JP7264649B2 - Flame-retardant extruded sheet - Google Patents

Description

The present invention relates to flame retardant extruded sheets.

Styrene-based resins are used in a wide range of applications due to their excellent moldability, dimensional stability, and impact resistance. Among them, flame-retardant polystyrene-based resin compositions are used in a wide variety of applications, including home appliances and OA equipment, and there is currently a demand for thinner products due to reduction and weight reduction.

JP 2014-95056 A Japanese Patent Publication No. 2002-507238

Here, various flame retardants such as bromine-based flame retardants and phosphorus-based flame retardants have been proposed in order to impart flame retardancy to styrene resins. Flame retardants are widely used. However, the addition of such a flame retardant is a problem that the extrusion moldability of the non-foamed extruded sheet obtained from the resin composition to which the flame retardant is added and the mechanical properties such as impact resistance and heat resistance are deteriorated. There is

For example, Patent Literature 1 discusses a phosphate ester-based flame retardant. Although flame retardancy can be imparted, the addition of a phosphate ester (Example 10) requires a large amount of addition, which reduces heat resistance and impact resistance. There is In addition, the result of the UL94 vertical burning test is V-2 with a wall thickness of 1.5 mm, and the intended flame retardancy cannot be obtained.

As a technique for imparting flame retardancy to styrene resins, Patent Document 2 discloses a technique for adding a specific NOR type hindered amine compound. Regarding polystyrene to which a NOR-type hindered amine compound is added, although there is a description that it exhibits flame retardancy and finds application in housings for office equipment (Example 16), 0.125 inch (about 3.2 mm) However, flame retardancy can be obtained with a thickness of 100.degree. Further, there is no description about the moldability and product properties of the non-foamed extruded sheet.

As described above, in the prior art, it is not possible to obtain a resin composition that exhibits sufficient flame retardancy for a non-foamed extruded sheet having a thickness of 0.5 mm or less. It is necessary to add a large amount of a retardant, and the deterioration of heat resistance and impact resistance makes it difficult to commercialize the composition, and the extrusion workability of the sheet is also deteriorated.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a flame-retardant extruded sheet having excellent flame retardancy, heat resistance, impact resistance, and formability.

As a result of intensive studies to solve the above problems, the present inventors have found that one or more flame retardants selected from the group consisting of a NOR hindered amine compound, a phosphorus flame retardant, and a bromine flame retardant are added to the styrene resin. By making a non-foamed extruded sheet with a specific ratio of a retardant added, it surprisingly exhibits high flame retardancy even with a thickness of 0.5 mm or less, and retains heat resistance, impact resistance, and moldability. The inventors have found that a flame-retardant extruded sheet can be obtained, and have completed the present invention.
That is, the present invention is as follows.

[1] (A) 97.0 to 99.8% by mass of a styrene resin, (B) 0.2 to 3.0% by mass of a NOR-type hindered amine compound, and (C) a phosphorus-based flame retardant and one or more flame retardants selected from the group consisting of bromine-based flame retardants, containing 0.0 to 5.0 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B) Obtained from a styrene resin composition that
A flame-retardant extruded sheet having a thickness of 0.5 mm or less.
[2] The flame-retardant extruded sheet according to [1] above, wherein the styrene-based resin composition has an MFR of 0.5 to 6.0 g/10 min.
[3] The above-mentioned [1] or [2], wherein the phosphorus-based flame retardant of component (C) is at least one selected from the group consisting of phosphoric acid ester compounds, phosphazene compounds, and phosphonic acid ester compounds. flame retardant extruded sheet.
[4] The flame-retardant extruded sheet according to any one of [1] to [3] above, wherein the (B) NOR-type hindered amine compound is oligomeric or polymeric.
[5] The flame-retardant extruded sheet according to any one of [1] to [4] above, wherein the flame-retardant extruded sheet is obtained by biaxial stretching and has a thickness of 50 μm or more and 0.5 mm or less. sheet.

SUMMARY OF THE INVENTION An object of the present invention is to provide a flame-retardant extruded sheet having excellent flame retardancy, heat resistance, impact resistance, and formability.

Hereinafter, embodiments of the present invention (hereinafter referred to as "present embodiments") will be described in detail. can be implemented.

[Flame-retardant extruded sheet]
The flame-retardant extruded sheet of the present embodiment is obtained from a styrene-based resin composition and is a non-foamed extruded sheet having a thickness of 0.5 mm or less, wherein the styrene-based resin composition comprises (A) styrene containing 97.0 to 99.8% by mass of a system resin, (B) 0.2 to 3.0% by mass of a NOR-type hindered amine compound, and (C) a phosphorus-based flame retardant and a bromine-based flame retardant. One or more flame retardants selected from the group are contained in an amount of 0.0 to 5.0 parts by mass per 100 parts by mass of the total amount of the component (A) and the component (B). The flame-retardant extruded sheet thus constructed can be excellent in flame retardancy, heat resistance, impact resistance, and formability. Furthermore, when a sheet is stretched, the molecular chain of the styrene-based resin is stretched by stretching, etc., so the combustion mode changes during combustion, and high flame retardancy is achieved even with a thin wall thickness. Obtainable. Moreover, it does not affect the heat resistance and non-foaming extrusion moldability of styrene resins.
In the present specification, one or more flame retardants selected from the group consisting of (A) styrene resins, (B) NOR hindered amine compounds, (C) phosphorus flame retardants and bromine flame retardants are , (A) component, (B) component, and (C) component.

<Styrene resin composition>
<(A) Styrene resin>
In the present embodiment, the content of (A) styrene resin is 97.0 to 99.8% by mass, preferably 97% by mass, based on 100% by mass of the total amount of components (A) and (B). .5 to 99.5% by mass, more preferably 98.0 to 99.0% by mass. By making the content 97.0% by mass or more, heat resistance, impact resistance, and non-foaming extrusion moldability can be improved, and by making the content 99.8% by mass or less, relative The content of component (B), which will be described later, is increased, and the flame retardancy can be improved.

The (A) styrene-based resin that can be used in the present embodiment is a styrene-based monomer and, if necessary, one or more selected from other vinyl monomers and rubber-like polymers copolymerizable therewith. It is a resin obtained by polymerizing Specific examples include, but are not limited to, polystyrene, a rubber-modified styrene resin in which particles of the rubber-like polymer (a) are dispersed in a matrix, and a copolymer resin.

<polystyrene>
In the present embodiment, polystyrene is a homopolymer of styrene-based monomers, and commonly available materials can be appropriately selected and used. Styrenic monomers constituting polystyrene include, in addition to styrene, α-methylstyrene, α-methyl-p-methylstyrene, ο-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, ethyl Styrene, isobutylstyrene, and styrene derivatives such as t-butylstyrene or bromostyrene and indene. Styrene is particularly preferred from an industrial point of view. These styrenic monomers can be used singly or in combination of two or more. 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 typically consists of styrene-based monomer units.

<Rubber modified styrene resin>
In the present embodiment, the rubber-modified styrenic resin is obtained by dispersing particles of the rubber-like polymer (a) in a styrene-based resin as a matrix. It can be produced by polymerizing monomers.

Examples of styrene-based monomers constituting the rubber-modified styrene-based resin of the present embodiment include styrene, α-methylstyrene, α-methyl p-methylstyrene, ο-methylstyrene, m-methylstyrene, Styrene derivatives such as p-methylstyrene, vinyltoluene, ethylstyrene, isobutylstyrene, and t-butylstyrene or bromostyrene and indene. Styrene is particularly preferred. These styrenic monomers can be used singly or in combination of two or more.

The rubber-like polymer (a) contained in the rubber-modified styrenic resin of the present embodiment includes, for example, a styrenic resin obtained from the above styrenic monomer on the inside and the styrenic resin on the outside. may be grafted.

As the rubber-like polymer (a), for example, polybutadiene, polyisoprene, natural rubber, polychloroprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, etc. can be used. coalescence is preferred. Both high cis polybutadiene with a high cis content and low cis polybutadiene with a low cis content can be used for the polybutadiene. Both a random structure and a block structure can be used as the structure of the styrene-butadiene copolymer. One or more of these rubber-like polymers (a) can be used. Saturated rubber obtained by hydrogenating butadiene rubber can also be used.
Examples of such rubber-modified styrene resins include HIPS (high impact polystyrene), ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AES resin ( acrylonitrile-ethylene propylene rubber-styrene copolymer) and the like.

When the rubber-modified styrene-based resin is a HIPS-based resin, among these rubber-like polymers (a), particularly preferred is a high-cis polybutadiene composed of 90 mol % or more of cis-1,4 bonds. In the high-cis polybutadiene, the vinyl 1,2 bond is preferably 6 mol % or less, particularly preferably 3 mol % or less.
The content of isomers having a cis 1,4, trans 1,4, or vinyl 1,2 structure as isomers related to the structural units of the high-cis polybutadiene was measured using an infrared spectrophotometer and measured by the Morero method. It can be calculated by data processing.
The high-cis polybutadiene can be easily obtained by polymerizing 1,3-butadiene using a known production method, for example, a catalyst containing an organoaluminum compound and a cobalt or nickel compound.

The content of the rubber-like polymer (a) contained in the rubber-modified styrenic resin is preferably 3-20% by mass, more preferably 5-15% by mass. If the content of the rubber-like polymer (a) is less than 3% by mass, the impact resistance of the styrene-based resin may deteriorate. Moreover, when the content of the rubber-like polymer (a) exceeds 20% by mass, the flame retardancy may be lowered.
In the present disclosure, the content of the rubber-like polymer (a) contained in the rubber-modified styrenic resin is a value calculated using pyrolysis gas chromatography.

The average particle size of the rubber-like polymer (a) contained in the rubber-modified styrenic resin is preferably 0.5 to 4.0 μm, more preferably 0, from the viewpoint of impact resistance and flame retardancy. 0.8 to 3.5 μm.
In the present disclosure, the average particle size of the rubber-like polymer (a) contained in the rubber-modified styrenic resin can be measured by the following method.
A 75 nm-thick ultra-thin section is prepared from a rubber-modified styrenic resin stained with osmium tetroxide, and photographed at a magnification of 10,000 using an electron microscope. In the photograph, black-stained particles are the rubber-like polymer. From the picture, the following formula (N1):
Average particle size = ΣniDri ³ /ΣniDri ² (N1)
(In the formula, ni is the number of rubber-like polymer (a) particles having a particle diameter Dri, and the particle diameter Dri is a particle diameter calculated as a circle-equivalent diameter from the area of the particles in the photograph.)
The area-average particle size is calculated by the method and taken as the average particle size of the rubber-like polymer (a). For this measurement, a photograph is loaded into a scanner at a resolution of 200 dpi and measured using particle analysis software of an image analyzer IP-1000 (manufactured by Asahi Kasei Co., Ltd.).

The reduced viscosity of the rubber-modified styrenic resin (which is an index of the molecular weight of the rubber-modified styrenic resin) is preferably in the range of 0.50 to 0.85 dL/g, more preferably 0.55 to 0.85 dL/g. It is in the range of 0.80 dL/g. If it is less than 0.50 dL/g, the impact strength may decrease, and if it exceeds 0.85 dL/g, the fluidity may decrease, resulting in a decrease in moldability.
In the present disclosure, the reduced viscosity of the rubber-modified styrenic resin is a value measured in a toluene solution at 30° C. and a concentration of 0.5 g/dL.

The method for producing the rubber-modified styrenic resin is not particularly limited, but bulk polymerization (or solution polymerization) in which a styrenic monomer (and a solvent) is polymerized in the presence of the rubber-like polymer (a), Alternatively, it can be produced by bulk-suspension polymerization that shifts to suspension polymerization during the reaction, or emulsion graft polymerization that polymerizes a styrenic monomer in the presence of the rubber-like polymer (a) latex. In bulk polymerization, a mixed solution containing a rubber-like polymer (a), a styrenic monomer, and optionally an organic solvent, an organic peroxide, and/or a chain transfer agent is added to a complete mixing reactor. Alternatively, it can be produced by continuously supplying to a polymerization apparatus constructed by connecting a tank reactor and a plurality of tank reactors in series.

<Copolymer resin>
In the present embodiment, the copolymer resin is a resin optionally containing styrene-based monomer units, unsaturated carboxylic acid-based monomer units, and further unsaturated carboxylic acid ester-based monomer units. When the total content of the styrene-based monomer unit, the unsaturated carboxylic acid-based monomer unit, and the unsaturated carboxylic acid ester-based monomer unit is 100% by mass, the copolymer resin is a styrene-based monomer The unit content is preferably 69 to 96% by mass, more preferably 74 to 92% by mass, still more preferably 77 to 87% by mass. By making the content 69% by mass or more, the fluidity of the resin can be improved, while by making the content 96% by mass or less, the unsaturated carboxylic acid-based monomer unit described later And it becomes difficult to allow the unsaturated carboxylic acid ester-based monomer units to exist in a desired amount, making it difficult to obtain the effects described later by these monomer units.

In the copolymer resin, the unsaturated carboxylic acid-based monomer unit plays a role of improving heat resistance. When the total content of the styrene-based monomer unit, the unsaturated carboxylic acid-based monomer unit, and the unsaturated carboxylic acid ester-based monomer unit of the copolymer resin is 100% by mass, the unsaturated carboxylic acid-based unit The content of the monomer units is preferably 4 to 16% by mass, more preferably 6 to 14% by mass, still more preferably 8 to 13% by mass. By setting the content to 4% by mass or more, the heat resistance can be further improved. can be improved, and the fluidity and mechanical properties of the resin can be improved.

In general, styrene-methacrylic acid-based resins including styrene-methacrylic acid-methyl methacrylate copolymer resins are produced by radical polymerization in most cases on an industrial scale. Various alcohols can be added to the polymerization system to suppress the polymerization reaction.

The unsaturated carboxylic acid ester-based monomer suppresses the dehydration reaction of the unsaturated carboxylic acid-based monomer through intermolecular interaction with the unsaturated carboxylic acid-based monomer, and the mechanical strength of the resin can be used to improve Furthermore, the unsaturated carboxylic acid ester monomer contributes to the improvement of resin properties such as weather resistance and surface hardness.

When the total content of styrene-based monomer units, unsaturated carboxylic acid-based monomer units, and unsaturated carboxylic acid ester-based monomer units is 100% by mass, unsaturated carboxylic acid ester-based monomer units The content of is preferably 0 to 15% by mass, more preferably 1 to 12% by mass, and still more preferably 2 to 10% by mass. By setting the content to 15% by mass or less, the fluidity of the resin can be improved and the water absorption can be suppressed. In addition, by setting the content of the unsaturated carboxylic acid ester-based monomer unit to 0% by mass, it is possible to improve heat resistance and reduce costs, but from the above viewpoint, the unsaturated carboxylic acid ester-based monomer The body unit content can also be greater than 0% by weight.

When an unsaturated carboxylic acid-based monomer and an unsaturated carboxylic acid ester-based monomer unit are bonded side by side, if a high-temperature, high-vacuum devolatilization apparatus is used, a dealcoholization reaction may occur depending on the conditions. Six-membered cyclic anhydrides may be formed. The copolymer resin of the present embodiment may contain this six-membered cyclic acid anhydride, but it is preferable that the content is as small as possible because it lowers the fluidity.

In the present embodiment, the contents of styrene monomer units, methacrylic acid monomer units, and methyl methacrylate monomer units in the copolymer resin are each measured using a proton nuclear magnetic resonance ( ¹ H-NMR) spectrometer. can be obtained from the integral ratio of the spectrum measured by

In the present embodiment, the copolymer resin contains monomer units other than styrene-based monomer units, unsaturated carboxylic acid-based monomer units, and unsaturated carboxylic acid ester-based monomer units. Although it is not excluded to further contain within a range that does not impair the , it typically consists of styrene-based monomer units, unsaturated carboxylic acid-based monomer units, and unsaturated carboxylic acid ester-based monomer units.

Examples of styrene-based monomers include, but are not limited to, styrene, α-methylstyrene, α-methyl-p-methylstyrene, ο-methylstyrene, m-methylstyrene, p-methylstyrene, and vinyltoluene. , ethylstyrene, isobutylstyrene, t-butylstyrene, bromostyrene, indene and other styrene derivatives. As the styrene-based monomer, styrene is preferable from an industrial point of view. These styrenic monomers can be used singly or in combination of two or more.

Examples of unsaturated carboxylic acid-based monomers include, but are not particularly limited to, methacrylic acid, acrylic acid, maleic anhydride, maleic acid, fumaric acid, and itaconic acid. As the unsaturated carboxylic acid-based monomer, methacrylic acid is preferable because it has a large effect of improving heat resistance and is liquid at room temperature and excellent in handleability. These unsaturated carboxylic acid-based monomers can be used singly or in combination of two or more.

Furthermore, the unsaturated carboxylic acid ester monomer is not particularly limited, but examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) ) cyclohexyl acrylate and the like. As the (meth)acrylic acid ester-based monomer, methyl (meth)acrylate is preferable because it has little effect on deterioration of heat resistance. These unsaturated carboxylic acid ester monomers can be used singly or in combination of two or more.

In the present embodiment, the weight average molecular weight (Mw) of the copolymer resin is preferably 100,000 to 350,000, more preferably 120,000 to 300,000, still more preferably 140,000 to 240,000. is. When the weight-average molecular weight (Mw) is from 100,000 to 350,000, a resin having excellent balance between mechanical strength and fluidity can be obtained, and gel matter is less mixed. The weight average molecular weight (Mw) is a value obtained by standard polystyrene conversion using gel permeation chromatography.

In the present embodiment, the method for polymerizing the copolymer resin is not particularly limited, but for example, a bulk polymerization method or a solution polymerization method can be suitably employed as a radical polymerization method. The polymerization method mainly includes a polymerization step of polymerizing raw materials for polymerization (monomer components) and a devolatilization step of removing volatile matter such as unreacted monomers and polymerization solvent from the polymerization product.

A method for polymerizing a copolymer resin that can be used in the present embodiment will be described below.
When polymerizing raw materials to obtain a copolymer resin, the raw material composition for polymerization typically contains a polymerization initiator and a chain transfer agent.
Examples of polymerization initiators include organic peroxides such as 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)cyclohexane, n-butyl-4,4-bis(t -Butylperoxy)valerate and other peroxyketals, dialkylperoxides such as di-t-butylperoxide, t-butylcumylperoxide and dicumylperoxide, diacylperoxides such as acetylperoxide and isobutyrylperoxide, diisopropylperoxydi Examples include peroxydicarbonates such as carbonates, peroxyesters such as t-butylperoxyacetate, ketone peroxides such as acetylacetone peroxide, and hydroperoxides such as t-butyl hydroperoxide. Among them, 1,1-bis(t-butylperoxy)cyclohexane is preferred from the viewpoint of decomposition rate and polymerization rate.
Examples of chain transfer agents include α-methylstyrene linear dimer, n-dodecylmercaptan, t-dodecylmercaptan, n-octylmercaptan and the like.

As a polymerization method, solution polymerization using a polymerization solvent can be employed as necessary. Examples of the polymerization solvent to be used include aromatic hydrocarbons such as ethylbenzene and dialkyl ketones such as methyl ethyl ketone, each of which 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 they do not reduce the solubility of the polymerization product. These polymerization solvents are preferably used in an amount not exceeding 25 parts by mass with respect to 100 parts by mass of the total monomers. If the amount of the polymerization solvent exceeds 25 parts by mass with respect to 100 parts by mass of the total monomers, the polymerization rate tends to decrease significantly and the mechanical strength of the resulting resin tends to decrease significantly. Addition of 5 to 20 parts by mass per 100 parts by mass of all monomers prior to polymerization facilitates homogenization of quality and is also preferable from the viewpoint of polymerization temperature control.

In this embodiment, the apparatus used in the polymerization step for obtaining the copolymer resin is not particularly limited, and may be appropriately selected according to the polymerization method of the styrene-based resin. For example, in the case of bulk polymerization, a polymerization apparatus in which one or a plurality of complete mixing reactors are connected can be used. The devolatilization step is not particularly limited, and in the case of bulk polymerization, the polymerization is continued until the final unreacted monomer is preferably 50% by mass or less, more preferably 40% by mass or less. In order to remove volatile matter such as, devolatilization treatment is performed by a known method. For example, ordinary devolatilizers such as flash drums, twin-screw devolatilizers, thin film evaporators and extruders can be used, but devolatilizers with a small stagnant portion are preferred. The temperature of the devolatilization treatment is usually about 190 to 280° C., and more preferably 190 to 260° C. from the viewpoint of suppressing the formation of a six-membered cyclic acid anhydride due to the adjacency of methacrylic acid and methyl methacrylate. . The pressure of the devolatilization treatment is usually about 0.13 to 4.0 kPa, preferably 0.13 to 3.0 kPa, more preferably 0.13 to 2.0 kPa. Desirable devolatilization methods include, for example, a method of reducing the pressure under heating to remove the volatile matter, and a method of removing the volatile matter through an extruder or the like designed for the purpose of removing the volatile matter.

In this embodiment, the fluidity of (A) the styrene resin preferably has a melt flow rate (MFR) measured according to ISO1133 in the range of 0.5 to 5.0 g/10 min. (A) If the fluidity of the styrene-based resin is less than the above range, the non-foaming extrusion moldability of the resin composition may deteriorate, which is not preferable. On the other hand, if the fluidity of the styrene-based resin (A) exceeds the above range, there is a risk that the thickness uniformity in the non-foaming extrusion moldability will deteriorate, and the flame retardancy and impact resistance will tend to deteriorate.

<(B) NOR hindered amine compound>
(B) The content of the NOR-type hindered amine compound is 0.2 to 3.0% by mass, preferably 0.5 to 3.0% by mass, based on 100% by mass of the total amount of components (A) and (B). 2.5% by mass, more preferably 1.0 to 2.0% by mass. By setting the content to 0.2% by mass or more, flame retardancy can be obtained in a thin and thick molded article. Moreover, by setting the content to 3.0% by mass or less, heat resistance, impact resistance, and moldability can be improved.
The (B) NOR-type hindered amine compound is well known as a light stabilizer, and can impart light resistance by adding it.
(B) The alkoxyimino group of the NOR (alkoxyimino group) type hindered amine compound is an NH type in which the imino group (>N—H) portion of the piperidine ring remains NH, and H is a methyl group. In contrast to the substituted N-methyl type, it has an N-alkoxyl group (>N-OR) structure, and the N-alkoxyl group easily becomes a radical by capturing an alkylperoxy radical (RO _2. ). Demonstrate flame retardant effect. On the other hand, in the case of N-methyl hindered amine compounds or NH hindered amine compounds, the flame retardancy may be lower than in the case of NOR hindered amine compounds.

The above alkoxyl group (-OR) is not limited to an alkoxyl group in which oxygen is bonded to an alkyl group, and R includes a cycloalkyl group, an aralkyl group, an aryl group, etc., in addition to the alkyl group.
Specific examples of these alkoxyl groups are preferably a methoxy group, a propoxy group, a cyclohexyloxy group and an octyloxy group. It is preferable from the viewpoint that bleeding out from the film can be suppressed.

The (B) NOR-type hindered amine compound used in the present embodiment is not particularly limited as long as it has a structure of an N-alkoxyl group (>N-OR). Specific examples include NOR-type hindered amine compounds described in JP-A-2002-507238, WO 2005/082852, WO 2008/003605, and the like.

Further, (B) the NOR-type hindered amine-based compound is particularly preferably of a polymer type. Macromolecular types are generally oligomeric or polymeric compounds. If it is a polymer type, mold deposits during molding can be reduced, and it is excellent in terms of flame retardancy and heat resistance.
The number of repeating units of the polymer type oligomeric or polymeric compound is preferably 2 to 100, more preferably 5 to 80.

Specific examples of (B) NOR-type hindered amine compounds include the following compounds: 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine; bis(1-octyloxy- 2,2,6,6-tetramethylpiperidin-4-yl) 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; 4,4′-hexamethylenebis(amino- 2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-octyloxy) end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine -oligomeric compounds which are condensation products with 2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine; 4,4′-hexamethylenebis(amino-2,2, 6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-cyclohexyloxy-2,2) end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine 2,4-bis[(1-cyclohexyloxy-2,2,6, 6-piperidin-4-yl)-6-chloro-s-triazine; peroxide-treated 4-butylamino-2,2,6,6-tetramethylpiperidine and 2,4,6-trichloro-s-triazine and the reaction product of cyclohexane and N,N′-ethane-1,2-diylbis(1,3-propanediamine) (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); (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate; 1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-one; bis(1-stearyl) Oxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate.

Commercially available products include Flamestab NOR116FF, TINUVIN NOR371, TINUVIN XT850FF, TINUVIN XT855FF, TINUVIN PA123 manufactured by BASF, and LA-81 manufactured by ADEKA Corporation.
(B) NOR-type hindered amine compounds may be used singly or in combination of two or more.

<(C) Phosphorus Flame Retardant, Bromine Flame Retardant>
The styrenic resin composition of the present embodiment may contain (C) one or more flame retardants selected from the group consisting of phosphorus-based flame retardants and bromine-based flame retardants. When a phosphorus-based flame retardant and/or a bromine-based flame retardant are used, a synergistic effect with (B) the NOR-type hindered amine-based compound makes it possible to obtain even higher flame retardancy.

The phosphorus-based flame retardant and the bromine-based flame retardant may be a single compound or a mixture, and both the phosphorus-based flame retardant and the bromine-based flame retardant may be used. In this embodiment, as the component (C), a phosphorus-based flame retardant is preferable in terms of flame retardancy, moldability, environmental friendliness, and the like.

The content of component (C) is 0.0 to 5.0 parts by mass, preferably 1.0 to 5.0 parts by mass, per 100 parts by mass of the total amount of components (A) and (B). parts, more preferably 2.0 to 4.0 parts by mass, still more preferably 3.0 to 4.0 parts by mass. In the present embodiment, the styrenic resin composition can improve flame retardancy without containing component (C). High flame retardancy can be obtained by a synergistic effect. By setting the content to 1.0 parts by mass or more, a synergistic effect can be effectively obtained. On the other hand, by setting the content to 5.0 parts by mass or less, heat resistance, impact resistance and moldability can be improved.
The content of component (C) in the resin composition can be measured by dissolving the styrenic resin composition in chloroform and conducting GS-MS analysis.

-Phosphorus Flame Retardant-
The phosphorus-based flame retardant is not particularly limited, and one obtained by a conventionally known method or a commercially available product can be used. Phosphate ester compounds, phosphazene compounds, or phosphonate ester compounds are preferred, and these may be used alone or in combination of two or more. Among them, (A) a phosphoric acid ester compound or a phosphonic acid ester compound having good compatibility with the styrene resin is most preferable.

When the phosphorous flame retardant has a phosphorus content of 3.0% by mass or more, a flame retardant synergistic effect with (B) the NOR hindered amine compound is exhibited, and high flame retardancy is achieved with a small amount added. You can get sex. A phosphorus content of 3.0% by mass or more means a phosphorus compound containing 3.0% by mass or more of elemental phosphorus in the phosphorus-based flame retardant.

The phosphorus-based flame retardant preferably has a phosphorus content of 3.0% by mass or more, more preferably 7.0% by mass or more. When the phosphorus content is 3.0% by mass or more, a synergistic effect is exhibited with (B) the NOR-type hindered amine compound and flame retardancy, so that high flame retardancy, that is, UL94 vertical burning test (UL94-V test), V-2 can be obtained at a thickness of 0.8 mm.
In addition, phosphorus content can be measured by an absorptiometric method.

As the phosphorus-based flame retardant, a flame retardant that is liquid at 150° C. to 300° C. and has a melting point of 300° C. or lower is preferable because it is well dispersed in the styrene-based resin composition. When a phosphorus-based flame retardant that is solid during melt-kneading (for example, a phosphorus-based flame retardant that does not have a melting point) is used, the phosphorus-based flame retardant is not liquid during melt-kneading, so it is uniformly dispersed in component (A). Otherwise, physical properties may deteriorate, and flame retardancy may deteriorate.

--Phosphate compound--
Phosphate ester compounds include, for example, trimethyl phosphate (TMP), triethyl phosphate (TEP), triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyl diphenyl phosphate (CDP ), resorcinol bis-dixylenyl phosphate, resorcinol bis-diphenyl phosphate, bisphenol A bis-diphenyl phosphate (BADP), bisphenol A bis-dicresyl phosphate, biphenol bis-diphenyl phosphate, biphenol Examples include aromatic condensed phosphate ester compounds such as bis-dixylenyl phosphate, which are reaction products of phosphorus oxychloride, dihydric phenol compounds and phenol (or alkylphenol).

Among these, triphenyl phosphate (TPP), tricresyl phosphate (TCP), resorcinol bis-dixylenyl phosphate, resorcinol bis-diphenyl phosphate, bisphenol A bis-diphenyl phosphate (BADP), and biphenol bis-diphenyl phosphate are preferred. , biphenol bis-dixylenyl phosphate, more preferably triphenyl phosphate (TPP), resorcinol bis-dixylenyl phosphate, resorcinol bis-diphenyl phosphate, still more preferably resorcinol bis-dixylenyl phosphate. be.

式（１）中、Ｒ_１～Ｒ_５は水素原子、炭素数１～１０のアルキル基、炭素数３～２０のシクロアルキル基、炭素数６～２０のアリール基、炭素数１～１０のアルコキシ基、又はハロゲン原子であり、Ｒ_１～Ｒ_５は同一でも異なっていてもよい。ｎは１～３０の整数であり、好ましくは０～１０の整数である。 In addition, the phosphate ester compound is preferably a condensed phosphate ester compound of the condensation type from the viewpoint of heat resistance, reduction of mold deposits during molding, etc., and is particularly represented by the following formula (1). An aromatic condensed phosphate compound is preferred.

In formula (1), R ₁ to R ₅ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. group, or a halogen atom, and R ₁ to R ₅ may be the same or different. n is an integer of 1-30, preferably an integer of 0-10.

Alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, amyl, tertiary amyl, hexyl, 2-ethylhexyl, n-octyl, nonyl, decyl and the like.

Cycloalkyl groups include cyclohexyl and the like.
Aryl groups include phenyl, cresyl, xylyl, 2,6-xylyl, 2,4,6-trimethylphenyl, butylphenyl, nonylphenyl and the like.
Alkoxy groups include methoxy, ethoxy, propoxy, butoxy and the like.
A fluorine atom, a chlorine atom, a bromine atom etc. are mentioned as a halogen atom.

Further, among the above phosphate ester compounds, as the phosphorus-based flame retardant of the component (C), from the viewpoint of achieving both flame retardancy and transparency, compound No. 1 below is preferred. Phosphate ester compounds of 1, 2, or 3 are preferred, compound no. 2 or 3 is more preferred, and compound No. 2 is more preferred.

compound no. 2 (resorcinol bis-dixylenyl phosphate), for example, PX-200 from Daihachi Chemical Industry Co., Ltd. is compound No. 2; As 3 (resorcinol bis-diphenyl phosphate), for example, CR-733S manufactured by Daihachi Chemical Industry Co., Ltd. can be used.

-Phosphazene compound-
Examples of phosphazene compounds include 1,1,3,3,5,5-hexa(methoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(ethoxy)cyclotriphosphazene, 1,1 ,3,3,5,5-hexa(n-propoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(iso-propoxy)cyclotriphosphazene, 1,1,3,3,5 ,5-hexa(n-butoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(iso-butoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(phenoxy) ) cyclotriphosphazene, 1,1,3,3,5,5-hexa(p-tolyloxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(m-tolyloxy)cyclotriphosphazene, 1 , 1,3,3,5,5-hexa(o-tolyloxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(4-ethylphenoxy)cyclotriphosphazene, 1,1,3, 3,5,5-hexa(4-n-propylphenoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(4-iso-propylphenoxy)cyclotriphosphazene, 1,1,3, 3,5,5-hexa(4-t-butylphenoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(4-t-octylphenoxy)cyclotriphosphazene, 1,1,3, 3,5,5-hexa(2,3-dimethylphenoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(2,4-dimethylphenoxy)cyclotriphosphazene, 1,1,3, 3,5,5-hexa(2,5-dimethylphenoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(2,6-dimethylphenoxy)cyclotriphosphazene, 1,3,5- Tris(methoxy)-1,3,5-tris(phenoxy)cyclotriphosphazene, 1,3,5-tris(ethoxy)-1,3,5-tris(phenoxy)cyclotriphosphazene, 1,3,5- tris(n-propoxy)-1,3,5-tris(phenoxy)cyclotriphosphazene, 1,3,5-tris(iso-propoxy)-1,3,5-tris(phenoxy)cyclotriphosphazene, 1, 3,5-tris(n-butoxy)-1,3,5-tris(phenoxy)cyclotriphosphazene, 1,3,5-tris(iso-butoxy)-1,3,5-tris(phenoxy)cyclotris Phosphazene, 1,3,5-tris(methoxy)-1,3,5-tris(p-tolyloxy)cyclotriphosphazene, 1,3,5-tris(methoxy)-1,3,5-tris(m- tolyloxy)cyclotriphosphazene, 1,3,5-tris(methoxy)-1,3,5-tris(o-tolyloxy)cyclotriphosphazene, 1,3,5-tris(ethoxy)-1,3,5- tris(p-tolyloxy)cyclotriphosphazene, 1,3,5-tris(ethoxy)-1,3,5-tris(m-tolyloxy)cyclotriphosphazene, 1,3,5-tris(ethoxy)-1, 3,5-tris(o-tolyloxy)cyclotriphosphazene, 1,3,5-tris(n-propoxy)-1,3,5-tris(p-tolyloxy)cyclotriphosphazene, 1,3,5-tris (n-propoxy)-1,3,5-tris(m-tolyloxy)cyclotriphosphazene, 1,3,5-tris(n-propoxy)-1,3,5-tris(o-tolyloxy)cyclotriphosphazene , 1,3,5-tris(iso-propoxy)-1,3,5-tris(p-tolyloxy)cyclotriphosphazene, 1,3,5-tris(n-butoxy)-1,3,5-tris (p-tolyloxy)cyclotriphosphazene, 1,3,5-tris(iso-butoxy)-1,3,5-tris(p-tolyloxy)cyclotriphosphazene, 1,3,5-tris(methoxy)-1 , 3,5-tris(4-t-butylphenoxy)cyclotriphosphazene, 1,3,5-tris(methoxy)-1,3,5-tris(4-t-octylphenoxy)cyclotriphosphazene, 1, 3,5-tris(n-propoxy)-1,3,5-tris(4-t-butylphenoxy)cyclotriphosphazene, 1,3,5-tris(n-propoxy)-1,3,5-tris (4-t-octylphenoxy)cyclotriphosphazene and the like.

Among these, preferably 1,1,3,3,5,5-hexa(methoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(ethoxy)cyclotriphosphazene, 1,1,3 , 3,5,5-hexa(phenoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(p-tolyloxy)cyclotriphosphazene, 1,3,5-tris(methoxy)-1, 3,5-tris(phenoxy)cyclotriphosphazene, 1,3,5-tris(ethoxy)-1,3,5-tris(phenoxy)cyclotriphosphazene, more preferably 1,1,3,3 ,5,5-hexa(ethoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(phenoxy)cyclotriphosphazene, 1,3,5-tris(ethoxy)-1,3,5- Tris(phenoxy)cyclotriphosphazene, more preferably 1,1,3,3,5,5-hexa(phenoxy)cyclotriphosphazene.

式（２）中、Ｒ^１～Ｒ^５は、水素原子、又は置換基を有していてもよい炭化水素基であり、Ｒ^１～Ｒ^５はそれぞれ同一でも異なっていてもよい。
炭化水素基としては、鎖状（直鎖及び分岐鎖のいずれでもよい）及び環状（単環、縮合多環、架橋環及びスピロ環のいずれでもよい）のいずれであってもよく、例えば、側鎖を有する環状炭化水素基が挙げられる。また、炭化水素基は、飽和及び不飽和のいずれでもよい。 -Phosphonic acid ester-
Phosphonate esters include, for example, those represented by the following formula (2).

In formula (2), R ¹ to R ⁵ are hydrogen atoms or optionally substituted hydrocarbon groups, and R ¹ to R ⁵ may be the same or different.
The hydrocarbon group may be either chain (either linear or branched) or cyclic (either monocyclic, condensed polycyclic, bridged or spirocyclic). A cyclic hydrocarbon group having a chain is mentioned. Also, the hydrocarbon group may be either saturated or unsaturated.

Examples of hydrocarbon groups include alkyl groups, cycloalkyl groups, allyl groups, aryl groups, alkylaryl groups, and arylalkyl groups.

Specific examples of the phosphonate represented by formula (2) include compounds represented by formulas (2)-1 to (2)-8 below.

- Bromine Flame Retardant -
In the present embodiment, the brominated flame retardant can be any brominated flame retardant (brominated flame retardant) that is commonly used in this field without limitation. or brominated bisphenol Ss, brominated bisphenol A carbonate oligomers, brominated bisphenol A epoxy resins, brominated styrenes, brominated cycloalkanes, brominated isocyanurates, etc. . These bromine-based flame retardants may be used singly or in combination of two or more. Moreover, from the viewpoint of transparency and dispersibility, one having a melting point of 300° C. or less is preferable.

Brominated bisphenol A compounds or brominated bisphenol S compounds include compounds in which 1 to 8 bromine atoms are bonded to the benzene ring of a bisphenol A residue or bisphenol S residue, examples of which include tetrabrom Bisphenol A, Tetrabromobisphenol A bis(2-hydroxyethyl ether), Tetrabromobisphenol A bis(allyl ether), Tetrabromobisphenol A bis(2-bromoethyl ether), Tetrabromobisphenol A bis(3-bromopropyl ether) ), tetrabromobisphenol A bis(2,3-dibromopropyl ether), tetrabromobisphenol S, tetrabromobisphenol S bis(2-hydroxyethyl ether) and tetrabromobisphenol S bis(2,3-dibromopropyl ether ) etc. can be mentioned.
Commercially available brominated bisphenol A or brominated bisphenol S include "FR-1524" from Brochem Far East Co., Ltd., "Great Lakes BA-50" from Great Lakes Chemical Co., Ltd., " Great Lakes BA-50P", "Great Lakes BA-59", "Great Lakes BA-59P" and "Great Lakes PE-68", Albemarle's "Saytex RB-100", Teijin Kasei Co., Ltd.'s Fireguard 2000", "Fireguard 3000", "Fireguard 3100" and "Fireguard 3600", Marubishi Yuka Kogyo Co., Ltd.'s "Nonen PR-2", Tosoh Corporation's "Frame Cut 121R", "Fire Cut P-680" manufactured by Suzuhiro Kagaku Co., Ltd. can be mentioned.

で示される基の重合物であって、オリゴマーとは、重合度（ｎ）が１～１０のものをいう。 The brominated bisphenol A-based carbonate oligomer has the following formula (3)

The term "oligomer" refers to a polymer having a degree of polymerization (n) of 1-10.

Examples of the polymer of the group represented by the above formula (3) include flame retardants represented by the following formula (4) or (5).

"Fireguard 7000" and "Fireguard 7500" available from Teijin Kasei Co., Ltd. can be cited as commercially available flame retardants of formula (4).
Examples of commercially available flame retardants of formula (5) include Great Lakes BC-52 and Great Lakes BC-58 available from Great Lakes Chemical Co., Ltd.

Examples of the brominated bisphenol A epoxy resin include compounds represented by the following formula (6).

As the commercially available flame retardant of the above formula (6), there are various products depending on the degree of polymerization (n). F-2400" and "F-2400H", Dainippon Ink and Chemicals Co., Ltd.'s "Platherm EP-16", "Platherm EP-30", "Platherm EP-100" and "Platherm EP-500", Sakamoto Yakuhin Examples include "SR-T1000", "SR-T2000", "SR-T5000" and "SR-T20000" manufactured by Kogyo Co., Ltd.

Further, examples of the brominated bisphenol A epoxy resin include a compound of the above formula (6) in which both terminal epoxy groups are blocked with a blocking agent and a compound in which one terminal epoxy group is blocked with a blocking agent. be able to. The blocking agent is not limited as long as it is a compound capable of ring-opening addition of an epoxy group. Among them, brominated phenols are preferred from the viewpoint of improving the flame retardant effect. be able to.

Examples of the flame retardant in which both terminal epoxy groups of the polymer are blocked with a blocking agent include flame retardants represented by the following formulas (7) and (8).

Commercially available flame retardants of formula (7) or (8) include "Platherm EC-14", "Platherm EC-20" and "Platherm EC-30" manufactured by Dainippon Ink and Chemicals Co., Ltd.; Examples include "TB-60" and "TB-62" manufactured by Kasei Co., Ltd., and "SR-T3040" and "SR-T7040" manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.

Examples of the flame retardant in which only one terminal epoxy group of the polymer is blocked with a blocking agent include flame retardants represented by the following formulas (9) and (10).

Commercially available flame retardants of the above formula (9) or (10) include "Platherm EPC-15F" from Dainippon Ink and Chemicals, Ltd., "E5354" from Yuka Shell Epoxy Co., Ltd., and the like. can be done.

Examples of brominated styrene flame retardants include brominated styrene monomers represented by the following formula (11) in which 1 to 5 bromine atoms are bonded to the benzene ring of the styrene skeleton, and polymers thereof represented by the following formula (12). is preferably a polymer.

Specific examples of brominated styrenes include bromstyrene and brominated polystyrene. Commercially available brominated polystyrene flame retardants include "Great Lakes PDBS" available from Great Lakes Chemical Co., Ltd. -10” and “Great Lakes PDBS-80”. "Pyrocheck 68PB" manufactured by Ferro Co., Ltd. can also be mentioned as an example of a brominated polystyrene-based flame retardant, although the production method is different from that of the flame retardant.

Brominated cycloalkane systems include brominated hydrocarbons in which from 1 to 6 bromo atoms are attached to cycloalkanes having from 6 to 12 carbon atoms (cycloaliphatic hydrocarbons). Examples of the cycloalkanes include cyclohexane and cyclododecane, and examples of brominated cycloalkanes include pentabromocyclohexane, hexabromocyclohexane, tetrabromocyclododecane, pentabromocyclododecane and hexabromocyclododecane. can be mentioned.

Examples of commercially available hexabromocyclododecane include "FR-1206" from Bromochem Far East Co., Ltd., "Saytex HBCD" from Albemarle Co., Ltd., and "Great Lakes CD-75P" from Great Lakes Chemical Co., Ltd. , Suzuhiro Chemical Co., Ltd. "Fire Cut P-880M" and Daiichi Kogyo Seiyaku Co., Ltd. "Pyroguard SR-103".

Brominated isocyanurates include compounds in which a bromine atom is bonded to an alkyl group having 2 to 6 carbon atoms (chain aliphatic hydrocarbon group) and an isocyanuric acid residue, and 1 to 5 Compounds in which a brominated phenoxy group in which a bromine atom is attached to a phenoxy group and an isocyanuric acid residue are exemplified. Specific examples include tris(monobromopropyl) isocyanurate, tris(2,3-dibromopropyl) isocyanurate, tris(tribromopropyl) isocyanurate, tris(tetrabromopropyl) isocyanurate, tris(pentabrom propyl)isocyanurate, tris(heptabromopropyl)isocyanurate, tris(octabromobutyl)isocyanurate, tris(monobromphenoxy)isocyanurate, tris(dibromophenoxy)isocyanurate, tris(tribromophenoxy)isocyanurate, tris(pentabromphenoxy)isocyanurate, tris(ethylmonobromphenoxy)isocyanurate and tris(propyldibromphenoxy)isocyanurate.

Commercially available brominated isocyanurates include "Taiku-6B" manufactured by Nippon Kasei Co., Ltd. and "Firecut P-660" manufactured by Suzuhiro Chemical Co., Ltd., and the like.
In addition to the widely used bromine-based flame retardants as described above, it is of course possible to use those listed in literature and catalogs of bromine-based flame retardant manufacturers. Brominated flame retardants include brominated phenols, brominated phenoxytriazines, brominated alkanes, brominated maleimides and brominated phthalates.

Brominated phenols are compounds in which 1 to 5 bromo atoms are bonded to a phenol group, such as monobromophenol, dibromophenol, tribromophenol, tetrabromophenol and pentabromophenol. can be done.

Brominated phenoxytriazines are compounds in which 1 to 5 bromo atoms are attached to the phenoxy group and 1 to 3 of the brominated phenoxy groups are attached to the triazine ring, such as mono(tribromophenoxy ) triazine, bis(monobromphenoxy)triazine, bis(tribromophenoxy)triazine, tris(dibromphenoxy)triazine and tris(tribromophenoxy)triazine, etc. Commercially available flame retardants include: Daiichi Kogyo Seiyaku Co., Ltd. "Pyrogard SR-245" can be mentioned.

A brominated alkane is a compound in which a bromine atom is bonded to an alkane having 2 to 6 carbon atoms (chain aliphatic hydrocarbon). Examples of said alkanes include ethane, propane, butane, pentane and hexane, and examples of brominated alkanes are dibromoethane, tetrabromoethane, monobromopropane, tribromopropane, hexabromopropane, octabrome. Propane, tetrabromobutane, hexabromobutane, octabromobutane, tribromopentane, pentabromopentane, octabromopentane, dibromohexane, tribromohexane, tetrabromohexane, hexabromohexane and octabromohexane and the like may be mentioned. can.

Brominated maleimides are compounds in which 1 to 5 bromo atoms are attached to a phenylmaleimide group, such as monobromophenylmaleimide, dibromophenylmaleimide, tribromophenylmaleimide and pentabromophenylmaleimide. be able to.

Bromated phthalates can include compounds having 1 to 4 bromo atoms attached to phthalic anhydride, examples of which include monobromo phthalic anhydride, dibromo phthalic anhydride, tribromo phthalic anhydride and tetrabromo phthalic anhydride. Phthalic acid and the like can be mentioned.
In order to further improve flame retardancy, flame retardant aids such as antimony trioxide are often used in combination. not something to give.

The amount of the flame retardant aid added is usually 0.5 to 10 parts by mass with respect to 100 parts by mass of the styrene resin (A). 7 parts by mass.

<Optional Addition Ingredients>
In the present embodiment, the styrenic resin composition, in addition to the above components (A) to (C), may optionally contain conventionally known additives, processing aids, etc. within a range that does not impair the effects of the present invention. Optional ingredients can be added. These additives, processing aids and the like include antioxidants, weathering agents, lubricants, antistatic agents, fillers and the like.

Antioxidants include phenol compounds, phosphorus compounds, thioether compounds and the like.

Phenolic antioxidants include, for example, 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)propionamide], 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-tert-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)methyl propionate]methane, thiodiethylene glycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl) ) propionate], 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyl 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. mentioned.
These may be used in combination of two or more.

Examples of phosphorus 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, tridecylphosphite, octyldiphenylphosphite, di(decyl)monophenylphosphite, di(tridecyl)pentaerythritol diphosphite, di(nonylphenyl) ) pentaerythritol diphosphite, bis(2,4-di-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) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis ( 4,6-tert-butylphenyl)-2-ethylhexylphosphite, 2,2′-methylenebis(4,6-tert-butylphenyl)-octadecylphosphite, 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, phosphites of 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol, and the like.
These may be used in combination of two or more.

Examples of thioether antioxidants include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra(β-alkylmercaptopropionates is mentioned.
These may be used in combination of two or more.

As the weather resistant agent, an ultraviolet absorber, a hindered amine light stabilizer, and the like can be used.
UV absorbers include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis(2-hydroxy-4-methoxybenzophenone) 2-hydroxybenzophenones such as; 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)-5-chlorobenzo triazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octyl Phenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-(benzotriazolyl)phenol ), 2-(2′-hydroxyphenyl)benzotriazoles such as 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 - benzoates such as di-tert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanylide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano- Cyanoacrylates such as β,β-diphenyl acrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; 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, 2-(2-hydroxy-4-propoxy -5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine and other triaryltriazines.
These may be used in combination of two or more.

Examples of hindered amine light stabilizers 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, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4- butane tetracarboxylate, 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-butanetetracarboxylate, 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-tetra methyl-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, 1,5,8,12-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, 1,6,11 - Hindered amine compounds such as tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane mentioned.
These may be used in combination of two or more.

Fatty acid amides, fatty acid esters, fatty acids, fatty acid metal salts and the like can be used as lubricants.
Examples of aliphatic amide lubricants include stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, ethylene bis erucic acid amide, and ethylene bis lauric acid amide. be done.
These may be used in combination of two or more.
Aliphatic ester lubricants include methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl erucate, methyl behenate, butyl laurate, butyl stearate, isopropyl myristate, and palmitic acid. Isopropyl, octyl palmitate, coconut fatty acid octyl ester, octyl stearate, tallow fatty acid octyl ester, lauryl laurate, stearyl stearate, behenyl behenate, cetyl myristate, C28-30 linear, unbranched saturated esters of monocarboxylic acid (hereinafter abbreviated as montanic acid) and ethylene glycol, esters of montanic acid and glycerin, 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, poly Oxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate and the like.
These may be used in combination of two or more.

Specific examples of saturated fatty acids among fatty acid-based lubricants include lauric acid (dodecanoic acid), isodecanoic acid, tridecylic acid, myristic acid (tetradecanoic acid), pentadecic acid, palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid), ), stearic acid (octadecanoic acid), isostearic acid, tubercrostearic acid (nonadecanic acid), 2-hydroxystearic acid, arachidic acid (icosanoic acid), behenic acid (docosanoic acid), lignoceric acid (tetradocosanoic acid), cerotic acid (hexadocosanoic acid), montanic acid (octadocosanoic acid), melissic acid and the like, particularly lauric acid, palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid and montanic acid.

Among fatty acid-based lubricants, unsaturated fatty acids specifically include myristoleic acid (tetradecenoic acid), palmitoleic acid (hexadecenoic acid), oleic acid (cis-9-octadecenoic acid), elaidic acid (trans-9-octadecene 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), nervonic acid (tetradocosanoic acid) and the like.
These may be used in combination of two or more.

Fatty acid metal salt-based lubricants include lithium salts, calcium salts, magnesium salts, and aluminum salts of fatty acids of the above fatty acid-based lubricants.
These may be used in combination of two or more.

Cationic, anionic, nonionic, amphoteric, and fatty acid partial esters such as glycerin fatty acid monoester can be used as antistatic agents.
Specifically, alkyltrimethylammonium salts, dialkyldimethylammonium salts, benzalkonium salts, N,N-bis(2-hydroxyethyl)-N-(3-dodecyloxy-2-hydroxypropyl)methylammonium mesosulphate , (3-laurylamidopropyl)trimethylammonium methylsulfate, stearamidopropyldimethyl-2-hydroxyethylammonium nitrate, stearamidopropyldimethyl-2-hydroxyethylammonium phosphate, cationic polymer, alkylsulfonate , Alkyl benzene sulfonate, Sodium alkyl diphenyl ether disulfonate, Alkyl nitrate ester salt, Phosphate alkyl ester salt, Alkyl phosphate amine salt, Stearate monoglyceride, Pentaerythritol fatty acid ester, Sorbitan monopalmitate, Sorbitan monostearate, Diglycerin 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, hydroxyethylimidazoline sulfate, and the like.
These may be used in combination of two or more.

Talc, calcium carbonate, barium sulfate, carbon fiber, mica, wollastonite, whiskers, and the like can be used as fillers.

In addition, anti-blocking agents, coloring agents, anti-blooming agents, surface treatment agents, antibacterial agents, anti-stain agents (silicone oil described in JP-A-2009-120717, monoamide compounds of higher aliphatic carboxylic acids, and higher fatty acid It is also possible to add a build-up inhibitor such as a monoester compound obtained by reacting a group carboxylic acid with a monohydric to trihydric alcohol compound.
The total content of optional components such as additives and processing aids may be 0.05 to 5% by mass in the styrenic resin composition.

The styrenic resin composition of the present embodiment may consist essentially of component (A), component (B), optional component (C), and optional additive components. In addition, it may consist only of (A) component, (B) component, and optional (C) component, or only (A) component, (B) component, optional (C) component, and optional additive component. .
"Consisting essentially of (A) component, (B) component, optional (C) component, and optional additive component" means 95 to 100% by mass (preferably 98 to 100% by mass) of the styrenic resin composition %) is (A) component, (B) component, optional (C) component, or (A) component, (B) component, optional (C) component, and optional additive component do.
The styrenic resin composition of the present embodiment contains unavoidable impurities in addition to the components (A), (B), optional components (C) and optional additives within a range that does not impair the effects of the present invention. You can

<Method for producing styrene resin composition>
The styrenic resin composition of the present embodiment can be produced by melt-kneading each component by an arbitrary method. For example, a method using a high-speed stirrer typified by a Henschel mixer, a batch type kneader typified by a Banbury mixer, a single-screw or twin-screw continuous kneader, a roll mixer, or the like, alone or in combination. The heating temperature during kneading is usually selected in the range of 180 to 260°C.

<Characteristics of styrene resin composition>
<MFR>
In this embodiment, the fluidity of the styrenic resin composition is preferably such that the melt flow rate measured according to ISO1133 is in the range of 0.5 to 6.0 g/10 min.
If the fluidity is less than the above range, the extrusion moldability of the resin composition may deteriorate, which is not preferable. On the other hand, if the fluidity exceeds the above range, the thickness of the sheet may become uneven, and flame retardancy and impact resistance may deteriorate.

[Method for producing flame-retardant extruded sheet]
The flame-retardant extruded sheet of the present embodiment is a sheet made of the styrene-based resin composition described above. A commonly known method can be used as a method for manufacturing the sheet.

The flame-retardant extruded sheet is extruded by a single-screw or twin-screw extruder equipped with a T-die, and then taken off by a uniaxial stretching machine or a biaxial stretching machine to form a uniaxially oriented sheet or a biaxially oriented sheet. can be done.
In addition, the uniaxially oriented sheet may be formed only by normal roll stretching at a low magnification, and the biaxially oriented sheet is stretched with a roll in the machine direction (MD) about 1.3 to 7 times, and then with a tenter. Stretching in the vertical direction (TD) by about 1.3 to 7 times is preferable in terms of strength.
The flame-retardant extruded sheet may be a non-stretched sheet.

[Characteristics of flame-retardant extruded sheet]
<Flame retardance>
The flame retardance of the flame-retardant extruded sheet of the present embodiment is within the standard in the UL94 vertical burning test (UL94-V test), that is, V-0 to V-2, or VTM-0 to VTM- A flame retardant class of 2 is preferred. In addition, in UL94 horizontal combustion (UL94-HB test), it is desirable that the burning rate is 75 mm / min or less, which is within the HB standard, and considering standards such as automobile flame retardant standards (FMVSS302), it is 85 mm / min or less. is preferred.
In the present disclosure, flame retardancy can be evaluated by the method described in the section [Examples] below.

<Heat-resistant>
The heat resistance of the flame-retardant extruded sheet of the present embodiment is preferably 86° C. or higher, more preferably 88° C. or higher at the Vicat softening temperature. If it is less than 86°C, there is a risk that the temperature will rise and the product will be deformed during use.
In the present disclosure, the Vicat softening temperature is a value measured under the conditions of a load of 49 N and a heating rate of 50° C./hour in accordance with ISO 306.

<Impact resistance>
The impact resistance of the flame-retardant extruded sheet of the present embodiment is preferably 1.0 kgf·cm or more, more preferably 1.1 kgf·cm or more in terms of sheet impact strength.
In the present disclosure, it can be evaluated by the method described in the section [Examples] below.

<size>
The thickness of the flame-retardant extruded sheet of this embodiment is 0.5 mm or less. Although the lower limit of the thickness is not particularly limited, it is preferably 50 μm or more from the viewpoint of manufacturing. Further, the thickness is more preferably 0.1 to 0.4 mm.

<Application>
The flame-retardant extruded sheet of the present embodiment may be used by being multilayered with a styrene-based resin such as polystyrene resin. Further, it may be used in a multi-layered manner with a resin other than a styrene-based resin. Examples of resins other than styrene-based resins include PET resins and nylon resins.
The molded article is suitably used for insulating films, housings and various parts of electrical and electronic equipment, interiors of automobiles and aircraft, building materials, and the like.

EXAMPLES The embodiments of the present invention will be described in more detail below based on Examples and Comparative Examples, but the present invention is not limited to these Examples.

<Measurement and evaluation method>
The physical properties of the resin compositions obtained in Examples and Comparative Examples were measured and evaluated according to the following methods.
(1) Melt mass flow rate (MFR)
Melt mass flow rate (grams/10 minutes) was measured at 200° C. and 49 N load according to ISO 1133.

(2) Flame retardancy A sheet test piece (a) (size: 150 mm × 50 mm, thickness: 0.2 mm) prepared by the method described later is wound into a cylinder, and a UL94 vertical burning test (UL94-V test) is performed using a 50 W test flame. ) was evaluated for flame retardancy.
The flame of a gas burner was applied to the test piece (a) to evaluate the degree of combustion.
The flame retardant grade is indicated by the flame retardant class classified by the UL94-V test. Five tests were performed on all test pieces, and judgment was made. The outline of the classification method is as follows.
VTM-0: 5 total burning time of 50 seconds or less, maximum burning time of 10 seconds or less, no dripping cotton ignition VTM-1: 5 total burning time of 250 seconds or less, maximum burning time of 30 seconds or less, dripping cotton ignition VTM-2: 5 total burning time 250 seconds or less, maximum burning time 30 seconds or less, with dripping cotton ignition Not V: Non-compliant with UL94 minutes) were measured.

(3) Vicat softening temperature The Vicat softening temperature (°C) was measured according to ISO 306 for the test piece (b) produced by the method described below. The load was 49N, and the temperature increase rate was 50°C/hour.

(4) Sheet formability The thickness of the sheet obtained by sheet forming described later was measured to measure the uneven thickness. The difference between the maximum thickness and the minimum thickness was measured to evaluate the uneven thickness.

(5) Non-foamed sheet impact strength The impact strength (kgf cm) was measured with a film impact tester (A121807502) manufactured by Toyo Seiki Co., Ltd. for a stretched sheet with a thickness of 0.1 mm produced under predetermined conditions using a resin composition. It was measured.

Each material used in the examples is as follows.
<(A) Component>
・ Styrene-based resin (GPPS-A):
Polystyrene (GPPS) with an MFR of 0.8 g/10 min was used.
・ Styrene-based resin (GPPS-B):
Polystyrene (GPPS) with an MFR of 4.8 g/10 min was used.
・ Styrene-based resin (GPPS-C):
Polystyrene (GPPS) with an MFR of 5.4 g/10 min was used.
・Styrene-based resin (HIPS):
A rubber-modified styrenic resin, which is high impact polystyrene (HIPS) with an MFR of 3.0 g/10 min, was used. The HIPS used polybutadiene as a rubber-like polymer, and the content of the rubber-like polymer (a) was 8.6% by mass.
・Styrene-based resin (PS copolymerization):
Styrene (ST) 71.3 parts by mass, methacrylic acid (MAA) 7.3 parts by mass, methyl methacrylate (MMA) 6.4 parts by mass, ethylbenzene 15.0 parts by mass, 1,1-bis(t-butyl per Oxy) Cyclohexane 0.025 parts by mass of a polymerization raw material composition solution at a rate of 1.1 liters / hour in a complete mixing reactor with a capacity of 4 liters, and then in a laminar flow reactor with a capacity of 2 liters. A resin was prepared by continuously and successively supplying to a polymerization apparatus and then to a devolatilization apparatus connected to a single-screw extruder for removing volatile matter such as unreacted monomers and a polymerization solvent.
The polymerization reaction conditions in the polymerization process 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 -5° C. refrigerant was passed, and recovered as an unreacted liquid.
The polymer content in the final polymerization liquid was measured by the formula [(sample mass after drying / sample mass before drying) x 100%] after drying the polymerization liquid for 30 minutes at 215 ° C. under a reduced pressure of 2.5 kPa. , 65.6% by mass, and the MFR was 0.9 g/10 min. The composition ratio of the resulting PS copolymer was 82.3% by mass of ST monomer units, 9.8% by mass of MAA monomer units, and 7.9% by mass of MMA monomer units.

The content of the rubber-like polymer (a) contained in the styrene-based resin (HIPS) as the rubber-modified styrene-based resin is determined by pyrolysis gas chromatography based on the bonding mode of the butadiene segments. was used to measure the butadiene segment content, and the content of the rubber-like polymer (a) was calculated from the butadiene segment content. The unit is % by mass.

The contents of styrene monomer units, methacrylic acid monomer units, and methyl methacrylate monomer units in the styrene resin (copolymer resin) were measured by the following methods.
The resin composition was quantified from the integral ratio of the spectrum measured with 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.
・Measurement equipment: JNM ECA-500 manufactured by JEOL Ltd.
・Measurement conditions: measurement temperature 25° C., observation core ¹ H, accumulation times 64 times, repetition time 11 seconds.

(Assignment of spectra)
For spectral assignments measured in dimethylsulfoxide deuterated solvent, the peaks at 0.5-1.5 ppm are the hydrogens of the α-methyl groups of methacrylic acid, methyl methacrylate, and the six-membered cyclic anhydride, 1.6 The peak at ~2.1 ppm is the hydrogen of the methylene group of the polymer main chain, the peak of 3.5 ppm is the hydrogen of the carboxylic acid ester ( _-COOCH3 ) of methyl methacrylate, and the peak of 12.4 ppm is the hydrogen of the carboxylic acid of methacrylic acid. is. Also, the peak at 6.5 to 7.5 ppm is the hydrogen of the aromatic ring of styrene. In addition, since the resins of the present examples and comparative examples have a small content of six-membered cyclic acid anhydride, quantification is usually difficult by this measurement method.

<(B) component>
・NOR type hindered amine compound A (NOR type-A) [manufactured by BASF, Flamestab NOR116FF, polymer type]
・NOR type hindered amine compound B (NOR type-B) [manufactured by ADEKA Co., Ltd., LA-81]

<Hindered amine compound>
・ N-methyl type hindered amine compound [LA-52 manufactured by ADEKA Co., Ltd.]
・ NH type hindered amine compound [LA-57 manufactured by ADEKA Co., Ltd.]

<(C) Component>
・ Phosphonate ester compound [Nonen 73 manufactured by Marubishi Yuka Kogyo Co., Ltd., melting point 100 ° C., phosphorus content 10% by mass]
· Phosphate ester A (compound No. 2): resorcinol bis-dixylenyl phosphate [manufactured by Daihachi Chemical Industry Co., Ltd., PX-200, melting point 92 ° C., phosphorus content 9.0% by mass, condensation type]
· Phosphate ester B: tris (tribromoneopentyl) phosphate [CR-900 manufactured by Daihachi Chemical Industry Co., Ltd., melting point 180 ° C., phosphorus content 2.9% by mass, monomer type]
Bromine-based flame retardant: brominated styrene/butadiene block copolymer [EMERALD INNOVATION 3000 bromine content: 60 mass% manufactured by Chemtura]

<Additive>
(Phenolic antioxidant)
· 3-(3,5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate [manufactured by BASF, Irganox1076]
(Phosphorus antioxidant)
- Tris (2,4-di-tert-butylphenyl) phosphite [BASF Co., Ltd., Irgafos168]

[Examples 1 to 17]
0.2 parts by mass of Irganox 1076 and Irgafos 168 were added to 100 parts by mass of each component and components (A) to (B) in the composition ratio shown in Table 1, and then premixed. The resulting preliminary mixture is mixed together, melt-extruded at 180 ° C. to 220 ° C. using a twin-screw extruder (Toshiba Machine Co., Ltd., TEM-26SS), and pellets of the styrene resin composition are kneaded. got At this time, the screw rotation speed was 150 rpm, and the discharge rate was 10 kg/hr.
A non-foamed extruded sheet (flame-retardant extruded sheet) was produced using the obtained resin pellets, and the physical properties and the like were evaluated by the methods described above.
As for the non-foamed extruded sheet, a sheet having a thickness of about 0.2 mm was produced using a 25 mmφ single-screw sheet extruder manufactured by Soken Co., Ltd., with a resin melting zone temperature of 220 to 230°C. A sample was cut out from the sheet, and each physical property was measured and evaluated. Table 1 shows the results.

[Comparative Examples 1 to 6]
In Comparative Examples 1 to 6, non-foamed extruded sheets were obtained in the same manner as in Examples except that the compositions were changed as shown in Table 2. Table 2 shows the results of measurement and evaluation of each physical property.

As shown in Table 1, Examples 1-17 have high flame retardancy (VTM-2 at 0.2 mm thickness, reduced burning rate) for thin sheets, heat resistance, impact strength, sheet extrusion Excellent in nature. Furthermore, by using a polymer-type NOR-type hindered amine compound, the sheet impact and sheet moldability are high.
As shown in Table 2, the GPPS of Comparative Example 1 does not exhibit flame retardancy, and when a large amount of NOR-type hindered amine compound is blended as in Comparative Example 2, impact strength and extrusion moldability are greatly reduced.
Regarding Comparative Examples 3 and 4, as shown in Table 2, flame retardancy cannot be obtained unless the hindered amine compound is of the NOR type.
Regarding Comparative Example 5, as shown in Table 2, when the amount of the phosphorus-based flame retardant exceeds a predetermined amount, the deterioration of various properties increases.
As for Comparative Example 6, as shown in Table 2, high flame retardancy cannot be obtained with only the phosphorus-based flame retardant.

The flame-retardant extruded sheet of the present invention and molded articles containing it can be suitably used for electronic/electric parts, building materials, flame-retardant sheets for automobiles, and the like.

Claims (5)

(A) 97.0 to 99.8% by mass of styrene resin, (B) 0.2 to 3.0% by mass of NOR hindered amine compound, and (C) phosphorus flame retardant One or more flame retardants selected from the group, from a styrene resin composition containing 0.0 to 5.0 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B) obtained,
The thickness is 0.5 mm or less,
A flame-retardant extruded sheet , wherein the MFR (200° C., 49N load) of the styrene-based resin composition is 0.5 to 6.0 g/10 min . The (A) styrenic resin is a rubber-modified styrenic resin or copolymer resin containing the rubber-like polymer (a),
The content of the rubber-like polymer (a) is 3 to 20% by mass with respect to the rubber-modified styrenic resin, and the average particle diameter of the particles of the rubber-like polymer (a) is 0.5 to 4. .0 μm,
When the total content of the styrene-based monomer unit, the unsaturated carboxylic acid-based monomer unit, and the unsaturated carboxylic acid ester-based monomer unit is 100% by mass, the copolymer resin has the styrene-based monomer Containing 69.0 to 96.0% by mass of a body unit, and containing 4.0 to 16.0% by mass of the unsaturated carboxylic acid monomer unit, and the unsaturated carboxylic acid ester unit 2. The flame-retardant extruded sheet according to claim 1, which is a styrene copolymer containing 0 to 15.0% by weight of the polymer unit. The flame-retardant extruded sheet according to claim 1 or 2, wherein the phosphorus-based flame retardant of component (C) is at least one selected from the group consisting of phosphate ester compounds, phosphazene compounds, and phosphonate ester compounds. . The flame-retardant extruded sheet according to any one of claims 1 to 3, wherein the (B) NOR-type hindered amine compound is oligomeric or polymeric. The flame-retardant extruded sheet according to any one of claims 1 to 4, which is obtained by biaxial stretching and has a thickness of 50 µm or more and 0.5 mm or less.