid monomer (unit)" includes unsaturated carboxylic acid monomer (unit) and unsaturated carboxylic acid ester monomer (unit). In the styrene copolymer resin of the present invention, when the total content of the styrene monomer unit and the unsaturated carboxylic acid monomer unit is taken as 100% by mass, the content of the styrene monomer unit is preferably 69 to 98% by mass, more preferably 74 to 96% by mass, and even more preferably 77 to 92% by mass. By making the content 69% by mass or more, the refractive index of the styrene resin (a) can be improved. On the other hand, by making the content 98% by mass or less, it becomes difficult to make the unsaturated carboxylic acid monomer unit and the unsaturated carboxylic acid ester monomer unit, which is an optional component, present in desired amounts, and it becomes difficult to obtain the effects described below due to these monomer units.
In addition, in the styrene-based copolymer resin of the present invention, when the total content of the styrene-based monomer units and the unsaturated carboxylic acid-based monomer units is taken as 100 mass%, the content of the unsaturated carboxylic acid-based monomer units is preferably 2 to 31 mass%, more preferably 4 to 26 mass%, and even more preferably in the range of 8 to 23 mass%.

In the styrene-based copolymer resin of this embodiment, the unsaturated carboxylic acid-based monomer unit plays a role in improving heat resistance. When the total content of the styrene-based monomer unit, the unsaturated carboxylic acid monomer unit, and the unsaturated carboxylic acid ester monomer unit in the styrene-based copolymer resin is taken as 100% by mass, the content of the unsaturated carboxylic acid monomer unit is preferably 2 to 16% by mass, more preferably 4 to 14% by mass, and even more preferably 8 to 13% by mass. By making the content 2% by mass or more, the dispersibility of paramylon (b) can be improved, and the light transmittance, appearance, and heat resistance can be further improved. On the other hand, by making the content 16% by mass or less, the fluidity and mechanical properties of the resin can be improved.

Generally, styrene-methacrylic acid-based resins, including styrene-methacrylic acid-methyl methacrylate copolymer resins, which are an example of styrene-based copolymer resins, are mostly produced on an industrial scale by radical polymerization, but in this embodiment, various alcohols can be added to the polymerization system to suppress the gelling reaction in the devolatilization process.

Unsaturated carboxylic acid ester monomers can be used to suppress the dehydration reaction of unsaturated carboxylic acid monomers through intermolecular interactions with the unsaturated carboxylic acid monomers, and to improve the mechanical strength of the resin. Furthermore, unsaturated carboxylic acid ester monomers also contribute to improving resin properties such as weather resistance and surface hardness.

In the styrene-based copolymer resin of this embodiment, when the total content of the styrene-based monomer units, the unsaturated carboxylic acid monomer units, and the unsaturated carboxylic acid ester monomer units is taken as 100% by mass, the content of the unsaturated carboxylic acid ester monomer units is preferably 0 to 15% by mass, more preferably 1 to 12% by mass, and even more preferably 2 to 10% by mass. By setting the content to 15% by mass or less, the light transmittance and fluidity of the resin can be improved. In addition, by setting the content of the unsaturated carboxylic acid ester monomer units to 0% by mass, it is possible to improve heat resistance and reduce costs, but from the above viewpoint, the content of the unsaturated carboxylic acid ester monomer units can also be set to more than 0% by mass.

When unsaturated carboxylic acid monomers and unsaturated carboxylic acid ester monomer units are bonded side by side, a dealcoholization reaction may occur under certain conditions when a high-temperature, high-vacuum devolatilizer is used, resulting in the formation of a six-membered cyclic acid anhydride. The styrene-based copolymer resin of this embodiment may contain this six-membered cyclic acid anhydride, but since this reduces fluidity, it is preferable that the amount of six-membered cyclic acid anhydride produced is as small as possible.

In the present embodiment, the contents of the styrene monomer unit (e.g., styrene monomer unit), the unsaturated carboxylic acid monomer unit (e.g., methacrylic acid monomer unit), and the unsaturated carboxylic acid ester monomer unit (e.g., methyl methacrylate monomer unit) in the styrene-based copolymer resin can be determined from the integral ratio of the spectrum measured by a proton nuclear magnetic resonance ( ^1H -NMR) measurement device.

In this embodiment, the styrene-based copolymer resin preferably contains a styrene-based monomer unit and an unsaturated carboxylic acid-based monomer unit, and preferably contains a styrene-based monomer unit and an unsaturated carboxylic acid monomer unit and/or an unsaturated carboxylic acid ester monomer unit. In addition, it is not excluded that the styrene-based copolymer resin further contains monomer units other than the unsaturated carboxylic acid monomer unit and the unsaturated carboxylic acid ester monomer unit within a range that does not impair the effects of the present invention. However, the styrene-based copolymer resin in the present invention is preferably typically composed of a styrene-based monomer unit, a (meth)acrylic acid carboxylic acid monomer unit, and/or a (meth)acrylic acid carboxylic acid ester monomer unit.

The styrene monomer constituting the styrene copolymer resin of this embodiment is the same as the styrene monomer constituting the rubber-modified styrene resin described above, so it will not be described here.

The unsaturated carboxylic acid monomer constituting the styrene-based copolymer resin of this embodiment is not particularly limited, but (meth)acrylic acid-based monomers are preferred, such as methacrylic acid, acrylic acid, maleic anhydride, maleic acid, fumaric acid, and itaconic acid. As the unsaturated carboxylic acid monomer, methacrylic acid is preferred because it has a large effect of improving heat resistance, is liquid at room temperature, and has excellent handleability. These unsaturated carboxylic acid monomers can be used alone or in combination of two or more.

The unsaturated carboxylic acid ester monomer constituting the styrene-based copolymer resin of this embodiment is not particularly limited, but (meth)acrylic acid ester monomers are preferred, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and cyclohexyl (meth)acrylate. As the (meth)acrylic acid ester monomer, methyl (meth)acrylate is preferred because it has little effect on the decrease in heat resistance. These unsaturated carboxylic acid ester monomers can be used alone or in combination of two or more.

As the styrene-based copolymer resin of this embodiment, a styrene-methyl (meth)acrylate copolymer, a styrene-ethyl (meth)acrylate copolymer, a styrene-propane (meth)acrylate copolymer, or a styrene-butyl (meth)acrylate copolymer, a styrene-methyl (meth)acrylate-butyl (meth)acrylate copolymer, or a styrene-methyl (meth)acrylate-methacrylic acid copolymer is preferred.

In this embodiment, the weight average molecular weight (Mw) of the styrene copolymer resin is preferably 100,000 to 350,000, more preferably 120,000 to 300,000, and even more preferably 140,000 to 240,000. When the weight average molecular weight (Mw) is 100,000 to 350,000, a resin with a better balance between mechanical strength and fluidity is obtained, and there is also little gel contamination. The weight average molecular weight (Mw) is a value obtained by using gel permeation chromatography and converting it into standard polystyrene.

As the styrene-based resin (a) of this embodiment, a mixture of one or more of the above-mentioned rubber-modified styrene-based resins and one or more of the styrene-based copolymer resins may be used. In this case, the mixing ratio of the rubber-modified styrene-based resin and the styrene-based copolymer resin can be appropriately changed depending on the purpose of use. For example, in a system in which the amount of the rubber-modified styrene-based resin is less than that of the styrene-based copolymer resin, it is preferable to contain 0.1 to 30 mass% of the styrene-based copolymer resin relative to the total amount (100 mass%) of the styrene-based resin (a). On the other hand, in a system in which the amount of the rubber-modified styrene-based resin is more than that of the styrene-based copolymer resin, it is preferable to contain 70 to 99.9 mass% of the styrene-based copolymer resin relative to the total amount (100 mass%) of the styrene-based resin (a).

In this embodiment, the polymerization method for the styrene copolymer resin is not particularly limited, but for example, a bulk polymerization method or a solution polymerization method can be suitably adopted as a radical polymerization method. The polymerization method mainly includes a polymerization process for polymerizing the polymerization raw materials (monomer components) and a devolatilization process for removing volatile matters such as unreacted monomers and polymerization solvents from the polymerization product.

Hereinafter, an example of a polymerization method for the styrene-based copolymer resin that can be used in the present embodiment will be described.
When the polymerization raw materials are polymerized to obtain the styrene-based copolymer resin, a polymerization initiator and a chain transfer agent are typically contained in the polymerization raw material composition.
Examples of the polymerization initiator used in the polymerization of the styrene-based copolymer resin include organic peroxides, for example, peroxyketals such as 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)cyclohexane, and n-butyl-4,4-bis(t-butylperoxy)valerate, dialkyl peroxides such as di-t-butyl peroxide, t-butylcumyl peroxide, and dicumyl peroxide, diacyl peroxides such as acetyl peroxide and isobutyryl peroxide, peroxydicarbonates such as diisopropyl peroxydicarbonate, peroxyesters such as t-butylperoxyacetate, ketone peroxides such as acetylacetone peroxide, and hydroperoxides such as t-butyl hydroperoxide. Among these, 1,1-bis(t-butylperoxy)cyclohexane is preferred from the viewpoints of decomposition rate and polymerization rate.
Examples of the chain transfer agent used in the polymerization of the styrene-based copolymer resin include α-methylstyrene linear dimer, n-dodecyl mercaptan, t-dodecyl mercaptan, and n-octyl mercaptan.

As a polymerization method for the styrene-based copolymer resin, solution polymerization using a polymerization solvent can be adopted as necessary. Examples of the polymerization solvent used include aromatic hydrocarbons, such as ethylbenzene, and dialkyl ketones, such as methyl ethyl ketone, and each of these may be used alone or in combination of two or more. Other polymerization solvents, such as aliphatic hydrocarbons, can be further mixed with the aromatic hydrocarbons as long as the solubility of the polymerization product is not reduced. It is preferable to use these polymerization solvents in an amount not exceeding 25 parts by mass per 100 parts by mass of the total monomers. If the amount of the polymerization solvent exceeds 25 parts by mass per 100 parts by mass of the total monomers, the polymerization rate decreases significantly and the mechanical strength of the obtained resin tends to decrease significantly. It is preferable to add 5 to 20 parts by mass per 100 parts by mass of the total monomers before polymerization, as this makes it easier to uniformize the quality and is also preferable in terms of polymerization temperature control.

In this embodiment, the apparatus used in the polymerization step for obtaining the styrene-based copolymer resin is not particularly limited, and may be appropriately selected according to the polymerization method of the styrene-based resin. For example, when bulk polymerization is employed, a polymerization apparatus having one or more completely mixed reactors connected together can be used. There is also no particular limit to the devolatilization step. For example, when bulk polymerization is employed, polymerization is continued until the final amount of unreacted monomer is preferably 50% by mass or less, more preferably 40% by mass or less, and devolatilization is performed by a known method to remove volatile matters such as unreacted monomer. More specifically, for example, a normal devolatilization apparatus such as a flash drum, a twin-screw devolatilizer, a thin film evaporator, or an extruder can be used, but a devolatilization apparatus with a small retention portion is preferred. The temperature of the devolatilization treatment is usually about 190 to 280°C, and from the viewpoint of suppressing the formation of a six-membered ring acid anhydride due to the adjacent methacrylic acid and methyl methacrylate, 190 to 260°C is more preferred. The pressure for the devolatilization process is usually about 0.13 to 4.0 kPa, preferably 0.13 to 3.0 kPa, and more preferably 0.13 to 2.0 kPa. Desirable devolatilization methods include, for example, a method of removing volatiles by reducing pressure under heating, and a method of removing volatiles through an extruder or the like designed for the purpose of removing volatiles.

<Paramylon (b) (hereinafter also referred to as component (b))>
Paramylon (b) in this embodiment is a β-1,3 glucan represented by the following formula (1), which is a linear polymer formed by polymerizing β-D-glucose molecules (β-D-glucopyranose) through β-1,3 glycosidic bonds. In general, paramylon has a polymer chain that can have a triple helix structure, and is a spheroid composed of fibers with a triple helix structure. Therefore, since paramylon (b) in this embodiment has this structure, it is possible to obtain a styrene-based resin composition from paramylon (b) that has good dispersibility and is excellent in thermal stability and dimensional accuracy.

In general, paramylon is easy to isolate and purify, so it is preferable to use paramylon separated from microalgae that synthesize paramylon intracellularly as the raw material for paramylon (b) or as paramylon (b). As the microalgae, Euglena (a microalgae belonging to the Euglenophyta) is preferable. This is because Euglena is easy to culture, has a fast growth cycle, and accumulates large amounts of paramylon particles as a photosynthetic product within the cells.
The content of paramylum (b) in the present invention is 5 to 55.0 mass%, preferably 10 to 50 mass%, and more preferably 15 to 40.0 mass%, relative to the total amount (100 mass%) of the styrene-based resin composition.
By making the content of the (b) component 5% by mass or more, it is possible to improve the dimensional accuracy and rigidity. On the other hand, if the content is too high, the impact strength is reduced and the moldability is significantly reduced due to the reduced fluidity. The content of paramylon (b) in the styrene resin composition can be determined by dissolving the composition in a solvent that dissolves the styrene resin (a), removing the undissolved matter, and measuring the mass of the product dried at 120°C for 4 hours.

In this embodiment, the average particle size of paramylon (b) is 2 to 20 μm, preferably 3 to 10 μm. If the average particle size is outside the above range, the dimensional accuracy or rigidity may not be fully exhibited, or the fluidity and molded appearance may be deteriorated. On the other hand, if the average particle size is within the above range, the aggregation of paramylon particles can be reduced, and the dispersibility in the styrene-based resin (a) is improved, improving the dimensional accuracy.
Furthermore, the aspect ratio of paramylon (b) (= the ratio of the maximum diameter to the minimum diameter (maximum diameter/minimum diameter)) is preferably 1.0 to 1.5, more preferably 1.0 to 1.3, and even more preferably 1.0 to 1.2. If the aspect ratio of paramylon (b) is too larger than 1.5, anisotropy will occur in the dimensions and fluidity will decrease. Since paramylon (b) is almost ellipsoidal and is not fibrous like cellulose fiber or wood flour, it has excellent dispersibility in the styrene-based resin (a) and has little decrease in fluidity and anisotropy in dimensional accuracy.
In the present invention, the average particle size of paramylum (b) and the ratio of the maximum diameter to the minimum diameter (=aspect ratio) are determined by measuring the diameters of 100 particles of paramylum (b) by observation under an optical microscope or a transmission electron microscope (magnified 1000 times) and taking the arithmetic average.

<Dispersant (c) (hereinafter also referred to as component (c))>
In this embodiment, for the purpose of improving the dispersibility of paramylon (b) in the composition or molded product, the dispersant (c) may be further contained in an amount of 0.5 to 10.0 parts by mass relative to the total amount (100 parts by mass) of the styrene-based resin composition, and more preferably, the dispersant (c) is contained in an amount of 0.8 to 5.0 parts by mass. By adding the dispersant (c) to the styrene-based resin composition, when the paramylon (b) and the styrene-based resin (a) are composited, the monodispersion of the paramylon (b) is promoted, and the interfacial adhesion with the styrene-based resin (a) is improved, and the dimensional accuracy and rigidity can be improved. This is thought to be because the dispersant (c) is impregnated into the paramylon (b), and a part of the surface of the paramylon (b) is defibrated to form nanofibers. For example, if the dispersant (c) is a phosphinic acid compound, it is easy to impregnate into the paramylon (b), and as a result, the interfacial adhesion is improved, and the dimensional accuracy and rigidity can be further improved. If the amount of the dispersant (c) is less than the specified amount, a significant effect cannot be expected, and if the amount is more than the specified amount, it is difficult to obtain a significant heat resistance. A dispersant (c) having excellent affinity with the styrene-based resin (a) tends to show a greater effect.

In this embodiment, the dispersant (c) may be a phosphinic acid compound, a NOR type hindered amine compound, a fatty acid ester compound, a polyethylene glycol compound, a terpene compound, a rosin compound, a fatty acid amide, a fatty acid compound, or a fatty acid metal salt compound. In particular, the dispersant (c) is preferably one or more compounds selected from the group consisting of a phosphinic acid compound, a NOR type hindered amine compound, a fatty acid ester compound, a polyethylene glycol compound, a terpene compound, and a rosin compound.

Examples of the phosphinic acid compounds include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. For example, HCA from Sanko Co., Ltd. can be used as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and for example, BCA from Sanko Co., Ltd. can be used as 10-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

The NOR type hindered amine compound is not particularly limited as long as it has an N-alkoxyl group (>N-OR) structure. Specific examples of suitable NOR type hindered amine compounds include those described in JP-T-2002-507238, WO-2005/082852, WO-2008/003605, etc.
Specific examples of the NOR type hindered amine compound include the following compounds: 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine; 2,2,6,6-tetramethyl-4-piperidyl)sebacate; 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-(2-hydroxyethylamino)-s-triazine; bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)adipate; 4, an oligomeric compound which is a condensation product of 4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) with 2,4-dichloro-6-[(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine; an oligomeric compound which is a condensation product of 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) with 2-chloro-4,6-bis(dibutylamino)-s-triazine end-capped with Oligomeric compounds which are condensation products of 2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine; 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)-6-chloro-s-triazine; peroxidized 4-butylamino-2,2,6,6-tetramethylpiperidine, 2,4,6-trichloro-s-triazine, cyclohexane, and N,N'-ethane-1,2-diylbis(1,3-propanediamine). Reaction products with (N,N',N'''-tris{2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)n-butylamino]-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine);bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate;1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-one; bis(1-stearyloxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate.
Furthermore, commercially available products may be used as the NOR type hindered amine compound. Examples of the commercially available products include Flamestab NOR116FF, TINUVIN NOR371, TINUVIN XT850FF, TINUVIN XT855FF, and TINUVIN PA123 manufactured by BASF Corporation, and LA-77Y, LA-81, and FP-T80 manufactured by ADEKA Corporation.
Examples of the aliphatic ester compounds include methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl erucate, methyl behenate, butyl laurate, butyl stearate, isopropyl myristate, isopropyl palmitate, octyl palmitate, coconut fatty acid octyl ester, octyl stearate, tallow fatty acid octyl ester, lauryl laurate, stearyl stearate, behenyl behenate, cetyl myristate, esters of linear, unbranched, saturated monocarboxylic acid having 28 to 30 carbon atoms (hereinafter abbreviated as montanic acid) and ethylene glycol, esters of montanic acid and glycerin, montanic acid, glycerin ... Examples of the montanic acid include esters of montanic acid and butylene glycol, esters of montanic acid and trimethylolethane, esters of montanic acid and trimethylolpropane, esters of montanic acid and pentaerythritol, glycerin monostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, etc. These may be used alone or in combination of two or more.

The polyethylene glycol compounds are not particularly limited, and examples thereof include polyethylene glycols, polypropylene glycols, polyethylene glycol alkyl ethers, polypropylene glycol alkyl ethers, polyethylene glycol aryl ethers, polypropylene glycol aryl ethers, polyethylene glycol alkyl aryl ethers, polypropylene glycol alkyl aryl ethers, polyethylene glycol glycerin esters, polypropylene glycol glycerin esters, polyethylene sorbitol esters, polypropylene glycol sorbitol esters, polyethylene glycolized ethylenediamines, polypropylene glycolized ethylenediamines, polyethylene glycolized diethylenetriamines, and polypropylene glycolized diethylenetriamines.

The terpene resin generally refers to a resin obtained by copolymerizing a terpene monomer alone, or a terpene monomer and an aromatic monomer, or a terpene monomer and a phenol in an organic solvent in the presence of a Friedel-Crafts catalyst, but is not limited thereto. Examples of the terpene monomer include, but are not limited to, hemiterpenes having 5 carbon atoms such as isoprene, monoterpenes having 10 carbon atoms such as α-pinene, β-pinene, dipentene, d-limonene, myrcene, alloocimene, ocimene, α-phellandrene, α-terpinene, γ-terpinene, terpinolene, 1,8-cineole, 1,4-cineole, α-terpineol, β-terpineol, γ-terpineol, sabinene, paramentadienes, and carenes, sesquiterpenes having 15 carbon atoms such as caryophyllene and longifolene, and diterpenes having 20 carbon atoms. Among these compounds, α-pinene, β-pinene, dipentene, and d-limonene are particularly preferred. Examples of the aromatic monomer include, but are not limited to, styrene, α-methylstyrene, vinyltoluene, and isopropenyltoluene. Examples of the phenols include, but are not limited to, phenol, cresol, xylenol, and bisphenol A.
Alternatively, the terpene resin may be a hydrogenated terpene resin obtained by subjecting the obtained terpene resin to a hydrogenation treatment. For example, preferred terpene resins include α-pinene resin, β-pinene resin, aromatic modified terpene resin, terpene phenol resin, hydrogenated terpene resin, and other terpene resins. The terpene resins may be used alone or in combination of two or more.

Examples of the rosin-based resin include rosins such as gum rosin, wood rosin, and tall oil rosin, as well as stabilized rosins obtained by disproportionating or hydrogenating the rosins, polymerized rosins (typically dimers) that are polymers of the rosins, and modified rosins modified with unsaturated acids such as maleic acid, fumaric acid, and (meth)acrylic acid. Examples of the rosin derivative resin include esters of the rosin-based resins, phenol-modified products, and esters thereof. The rosin-based resins may be used alone or in a mixture of two or more types. The rosin-based resins or rosin derivative resins used in the present invention are not limited to these resins.

Examples of the aliphatic amides include stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, ethylene bisstearic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, ethylene bislauric acid amide, etc. These may be used alone or in combination of two or more.

Specific examples of saturated fatty acids among the above fatty acid compounds include lauric acid (dodecanoic acid), isodecanoic acid, tridecanoic acid, myristic acid (tetradecanoic acid), pentadecylic acid, palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid), isostearic acid, tuberculostearic acid (nonadecanoic acid), 2-hydroxystearic acid, arachidic acid (icosanoic acid), behenic acid (docosanoic acid), lignoceric acid (tetradocosanoic acid), cerotic acid (hexadocosanoic acid), montanic acid (octadocosanoic acid), and melissic acid, and in particular, lauric acid, palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid, and montanic acid. These may be used alone or in a mixture of two or more.

Specific examples of unsaturated fatty acids among the above fatty acid compounds include myristoleic acid (tetradecenoic acid), palmitoleic acid (hexadecenoic acid), oleic acid (cis-9-octadecenoic acid), elaidic acid (trans-9-octadecenoic acid), ricinoleic acid (octadecadienoic acid), vaccenic acid (cis-11-octadecenoic acid), linoleic acid (octadecadienoic acid), linolenic acid (9,11,13-octadecatrienoic acid), elestearic acid (9,11,13-octadecatrienoic acid), gadoleic acid (icosanoic acid), erucic acid (docosanoic acid), and nervonic acid (tetradocosanoic acid). These may be used alone or in combination of two or more.

Examples of fatty acid metal salts include lithium salts, calcium salts, magnesium salts, zinc salts, and aluminum salts of the fatty acids of the above fatty acid compounds. These may be used alone or in combination of two or more.

<Optional added ingredients>
In addition to the above components (a) to (c), the styrene-based resin composition of the present embodiment may contain, as necessary, known additives, processing aids, and other additive components within the range that does not impair the effects of the present invention. Examples of such additives and processing aids include antioxidants, weather resistance agents, antistatic agents, and fillers.

Examples of the antioxidant include phenol-based compounds, phosphorus-based compounds, and thioether-based compounds.
Examples of the phenol-based antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide], 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis(6-tert-butyl- m-cresol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2-tert-butyl- 4-Methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, stearyl[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)methylpropionate]methane, thiodiethylene glycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylene bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid ] glycol ester, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, 3,9-bis[1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], etc. These may be used alone or in combination of two or more.

Examples of the phosphorus-based antioxidants include tris(2,4-di-tert-butylphenyl)phosphite, trisnonylphenyl phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tridecyl phosphite, octyldiphenyl phosphite, di(decyl)monophenyl phosphite, di(tridecyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, tetra(tridecyl)-4,4'-n-pentaerythritol diphosphite, bis(2,4-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tetra(tridecyl)isopropylidenediphenol diphosphite, tetra(tridecyl)-4,4'-n- Butylidenebis(2-tert-butyl-5-methylphenol)diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis(4,6-tert-butylphenyl)-2-ethylhexylphospha phosphite, 2,2'-methylenebis(4,6-tert-butylphenyl)-octadecyl phosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol, etc. These may be used alone or in combination of two or more.

The above-mentioned thioether-based antioxidants include, for example, dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra(β-alkyl mercaptopropionate esters. These may be used alone or in combination of two or more.

As the weather resistance agent, an ultraviolet absorber or a hindered amine light stabilizer can be used. Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3'-tert-butylphenyl)-5-chlorobenzotriazole. 2-(2'-hydroxyphenyl)benzotriazoles such as 2-(2'-hydroxy-5'-tert-octylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-(benzotriazolyl)phenol), and 2-(2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl)benzotriazole; phenyl salicylate , resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, and other benzoates; 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide, and other substituted oxanilides; ethyl-α-cyano-β,β-diphenylacrylate cyanoacrylates such as methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; and triaryltriazines such as 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, and 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine. These may be used alone or in combination of two or more.

Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, and tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarbo xylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl) di(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) di(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2, 6,6-tetramethyl-4-piperidinol/diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1, Examples of hindered amine compounds include 5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8-12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, and 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane. These may be used alone or in combination of two or more.

As the antistatic agent, cationic, anionic, nonionic, amphoteric, fatty acid partial esters such as glycerin fatty acid monoesters, and the like can be used.
Specifically, alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, benzalkonium salts, N,N-bis(2-hydroxyethyl)-N-(3-dodecyloxy-2-hydroxypropyl)methyl ammonium methosulfate, (3-lauryl amidopropyl)trimethyl ammonium methyl sulfate, stearamidopropyl dimethyl-2-hydroxyethyl ammonium nitrate, stearamidopropyl dimethyl-2-hydroxyethyl ammonium phosphate, cationic polymers, alkyl sulfonates, alkyl benzene sulfonates, sodium alkyl diphenyl ether disulfonate, alkyl nitrate ester salts, phosphorus Examples of such esters include alkyl ester salts, alkyl phosphate amine salts, stearic acid monoglyceride, pentaerythritol fatty acid esters, sorbitan monopalmitate, sorbitan monostearate, diglycerol fatty acid esters, alkyldiethanolamines, alkyldiethanolamine fatty acid monoesters, alkyldiethanolamides, polyoxyethylene dodecyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol monolaurates, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyether block copolymers, cetyl betaine, and hydroxyethyl imidazoline sulfate esters. These may be used alone or in combination of two or more.

As the filler, talc, calcium carbonate, barium sulfate, carbon fiber, mica, wollastonite, whisker, etc. can be used.
In addition, optional additives such as antiblocking agents, colorants, antiblooming agents, surface treatment agents, antibacterial agents, and eye discharge inhibitors (eye discharge inhibitors such as silicone oils described in JP 2009-120717 A, monoamide compounds of higher aliphatic carboxylic acids, and monoester compounds obtained by reacting higher aliphatic carboxylic acids with monohydric to trihydric alcohol compounds) may be added.

The total content of any of the above-mentioned additives, processing aids, etc., in the styrene-based resin composition may be 0.05 to 5% by mass.

The styrene-based resin composition of the present embodiment may consist essentially of only the components (a) to (c) and any optional additional components, or may consist of only the components (a) to (c), or only the components (a) to (c) and any optional additional components.
The phrase "consisting essentially of only the components (a) to (c) and any optional additional components" means that 95 to 100 mass % (preferably 98 to 100 mass %) of the styrene-based resin composition is made up of the components (a) to (c) or the components (a) to (c) and any optional additional components.
The styrene-based resin composition of the present embodiment may contain inevitable impurities in addition to the components (a) to (c) and any optional additive components, as long as the effects of the present invention are not impaired.

[Physical properties of styrene-based resin composition]
<Linear expansion coefficient>
The linear expansion coefficient of the molded article obtained from the styrene-based resin composition of this embodiment is preferably 6×10 ⁻⁵ /° C. or less, more preferably 5×10 ⁻⁵ /° C. or less. In addition, the ratio of the linear expansion coefficient in the MD direction (flow direction during molding) to the TD direction (perpendicular to the MD direction) (TD/MD ratio) is preferably 0.8 to 1.3, more preferably 0.9 to 1.2. If the linear expansion coefficient is greater than 6×10 ⁻⁵ /° C., thermal expansion may cause defects in the product, or the metal may peel off in products bonded to metals, etc. In addition, if the TD/MD ratio is outside the range, the product may warp due to heat. In this disclosure, the linear expansion coefficient is a value measured in accordance with the TMA method of JIS K7197. In addition, the dimensional accuracy of the molded article produced using the styrene-based resin composition of this embodiment is evaluated by the value of the linear expansion coefficient.

<Melt flow rate (MFR)>
The melt flow rate of the styrene-based resin composition of the present embodiment is preferably 1 g/10 min or more, more preferably 2 g/10 min or more. If it is less than 1 g/10 min, the flowability is low, and the processing temperature needs to be increased, and (b) there is a risk of the physical properties being reduced due to deterioration of the porous paramylon or the molded product being discolored.
In this disclosure, the melt flow rate is a value measured in accordance with ISO 1133 at a temperature of 200° C. and a load of 49 N.

<Density>
The true density of the molded article obtained from the styrene-based resin composition of the present embodiment is preferably 1.25 or less, more preferably 1.20 or less. If it is more than 1.25, the weight reduction of the product may be insufficient.
In the present disclosure, the density is a value measured in accordance with ISO 1183. When the true density of a molded article obtained from the styrene-based resin composition of the present embodiment is 1.25 or less, a styrene-based resin composition excellent in dimensional accuracy, flowability, light weight and high rigidity, and molded appearance, and a molded article using the styrene-based resin composition can be provided.

<Flexural modulus>
The flexural modulus of the styrene-based resin composition of the present embodiment is preferably 2500 MPa or more, more preferably 3000 MPa or more. If it is less than 2500 MPa, the product cannot be made thin, and the weight cannot be reduced.
In this disclosure, the flexural modulus is a value measured in accordance with ISO 178.

[Method of producing styrene-based resin composition]
The styrene-based resin composition of the present embodiment can be produced by melt-kneading each component by any method. For example, a high-speed agitator such as a Henschel mixer, a batch-type kneader such as a Banbury mixer, a single-screw or twin-screw continuous kneader, a roll mixer, or the like can be used alone or in combination. The heating temperature during kneading is usually selected in the range of 180 to 250°C.

[Molding]
The molded article of the present invention is characterized by containing the above-mentioned styrene-based resin composition.
The styrene-based resin composition of the present embodiment can be used to produce a molded article by the above-mentioned melt kneading molding machine, or by using pellets of the obtained styrene-based resin composition as a raw material, through injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, foam molding, or the like.

Molded articles containing the styrene-based resin composition of this embodiment, particularly injection molded articles (including injection compression), are suitable for use in office equipment such as copiers, fax machines, personal computers, printers, information terminals, refrigerators, vacuum cleaners, and microwave ovens, home appliances, housings and various parts for electric and electronic equipment, interior and exterior components for automobiles, construction materials, foam insulation materials, insulating films, etc.

The following provides a more detailed explanation of the present invention based on examples and comparative examples, but the present invention is not limited to these examples.

<Measurement and evaluation methods>
The physical properties of the resin compositions obtained in each of the Examples and Comparative Examples were measured and evaluated according to the following methods.
(1) Contents of styrene monomer units, methacrylic acid monomer units, and methyl methacrylate monomer units in styrene-based resin (a) The resin composition was quantified from the integral ratio of the spectrum measured by a proton nuclear magnetic resonance ( ¹ H-NMR) spectrometer.
Sample preparation: 30 mg of resin pellets were dissolved in 0.75 mL of d ₆ -DMSO by heating at 60° C. for 4 to 6 hours.
・Measuring equipment: JNM ECA-500 manufactured by JEOL Ltd.
Measurement conditions: measurement temperature 25°C, observation nucleus ^1H , number of integrations 64, repetition time 11 seconds.

(Spectral assignment)
Regarding the attribution of the spectrum measured in dimethyl sulfoxide deuterated solvent, the peaks at 0.5 to 1.5 ppm are peaks derived from hydrogen of α-methyl group of methacrylic acid, methyl methacrylate, and six-membered cyclic acid anhydride, the peaks at 1.6 to 2.1 ppm are peaks derived from hydrogen of methylene group of polymer main chain, the peak at 3.5 ppm is peak derived from hydrogen of carboxylate ester (-COOCH ₃ ) of methyl methacrylate, and the peak at 12.4 ppm is peak derived from hydrogen of carboxylic acid of methacrylic acid. In addition, the peaks at 6.5 to 7.5 ppm are peaks derived from hydrogen of aromatic ring of styrene. Note that since the content of six-membered cyclic acid anhydride is small in the resins of the present embodiment and the comparative example, quantification is usually difficult by this measurement method.

(2) Weight Average Molecular Weight of Styrene-Based Resin (a) The weight average molecular weight of the styrene-based resin (a) was measured under the following conditions and by the following procedures.
Sample preparation: The resin was dissolved in tetrahydrofuran at about 0.05% by mass.
Measurement conditions: Instrument: TOSOH HLC-8220GPC
(Gel Permeation Chromatography)
Column: super HZM-H
Temperature: 40°C
Carrier: THF 0.35 mL/min
Detector: RI, UV: 254 nm
Calibration curve: Prepared using standard PS manufactured by TOSOH.

(3) Linear expansion coefficient The linear expansion coefficient (/°C) was measured in the MD and TD directions by cutting the center of a test piece (a) prepared by the method described below into a size of 10 × 5 × 4 mm in the MD and TD directions in accordance with the TMA method (−30°C to 80°C) of JIS K7197.

(4) Melt flow rate (MFR)
The melt mass flow rate (g/10 min) of the styrene-based resin (a) was measured in accordance with ISO 1133 (200° C., load 49 N).

(5) Density The density was measured in accordance with ISO 1183 using a test piece (a) prepared by the method described below.

(6) Flexural Modulus The flexural modulus (MPa) was measured in accordance with ISO 178 using a test piece (a) prepared by the method described below.

(7) Surface Appearance The surface appearance was evaluated by observing one surface of a test piece (b) prepared by the method described below. When there were less than 10 dents with an opening of 0.1 mm or more, the surface appearance was evaluated as "passed: ○", and when there were 20 or more dents, the surface appearance was evaluated as "poor: ×".

The materials used in the examples and comparative examples are as follows.
[Styrene-based resin (a)]
[GPPS]
Polystyrene with MFR 7.8 (GPPS, manufactured by PS Japan, HF77) was used.
[Rubber-modified styrene resin (HIPS)]
Polystyrene with MFR 3.0 (HIPS, manufactured by PS Japan, HT478) was used.
[Styrene-based copolymer resin]
A polymerization raw material composition liquid consisting of 70.0 parts by mass of styrene (ST), 15.0 parts by mass of butyl methacrylate (BA), 15.0 parts by mass of ethylbenzene, and 0.025 parts by mass of 1,1-bis(t-butylperoxy)cyclohexane was continuously supplied at a rate of 1.1 L/hour to a 4-L complete mixing reactor, then to a polymerization apparatus consisting of a 2-L laminar flow reactor, and further to a devolatilizer connected to a single-screw extruder for removing volatile matters such as unreacted monomers and polymerization solvent, successively to prepare a styrene-based copolymer resin, copolymer resin (1).
The polymerization reaction conditions in the polymerization step were a polymerization temperature of 122° C. in the complete mixing reactor and a polymerization temperature of 120 to 142° C. in the laminar flow reactor. The devolatilized unreacted gas was condensed in a condenser through which a coolant of −5° C. was passed, and recovered as an unreacted liquid.
The polymer content in the final polymerization solution was measured after drying the polymerization solution at 215° C. under a reduced pressure of 2.5 kPa for 30 minutes according to the formula [(mass of sample after drying/mass of sample before drying)×100%], and was found to be 65.6% by mass, and the MFR was 4.6.
[Blend 1]
The above HIPS (HT478) was blended with 5% by mass of styrene-maleic anhydride (SMA) copolymer (XIBOND250, manufactured by POLYSCOPE), and the MFR was 3.8.

[Paramylon (b)] (manufactured by Eugleid Co., Ltd., average particle size 5 μm, aspect ratio 1.1)

[Dispersant]
Phosphinic acid compound: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA, manufactured by Sanko Co., Ltd.)
NOR type hindered amine compound: bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate (manufactured by ADEKA Corporation: LA81)
Fatty acid ester: Glycerin monostearate (Riken Vitamin Co., Ltd.: S-100)

[Additive]
(Phenol-based antioxidant)
3-(3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate (manufactured by BASF, Irganox 1076)
(Phosphorus-based antioxidant)
Tris(2,4-di-tert-butylphenyl)phosphite (BASF Corporation, Irgafos 168)

[Examples 1 to 10]
Each component was added in the composition ratio shown in Table 1, and 0.2 parts by mass of Irganox 1076 and Irgafos 168 were added as antioxidants to 100 parts by mass of components (a) to (c), and then premixed. The resulting premix was mixed together and melt-extruded in the range of 180°C to 220°C using a twin-screw extruder (Toshiba Machine Co., Ltd., TEM-26SS) to obtain pellets of a styrene-based resin composition as a kneaded product. At this time, the screw rotation speed was 150 rpm and the discharge rate was 10 kg/hr. The pellets thus obtained were molded using an injection molding machine manufactured by Japan Steel Works Co., Ltd. equipped with an ISO standard test piece type (a) mold at a cylinder temperature of 220°C, a mold temperature of 50°C, an injection pressure (gauge pressure 40-60 MPa), an injection speed (panel setting value) of 50%, and an injection time/cooling time = 5 sec/20 sec to prepare a test piece (a). The obtained test piece (a) was used to evaluate the linear expansion coefficient, density, and flexural modulus.
Similarly, a test piece (b) was prepared by molding under the same conditions as above using an injection molding machine manufactured by Japan Steel Works, Ltd., equipped with a mold (b) measuring 50×120 mm and having a thickness of 1 mm. The test piece (b) was then used to evaluate the appearance of the molded product. The evaluation results are shown in Table 1.

[Comparative Examples 1 to 5]
Comparative Examples 1 to 11 were carried out in the same manner as Example 1, except that the compositions were changed as shown in Table 2. The results of the measurements and evaluations of the various physical properties are shown in Table 2.

As shown in Table 1, when comparing the linear expansion coefficients of Examples 1 to 10 with those of Comparative Examples 1 to 5, it can be seen that the linear expansion coefficients of the Examples are lower. It can also be seen that the TD/MD ratios of the Examples are close to 1 and have little anisotropy. Therefore, it is considered that the dimensional accuracy of Examples 1 to 10 is good. Furthermore, it can be seen that there is little decrease in fluidity and high rigidity is possible. In addition, the true density of the molded bodies obtained from the styrene-based resin compositions of Examples 1 to 10 was 1.22 or less in all cases.
On the other hand, the results of Comparative Examples 1 to 4 shown in Table 2 confirm that when paramylon (b) is not contained, the linear expansion coefficient is large across the board and the elastic modulus is low. Moreover, as in Comparative Example 5, it was confirmed that adding a large amount of paramylon (b) reduces fluidity and results in poor molded appearance. Furthermore, the true density of the molded article obtained with the composition of Comparative Example 5 was 1.26.

Molded articles containing the styrene-based resin composition of the present invention can be suitably used for packaging materials, building materials, electronic and electric parts, automobiles, etc.

Claims (5)

45.0 to 99.5% by mass of a styrene-based resin (a);
0.5 to 55.0% by mass of paramylon (b);
A styrene-based resin composition comprising: The styrene-based resin composition according to claim 1, wherein the styrene-based resin (a) contains a styrene-based monomer unit and an unsaturated carboxylic acid-based monomer unit. The styrene-based resin composition according to claim 1 or 2, further comprising 0.5 to 10.0 parts by mass of a dispersant (c) per 100 parts by mass of the total amount of the styrene-based resin composition. The styrene-based resin composition according to claim 3, wherein the dispersant (c) is one or more compounds selected from the group consisting of phosphinic acid compounds, NOR-type hindered amine compounds, fatty acid ester compounds, polyethylene glycol compounds, terpene compounds, and rosin compounds. A molded article comprising the styrene-based resin composition according to claim 1 or 2.