JP2022007567A - Flame-retardant styrene resin composition and molded article - Google Patents

Abstract

To provide a flame-retardant styrene resin composition which exhibits high flame retardance and excels in impact resistance, light resistance and molding appearance and to provide a molded article containing the flame-retardant styrene resin composition.SOLUTION: There are provided a flame-retardant styrene resin composition which comprises 40 to 85 mass% of a rubber modified styrene resin (A), 5.0 to 30 mass% of a copolymer resin (B) containing a styrene monomer unit (b1), an unsaturated carboxylic acid monomer unit and an unsaturated carboxylic ester monomer unit and 10 to 30 mass% of a flame retardant (C) composed of phosphinates and a molded article of the same.SELECTED DRAWING: None

Description

The present invention relates to a flame-retardant styrene resin composition and a molded product containing the flame-retardant styrene resin composition.

Styrene-based resins are used in a wide range of applications because they have excellent impact resistance in addition to moldability and dimensional stability. Among them, the polystyrene-based resin composition imparted with flame retardancy is widely used in home appliances and OA equipment, and at present, there is a demand for thinning of products from reduction or weight reduction.
Conventionally, various flame retardants have been proposed in order to impart flame retardancy to styrene-based resins, and among them, brom-based flame retardants, which are inexpensive and have an excellent balance of physical properties, are often used. However, in recent years, the movement to regulate halogen-containing organic compounds has become active mainly in Europe, and therefore, the demand for flame-retardant resins and flame-retardant resin compositions containing no brom element is increasing.

As an alternative flame retardant to such a brom-based flame retardant, for example, Patent Document 1 discloses a technique for adding a phosphinate to a thermoplastic polymer. Further, Patent Document 2 discloses a technique for adding phosphinate to polyphenylene ether and polystyrene.

Japanese Unexamined Patent Publication No. 11-124466 Japanese Unexamined Patent Publication No. 2008-37970

Although the above-mentioned Patent Document 1 describes that polystyrene can be flame-retardant, these flame retardants have poor dispersibility in polystyrene and have insufficient flame retardancy, resulting in a decrease in impact strength or molding. There were problems such as causing poor appearance of the product. Further, since Patent Document 2 contains polyphenylene ether, it has excellent flame retardancy, but has a problem in light resistance such as discoloration to light. Therefore, there is a problem that it is difficult to use it for housings such as OA or home appliances.
Therefore, an object of the present invention is a molding containing a flame-retardant styrene resin composition which exhibits high flame retardancy and is excellent in impact resistance, light resistance, and molded appearance, and the flame-retardant styrene resin composition. To provide goods.

As a result of diligent studies to solve the above problems, the present inventor has obtained a rubber-modified styrene resin (A), a styrene-based monomer unit (b1), an unsaturated carboxylic acid-based monomer unit, and an unsaturated styrene-based resin. The flame-retardant styrene resin composition containing a copolymerized resin (B) containing a carboxylic acid ester-based monomer unit and phosphinates (C) in a specific ratio is surprisingly very very. We have found that it exhibits high flame retardancy, excellent impact resistance, light resistance, and low dielectric property, and have completed the present invention.

［上記式（１）中、Ｒ¹¹及びＲ¹²は、各々独立して、直鎖状若しくは分岐状の炭素原子数１～６のアルキル基又は炭素原子数６～１０のアリール基であり；Ｍ¹は、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、亜鉛イオン、ビスマスイオン、マンガンイオン、ナトリウムイオン、カリウムイオン及びプロトン化された窒素塩基からなる群より選ばれる少なくとも１種であり；ａはＭ¹のイオン価を表し、１～３の整数であり；ｍ¹は、１～３の整数であり；ａ＝ｍ¹である。］で表されるホスフィン酸塩、及び
下記式（２）：

［式中、Ｒ²¹及びＲ²²は、各々独立して、直鎖状若しくは分岐状の炭素原子数１～６のアルキル基又は炭素原子数６～１０のアリール基であり；Ｌ²³は、直鎖状若しくは分岐状の炭素原子数１～１０のアルキレン基、炭素原子数６～１０のアリーレン基、炭素原子数６～１０のアルキルアリーレン基又は炭素原子数６～１０のアリールアルキレン基であり；Ｍ²は、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、亜鉛イオン、ビスマスイオン、マンガンイオン、ナトリウムイオン、カリウムイオン及びプロトン化された窒素塩基からなる群より選ばれる少なくとも１種であり；ｂはＭ²のイオン価を表し、１～３の整数であり；ｍ²は、１～３の整数であり；ｉは、１又は２の整数であり；ｂ×ｉ＝２ｎである］で表されるジホスフィン酸塩からなる群より選ばれる少なくとも１種のホスフィン酸塩類を含む難燃剤（Ｃ）を１０～３０質量％と、
を含有することを特徴とする難燃性スチレン系樹脂組成物。 That is, the present invention is as follows.
[1] The amount of the rubber-modified styrene resin (A) is 40 to 85% by mass.
The copolymer resin (B) containing the styrene-based monomer unit (b1), the unsaturated carboxylic acid-based monomer unit, and the unsaturated carboxylic acid ester-based monomer unit is 5.0 to 30% by mass.
The following general formula (1):

[In the above formula (1), R ¹¹ and R ¹² are linear or branched alkyl groups having 1 to 6 carbon atoms or aryl groups having 6 to 10 carbon atoms, respectively; M. ¹ is at least one selected from the group consisting of calcium ion, magnesium ion, aluminum ion, zinc ion, bismuth ion, manganese ion, sodium ion, potassium ion and protonated nitrogen base; a is M ¹ . Representing the ionic value, it is an integer of 1 to 3; m ¹ is an integer of 1 to 3; a = m ¹ . ], And the following formula (2):

[In the formula, R ²¹ and R ²² are each independently a linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms; L ²³ is an integer. A chain or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkyl arylene group having 6 to 10 carbon atoms, or an arylalkylene group having 6 to 10 carbon atoms; M ² is at least one selected from the group consisting of calcium ion, magnesium ion, aluminum ion, zinc ion, bismuth ion, manganese ion, sodium ion, potassium ion and protonated nitrogen base; b is M ² Is an integer of 1 to 3; m ² is an integer of 1 to 3; i is an integer of 1 or 2; b × i = 2n]. A flame retardant (C) containing at least one phosphinic acid salt selected from the group consisting of acid salts was added to 10 to 30% by mass.
A flame-retardant styrene-based resin composition comprising.

[2] 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 copolymerized resin (B) was set to 100% by mass. When, the styrene-based monomer unit (b1) is contained in an amount of 67.0 to 96.0% by mass, and the unsaturated carboxylic acid-based monomer unit is contained in an amount of 4.0 to 18.0% by mass. The flame-retardant styrene-based resin composition according to [1], which contains 0.0 to 15.0% by mass of the unsaturated carboxylic acid ester-based monomer unit.

[3] The flame-retardant styrene-based resin according to claim 1 or 2, wherein the flame retardant (C) is granular and the average particle size of the flame retardant (C) is more than 0.5 μm and 10 μm or less. Composition.

[4] A molded product comprising the flame-retardant styrene resin composition according to any one of the above [1] to "3".

According to the present invention, a flame-retardant styrene resin composition exhibiting high flame retardancy and excellent impact resistance, light resistance, and molded appearance, and a molded product containing the flame-retardant styrene resin composition are provided. Can be provided.

Hereinafter, embodiments of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail, but the present invention is not limited to the following description and is variously modified within the scope of the gist thereof. Can be carried out.

[Flame-retardant styrene resin composition]
The flame-retardant styrene-based resin composition of the present embodiment contains 40 to 85% by mass of the rubber-modified styrene-based resin (A), a styrene-based monomer unit (b1), and an unsaturated carboxylic acid-based monomer unit. And 5.0 to 30% by mass of the copolymer resin (B) containing an unsaturated carboxylic acid ester-based monomer unit, and a flame retardant (C) containing phosphinates having a specific chemical structure. do.

<Rubber-modified styrene resin (A): component (A)>
The flame-retardant styrene resin composition of the present embodiment uses a rubber-modified styrene resin (A) in order to increase the impact strength. The content of the rubber-modified styrene resin (A) is 40 to 85% by mass, preferably 50 to 80% by mass, and more preferably 55 to 75% by mass with respect to 100% by mass of the flame-retardant styrene resin composition. It is mass%. If it exceeds 85% by mass, the flame retardancy decreases.

The rubber-modified styrene resin (A) of the present embodiment is one in which particles of the rubber-like polymer (a1) are dispersed in a matrix of the styrene-based resin, and in the presence of the rubber-like polymer (a1). It can be produced by polymerizing a styrene-based monomer.

Examples of the styrene-based monomer (a2) contained in the styrene-based resin, which is the matrix constituting the rubber-modified styrene-based resin (A) of the present embodiment, include α-methylstyrene and α-methyl, in addition to styrene. Examples thereof include p-methylstyrene, ο-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, ethylstyrene, isobutylstyrene, and t-butylstyrene or bromostyrene, chlorostyrene, and inden. In particular, styrene is preferable. These styrene-based monomers can be used alone or in combination of two or more.

The rubber-like polymer (a1) contained in the rubber-modified styrene-based resin (A) of the present embodiment contains a styrene-based resin inside (including a salami structure and a core-shell structure) and is styrene-based on the outside. It may be grafted with resin.

As the rubber-like polymer (a1), for example, polybutadiene, polyisoprene, natural rubber, polychloroprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer and the like can be used, but polybutadiene or styrene-butadiene copolymer weight can be used. Coalescence 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. Further, as the structure of the styrene-butadiene copolymer, both a random structure and a block structure can be used. These rubber-like polymers (a1) can be used alone or in combination of two or more. Further, saturated rubber obtained by hydrogenating butadiene rubber can also be used.

Examples of such a rubber-modified styrene resin (A) include HIPS (high impact polystyrene), ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), and the like. Examples thereof include AES resin (acrylonitrile-ethylene propylene rubber-styrene copolymer).

When the rubber-modified styrene-based resin (A) is a HIPS-based resin, particularly preferable among these rubber-like polymers (a1) is high-cis polybutadiene in which cis 1,4 bonds are 90 mol% or more. Is. In the high cis polybutadiene, the vinyl 1 and 2 bonds are preferably composed of 6 mol% or less, and 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 constituent unit of the high cis polybutadiene was measured using an infrared spectrophotometer and measured by the morero method. It can be calculated by processing the data.
Further, 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 (a1) contained in the rubber-modified styrene resin (A) is preferably 3 to 20% by mass, more preferably 5 to 20% by mass. If the content of the rubber-like polymer (a1) is less than 3% by mass, the impact resistance of the styrene resin is lowered. Further, when the content of the rubber-like polymer (a1) exceeds 20% by mass, the flame retardancy decreases.
In the present disclosure, the content of the rubber-like polymer (a1) contained in the rubber-modified styrene resin (A) is a value calculated by using a pyrolysis gas chromatograph.

The average particle size of the rubber-like polymer (a1) contained in the rubber-modified styrene resin (A) is preferably 0.5 to 4.0 μm from the viewpoint of impact resistance and flame retardancy. It is preferably 0.8 to 3.5 μm.
In the present disclosure, the average particle size of the rubber-like polymer (a1) contained in the rubber-modified styrene resin (A) is a value measured by the procedure described in the section of [Example] described later.

The reduced viscosity of the rubber-modified styrene-based resin (A) (which is an index of the molecular weight of the rubber-modified styrene-based resin (A)) is preferably in the range of 0.50 to 0.85 dL / g, and further. It is preferably in the range of 0.55 to 0.80 dL / g. If it is less than 0.50 dL / g, the impact strength is lowered, and if it exceeds 0.85 dL / g, the fluidity is lowered and the moldability is lowered.
In the present disclosure, the reduced viscosity of the rubber-modified styrene resin (A) is a value measured in a toluene solution under the conditions of 30 ° C. and a concentration of 0.5 g / dL. Example] This is the value measured by the procedure described in the section.

The method for producing the rubber-modified styrene resin (A) is not particularly limited, but is a massive polymerization (or solution) in which the styrene-based monomer (and solvent) is polymerized in the presence of the rubber-like polymer (a1). It can be produced by polymerization), massive-suspension polymerization that shifts to suspension polymerization in the middle of the reaction, or emulsified graft polymerization that polymerizes a styrene-based monomer in the presence of a rubber-like polymer (a1) latex. .. In bulk polymerization, a mixed solution containing a rubbery polymer (a1), a styrene-based monomer (a2), and if necessary, an organic solvent, an organic peroxide, and / or a chain transfer agent is completely mixed. It can be manufactured by continuously supplying a type-reactor or a tank-type reactor and a plurality of tank-type reactors to a polymerization apparatus configured by connecting them in series.

<Copolymer resin (B): (B) component>
In the present embodiment, the content of the copolymer resin (B) containing the styrene-based monomer unit (b1), the unsaturated carboxylic acid-based monomer unit, and the unsaturated carboxylic acid ester-based monomer unit is the content. It is 5 to 30% by mass, preferably 8 to 25% by mass, and more preferably 10 to 20% by mass with respect to 100% by mass of the flame-retardant styrene resin composition. If the content is less than 5% by mass, the dispersibility of the flame retardant (c) is insufficient, and the impact strength and the molded appearance are deteriorated. On the other hand, if the content is more than 30% by mass, the impact strength is lowered.

In the above copolymer resin (B), the total content of the styrene-based monomer unit (b1), the unsaturated carboxylic acid-based monomer unit, and the unsaturated carboxylic acid ester-based monomer unit was set to 100% by mass. The content of the styrene-based monomer unit (b1) is preferably 67.0 to 96.0% by mass, more preferably 74.0 to 92.0% by mass, and even more preferably 77. It is in the range of 0 to 87.0% by mass. By setting the content to 67.0% by mass or more, the fluidity of the resin can be improved, while by setting the content to 96.0% by mass or less, the unsaturated carboxylic acid system described later will be used. A desired amount of a monomer unit and an unsaturated carboxylic acid ester-based monomer unit are present, and the effects described below are exhibited by these monomer units.

In the flame-retardant styrene resin composition of the present embodiment, the unsaturated carboxylic acid-based monomer unit plays a role of improving heat resistance. In the above copolymer resin (B), the total content of the styrene-based monomer unit (b1), the unsaturated carboxylic acid-based monomer unit, and the unsaturated carboxylic acid ester-based monomer unit was set to 100% by mass. The content of the unsaturated carboxylic acid-based monomer unit is preferably 4.0 to 18.0% by mass, more preferably 6.0 to 16.0% by mass, and even more preferably 8. It is 0 to 13.0% by mass. By setting the content to 4.0% by mass or more, the heat resistance can be further improved, while by setting the content to 18.0% by mass or less, high flame retardancy can be exhibited and at the same time, high flame retardancy can be exhibited. In addition, the fluidity and mechanical properties of the resin can be improved.

Generally, a styrene-methacrylic acid-based resin containing a styrene-methacrylic acid-methyl methacrylate copolymer resin is produced by radical polymerization in most cases on an industrial scale, but suppresses the gelation reaction in the devolatile step. Therefore, various alcohols may be added to the polymerization system to carry out the polymerization.

In the present embodiment, the unsaturated carboxylic acid ester-based monomer is used to suppress the dehydration reaction of the unsaturated carboxylic acid-based monomer by intermolecular interaction with the unsaturated carboxylic acid-based monomer, and. It can be used to improve the mechanical strength of the resin. Furthermore, the unsaturated carboxylic acid ester-based monomer also contributes to the improvement of resin properties such as weather resistance and surface hardness.
In the copolymerized resin (B), the total content of the styrene-based monomer unit (b1), the unsaturated carboxylic acid-based monomer unit, and the unsaturated carboxylic acid ester-based monomer unit was set to 100% by mass. The content of the unsaturated carboxylic acid ester-based monomer unit is preferably 0 to 15% by mass, more preferably 1 to 12% by mass, and further 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. Further, by setting the content of the unsaturated carboxylic acid ester-based monomer unit to 0% by mass, the heat resistance can be improved and the cost can be reduced. However, from the above viewpoint, the unsaturated carboxylic acid ester-based single amount The content of the body unit can be more than 0% by mass.

When an unsaturated carboxylic acid-based monomer unit and an unsaturated carboxylic acid ester-based monomer unit are bonded side by side, a de-alcohol reaction may occur depending on the conditions when a high-temperature, high-vacuum devolatilizer is used. , Six-membered cyclic acid anhydride may be formed. The copolymer resin (B) of the present embodiment may contain this 6-membered cyclic acid anhydride, but it is preferable that the copolymer resin (B) is less than the copolymer resin (B) because it lowers the fluidity.

In the present embodiment, the styrene-based monomer unit (b1), the unsaturated carboxylic acid-based monomer unit (for example, the methacrylic acid monomer unit) and the unsaturated carboxylic acid ester-based unit in the copolymerized resin (B). The content of each monomer unit (for example, methyl methacrylate monomer unit) can be determined from the integral ratio of the spectra measured by a proton nuclear magnetic resonance ( ¹ H-NMR) measuring machine. Further, the content of each monomer unit in the copolymerized resin (B) described later can also be determined by proton nuclear magnetic resonance measurement in the same manner.

In the present embodiment, the copolymerized resin (B) is a monomer unit other than the styrene-based monomer unit (b1), the unsaturated carboxylic acid-based monomer unit, and the unsaturated carboxylic acid ester-based monomer unit. Is not excluded to the extent that the effect of the present invention is not impaired, but typically, a styrene-based monomer unit (b1), an unsaturated carboxylic acid-based monomer unit, and an unsaturated carboxylic acid. It consists of an ester-based monomer unit.

Here, the styrene-based monomer (b1) is not particularly limited, but for example, styrene, α-methylstyrene, α-methyl-p-methylstyrene, ο-methylstyrene, m-methylstyrene, p-methyl. Examples thereof include styrene derivatives such as styrene, vinyl toluene, ethyl styrene, isobutyl styrene, t-butyl styrene, bromo styrene, chloro styrene and inden. As the styrene-based monomer (b1), styrene is preferable from an industrial point of view. These styrene-based monomers (b1) can be used alone or in combination of two or more.

The unsaturated carboxylic acid-based monomer is not particularly limited, and examples thereof include 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 has excellent handleability. These unsaturated carboxylic acid-based monomers can be used alone or in combination of two or more.

Further, the unsaturated carboxylic acid ester-based monomer is not particularly limited, and for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (. Meta) Cyclohexyl acrylate and the like can be mentioned. As the (meth) acrylate-based monomer, methyl (meth) acrylate is preferable because it has a small effect on the decrease in heat resistance. These unsaturated carboxylic acid ester-based monomers can be used alone or in combination of two or more.

In the present embodiment, the weight average molecular weight (Mw) of the copolymerized resin (B) is preferably 100,000 to 350,000, more preferably 120,000 to 300,000, still more preferably 140,000 to. It is 240,000. When the weight average molecular weight (Mw) is 100,000 to 350,000, a resin having an excellent balance between mechanical strength and fluidity can be obtained, and gels are less mixed. The weight average molecular weight (Mw) is a value obtained in terms of standard polyslen using gel permeation chromatography.

In the present embodiment, the melt flow rate of the copolymerized resin (B) is preferably 0.3 to 3.0 g / 10 min, more preferably 0.4 to 2.5 g / 10 min, and even more preferably 0.4 to 2.5 g / 10 min. It is 0.4 to 2.0 g / 10 min. When the melt flow rate is 0.3 g / 10 min or more, it is preferable from the viewpoint of fluidity, and when it is 3.0 g / 10 min or less, it is preferable from the viewpoint of mechanical strength of the resin. The melt flow rate is a value measured at 200 ° C. and a load of 49 N in accordance with ISO 1133.

In the present embodiment, the polymerization method of the copolymer resin (B) is not particularly limited, but for example, a bulk polymerization method or a solution polymerization method can be preferably adopted as the radical polymerization method. The polymerization method mainly includes a polymerization step of polymerizing a polymerization raw material (monomer component) and a devolatile step of removing volatile components such as unreacted monomers and polymerization solvent from the polymerization product.
Hereinafter, the polymerization method of the copolymer resin (B) that can be used in this embodiment will be described.

When the polymerization raw material is polymerized for the purpose of obtaining the copolymerized resin (B), a polymerization initiator and a chain transfer agent are typically contained in the polymerization raw material composition. Examples of the polymerization initiator include organic peroxides such as 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-butylperoxy) cyclohexane, and n-butyl-4,4-bis (. t-butylperoxy) Peroxyketals such as valerate, di-t-butyl peroxides, dialkyl peroxides such as t-butylcumyl peroxides and dicumyl peroxides, diacyl peroxides such as acetyl peroxides and isobutyryl peroxides, and diisopropyl peroxy. Examples thereof include peroxydicarbonates such as dicarbonates, peroxyesters such as t-butylperoxyacetate, ketone peroxides such as acetylacetone peroxide, and hydroperoxides such as t-butylhydroperoxide. From the viewpoint of decomposition rate and polymerization rate, 1,1-bis (t-butylperoxy) cyclohexane is particularly preferable.

Examples of the chain transfer agent include α-methylstyrene linear dimer, n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan and the like.

As the polymerization method of the copolymerized resin (B), solution polymerization using a polymerization solvent can be adopted, if necessary. Examples of the polymerization solvent used include aromatic hydrocarbons such as ethylbenzene and dialkyl ketones such as methyl ethyl ketone, which may be used alone or in combination of two or more. Other polymerization solvents, such as aliphatic hydrocarbons, can be further mixed with aromatic hydrocarbons as long as the solubility of the polymerization product is not reduced. It is preferable to use these polymerization solvents in a range not exceeding 25 parts by mass with respect to 100 parts by mass of all the monomers. When the amount of the polymerization solvent exceeds 25 parts by mass with respect to 100 parts by mass of all the monomers, the polymerization rate tends to be remarkably lowered and the mechanical strength of the obtained resin tends to be greatly lowered. It is preferable to add 5 to 20 parts by mass with respect to 100 parts by mass of all the monomers before the polymerization because the quality can be easily made uniform and the polymerization temperature can be controlled.

In the present embodiment, the apparatus used in the polymerization step for obtaining the copolymerized resin (B) is not particularly limited and may be appropriately selected according to the polymerization method of the styrene resin. For example, in the case of bulk polymerization, a polymerization apparatus in which one or a plurality of completely mixed reactors are linked can be used. The devolatilization step is also not particularly limited, and in the case of bulk polymerization, the polymerization is finally proceeded until the unreacted monomer is preferably 50% by mass or less, more preferably 40% by mass or less, and the unreacted monomer is obtained. In order to remove the volatile components such as, the volatilization treatment is carried out by a known method. For example, a normal volatilization device such as a flash drum, a twin-screw volatilizer, a thin film evaporator, or an extruder can be used, but a volatilization device having a small retention portion is preferable. The temperature of the devolatilization treatment is usually about 190 to 280 ° C., more preferably 190 to 260 ° C. from the viewpoint of suppressing the formation of a six-membered cyclic 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, and more preferably 0.13 to 2.0 kPa. As the devolatile method, for example, a method of removing volatile matter by reducing the pressure under heating and a method of removing volatile matter through an extruder designed for the purpose of removing volatile matter are desirable.

<Flame retardant (C): (C) component>
The flame-retardant styrene resin composition of the present embodiment contains 10 to 30% by mass of the flame retardant (C) and 11 to 29% by mass with respect to 100% by mass of the flame-retardant styrene resin composition. It is preferably contained in an amount of 12 to 28% by mass, more preferably 15 to 25% by mass.
In the present embodiment, the flame retardant (C) contains at least one phosphinate salt selected from silver consisting of phosphinate and diphosphinate, preferably in the whole flame retardant (C) (100% by mass). On the other hand, phosphinates account for 70% by mass or more. Therefore, the flame retardant (C) in the present embodiment may contain 30% by mass or less of a known flame retardant other than the above phosphinates with respect to the entire flame retardant (C) (100% by mass).

［上記式（１）中、Ｒ¹¹及びＲ¹²は、各々独立して、直鎖状若しくは分岐状の炭素原子数１～６のアルキル基又は炭素原子数６～１０のアリール基であり；Ｍ¹は、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、亜鉛イオン、ビスマスイオン、マンガンイオン、ナトリウムイオン、カリウムイオン及びプロトン化された窒素塩基からなる群より選ばれる少なくとも１種であり；ａはＭ¹のイオン価を表し、１～３の整数であり；ｍ¹は、１～３の整数であり；ａ＝ｍ¹である。Ｒ¹¹及びＲ¹²がそれぞれ複数存在する場合は、それぞれのＲ¹¹及びＲ¹²が同一であってもあるいは異なっていてもよい。］ In the present embodiment, the phosphinate is as represented by the following general formula (1).

[In the above formula (1), R ¹¹ and R ¹² are linear or branched alkyl groups having 1 to 6 carbon atoms or aryl groups having 6 to 10 carbon atoms, respectively; M. ¹ is at least one selected from the group consisting of calcium ion, magnesium ion, aluminum ion, zinc ion, bismuth ion, manganese ion, sodium ion, potassium ion and protonated nitrogen base; a is M ¹ . Representing the ionic value, it is an integer of 1 to 3; m ¹ is an integer of 1 to 3; a = m ¹ . When a plurality of R ¹¹ and R ¹² are present, the respective R ¹¹ and R ¹² may be the same or different. ]

［上記式（２）中、Ｒ²¹及びＲ²²は、各々独立して、直鎖状若しくは分岐状の炭素原子数１～６のアルキル基又は炭素原子数６～１０のアリール基であり；Ｌ²³は、直鎖状若しくは分岐状の炭素原子数１～１０のアルキレン基、炭素原子数６～１０のアリーレン基、炭素原子数６～１０のアルキルアリーレン基又は炭素原子数６～１０のアリールアルキレン基であり；Ｍ²は、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、亜鉛イオン、ビスマスイオン、マンガンイオン、ナトリウムイオン、カリウムイオン及びプロトン化された窒素塩基からなる群より選ばれる少なくとも１種であり；ｂはＭ²のイオン価を表し、１～３の整数であり；ｍ²は、１～３の整数であり；ｉは、１又は２の整数であり；ｂ×ｉ＝２ｍ²である。Ｒ²¹及びＲ¹²がそれぞれ複数存在する場合は、それぞれのＲ²¹及びＲ²²が同一であってもあるいは異なっていてもよい。］からなる群より選ばれる少なくとも１種が挙げられる。 In the present embodiment, the diphosphane salt is as represented by the following general formula (2).

[In the above formula (2), R ²¹ and R ²² are linear or branched alkyl groups having 1 to 6 carbon atoms or aryl groups having 6 to 10 carbon atoms, respectively; L. Reference numeral ²³ is a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkyl arylene group having 6 to 10 carbon atoms, or an arylalkylene having 6 to 10 carbon atoms. It is a group; M ² is at least one selected from the group consisting of calcium ion, magnesium ion, aluminum ion, zinc ion, bismuth ion, manganese ion, sodium ion, potassium ion and protonated nitrogen base; b represents the ionic value of M ² and is an integer of 1 to 3; m ² is an integer of 1 to 3; i is an integer of 1 or 2; b × i = 2 m ² . When a plurality of R ²¹ and R ¹² are present, the respective R ²¹ and R ²² may be the same or different. ] At least one selected from the group consisting of.

Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include a linear alkyl group having a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, or a hexyl group, and an isopropyl group. , Isobutyl group, s-butyl group, t-butyl group, isoamyl group, t-amyl group and other branched alkyl groups.
The aryl group having 6 to 10 carbon atoms may have a monocyclic structure or a condensed ring structure. For example, a phenyl group or a naphthyl group can be mentioned.
Examples of the linear or branched alkylene group having 1 to 10 carbon atoms include a group obtained by removing one hydrogen atom from the linear or branched alkyl group having 1 to 6 carbon atoms.
Examples of the arylene group having 6 to 10 carbon atoms include a group obtained by removing one hydrogen atom from the aryl group having 6 to 10 carbon atoms.
Examples of the alkylarylene group having 6 to 10 carbon atoms include a methylphenylene group, an ethylphenylene group, a tert-butylphenylene group, a methylnaphthylene group, an ethylnaphthylene group and a tert-butylnaphthylene group.
Examples of the arylalkylene group having 6 to 10 carbon atoms include a phenylmethylene group, a phenylethylene group, a phenylpropylene group and a phenylbutylene group.
In the above formula (1), R ¹¹ and R ¹² are preferably linear alkyl groups having 1 to 6 carbon atoms or aryl groups having 6 to 10 carbon atoms, respectively.
In the above formula (1), M ¹ is preferably calcium, magnesium, aluminum, or zinc. Further, a represents the ionic value of M ¹ and is 2 or 3.
In the above formula (2), R ²¹ and R ²² are preferably linear alkyl groups having 1 to 6 carbon atoms or aryl groups having 6 to 10 carbon atoms, respectively.
In the above formula (2), each of L ²³ is preferably a linear alkylene group having 1 to 6 carbon atoms or an arylene group having 6 to 10 carbon atoms.
In the above formula (2), M ² is preferably calcium, magnesium, aluminum, or zinc. Further, b represents the ionic value of M ² and is 2 or 3.
Since phosphinate has excellent electrical properties, it is suitable for flame-retardant materials that require insulation, and because it has excellent hydrolyzability, it can be used in high temperature and high humidity, and is also excellent in recyclability.

The phosphinates used in the present embodiment are produced in an aqueous solution using phosphinic acid and a metal carbonate, a metal hydroxide or a metal oxide, and are essentially monomeric compounds, but they are subject to reaction conditions. Depending on the environment, polymer phosphinates having a degree of condensation of 1 to 3 are also included.

Such phosphinates are not particularly limited, and for example, calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, and the like. Aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, Aluminum methyl-n-propylphosphinate, zinc methyl-n-propylphosphinate, calcium methanedi (methylphosphinic acid), magnesium methanedi (methylphosphinic acid), aluminum methanedi (methylphosphinic acid), zinc methanedi (methylphosphinic acid), Benzene-1,4- (dimethylphosphinic acid) calcium, benzene-1,4- (dimethylphosphinic acid) magnesium, benzene-1,4- (dimethylphosphinic acid) aluminum, benzene-1,4- (dimethylphosphinic acid) Zinc, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, zinc diphenylphosphite, dimethyl Calcium phosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, aluminum ethylbutylphosphinate, aluminum dibutylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, diethylphosphine Aluminum acetate, zinc diethylphosphinate is preferable, and aluminum diethylphosphinate is more preferable.
Commercially available products of phosphinates are not particularly limited, and examples thereof include Exolit (registered trademark) OP1230, OP1240, OP1311, OP1312, OP930, OP935 manufactured by Clariant Japan.

In this embodiment, the phosphinates are preferably granular. When the phosphinates are granular, the average particle size of the phosphinates improves the mechanical strength of the molded product obtained by molding the flame-retardant resin composition of the present embodiment and the appearance of the molded product. Therefore, it is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 20 μm or less, and it is preferable to use powder pulverized to this particle size for the phosphinates. It is preferably more than 0.5 and 10 μm, and more preferably more than 1 μm and 10 μm or less. It is particularly preferable to use a powder having a preferable particle size because not only high flame retardancy is exhibited but also the impact strength is remarkably increased.
The method for measuring the average particle size of granular phosphinates is based on the volume-based particle size measured using a laser diffraction / scattering type particle size distribution measuring device. Further, it is a value measured by using a 3% isopropanol aqueous solution as a dispersion medium for phosphinates. Specifically, a blank measurement is performed with a dispersion medium of a 3% isopropanol aqueous solution using a laser diffraction / scattering particle size distribution measuring device LA-910 (manufactured by HORIBA, Ltd.), and then the measurement sample is transmitted through the specified value. It can be obtained by putting it in a rate (95% to 70%) and measuring it. The sample is dispersed in the dispersion medium by irradiating it with ultrasonic waves for 1 minute.

<Arbitrary additive component>
In addition to the above-mentioned components (A) to (C), the flame-retardant styrene resin composition of the present embodiment contains conventionally known additives and processing aids, if necessary, as long as the effects of the present invention are not impaired. Any additive component such as can be added. Examples of these additives, processing aids and the like include antioxidants, weathering agents, lubricants, antistatic agents, fillers and flame retardant aids (fluorine-based resins such as polytetrafluoroethylene or polytetrafluoroethylene). % Content of PS-coated PTFE) and the like.

Examples of the antioxidant in the present embodiment include phenol-based compounds, phosphorus-based compounds, thioether-based compounds and the like.
Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, and 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'-ethylidenevis (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) isocia Nurate, 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 glycolbis [(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) 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] and the like can be mentioned. These may be used by mixing two or more kinds.

Examples of the phosphorus-based antioxidant include tris (2,4-di-tert-butylphenyl) phosphite, trisnonylphenylphosphite, and 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) isopropridendiphenol 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) butanetriphosphite, 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-tetrakiss-tert-butyldibenzo [d, f] [1,3,2] dioxa) Phosfepin-6-yl) oxy] ethyl) amine, 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol phosphite and the like can be mentioned. These may be used by mixing two or more kinds.

Examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra (β-alkyl mercaptopropionic acid ester). These may be used in admixture of two or more.

As the weather resistant agent, an ultraviolet absorber, a hindered amine light stabilizer, or the like can be used.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 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. Chlorobenzotriazol, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazol, 2- (2'-hydroxy-5'- -Tert-Octylphenyl) benzotriazol, 2- (2'-hydroxy-3', 5'-dicumylphenyl) benzotriazol, 2,2'-methylenebis (4--tert-octyl-6- (benzo) 2- (2'-Hydroxyphenyl) benzotriazoles such as triazolyl) phenol), 2- (2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl) benzotriazole; phenylsalicylate, resorcinol Monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl-3,5-di-tert-butyl- Phenylates such as 4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide, etc. Substitution of oxanilides; cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate, 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- Examples thereof include triaryltriazines such as triazine and 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2,4-di-tert-butylphenyl) -s-triazine. These may be used by mixing two or more kinds.

Examples of the hindered amine-based 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-piperidylbenzoate, 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) Sevacate, Tetrakiss (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-Butanetetracarboxylate, 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-triazine-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-triazine-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-triazine-6-yl] aminoundecane, 1,6 11-Tris [2,4-bis (N-butyl-N- (N-butyl-N- ( 1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6-yl] Amino undecane and other hindered amine compounds can be mentioned. These may be used by mixing two or more kinds.

As the lubricant, an aliphatic amide type, an aliphatic ester type, a fatty acid type, a fatty acid metal salt type and the like can be used.

Examples of the aliphatic amide-based lubricant include stearate amide, oleic acid amide, erucic acid amide, behenic acid amide, ethylene bisstearic acid amide, ethylene bisoleic acid amide, ethylene biserukaic acid amide, and ethylene bislauryl acid amide. Can be mentioned.
These may be used by mixing two or more kinds.

Examples of the aliphatic ester-based lubricant include methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl erkaate, methyl behenate, butyl laurate, butyl stearate, and isopropyl myristate. Isopropyl palmitate, octyl palmitate, octyl coconut ester, octyl stearate, octyl ester beef fatty acid, lauryl lauryl, stearyl stearate, behenyl behenate, cetyl myristate, linear branching with 28-30 carbon atoms Not saturated monocarboxylic acid (hereinafter abbreviated as montanic acid) and ethylene glycol ester, montanic acid and glycerin ester, montanic acid and butylene glycol ester, montanic acid and trimethylolethane ester, montanic acid and trimethylolpropane Ester, ester of montanic acid and pentaerythritol, glycerin monostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquilate, sorbitan triorate, polyoxyethylene sorbitan monolaurate , Polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triolate and the like. These may be used by mixing two or more kinds.

Among the fatty acid-based lubricants, the saturated fatty acids include, specifically, lauric acid (dodecanoic acid), isodecanoic acid, tridecic acid, myristic acid (tetradecanoic acid), pentadecic acid, palmitic acid (hexadecanoic acid), and margaric acid (hexadecanoic acid). Heptadecanoic acid), stearic acid (octadecanoic acid), isostearic acid, tubercrostearic acid (nonadecanic acid), 2-hydroxystearic acid, arachidic acid (icosaic acid), behenic acid (docosic acid), lignoseric acid (tetradocosic acid), Examples thereof include serotic acid (hexadocosanoic acid), montanic acid (octadocosanoic acid), melicic acid and the like, and in particular, lauric acid, palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid and montanic acid and the like.
Among the above-mentioned fatty acid-based lubricants, the unsaturated fatty acids include, specifically, myristoleic acid (tetradecenoic acid), palmiterenic acid (hexadecenoic acid), oleic acid (cis-9-octadecenoic acid), and elaidic acid (trans-9). -Octadecenoic acid), ricinoleic acid (octadecadienoic acid), baxenoic acid (cis-111-octadecenoic acid), linoleic acid (octadecadienoic acid), linolenic acid (9,11,13-octadecatrienoic acid), ele Examples thereof include stearic acid (9,11,13-octadecatorienic acid), gadrain acid (icosanoic acid), erucic acid (docosic acid), nervonic acid (tetradocosic acid) and the like. These may be used by mixing two or more kinds.

Examples of the fatty acid metal salt-based lubricant include lithium salts, calcium salts, magnesium salts, aluminum salts and the like of the fatty acids of the fatty acid-based lubricants. These may be used by mixing two or more kinds.

As the antistatic agent, fatty acid partial esters such as cationic type, anion type, nonionic type, amphoteric type, and glycerin fatty acid monoester can be used.
Specifically, alkyltrimethylammonium salt, dialkyldimethylammonium salt, benzalconium salt, N, N-bis (2-hydroxyethyl) -N- (3-dodecyloxy-2-hydroxypropyl) methylammonium mesosulfate. , (3-laurylamide propyl) trimethylammonium methyl sulfate, stearoamide propyldimethyl-2-hydroxyethylammonium nitrate, stearoamide propyldimethyl-2-hydroxyethylammonium phosphate, cationic polymer, alkylsulfonate , Alkylbenzene sulfonate, alkyl diphenyl ether disulfonate sodium, alkyl nitrate ester salt, phosphoric acid alkyl ester salt, alkyl phosphate amine salt, stearic acid monoglyceride, pentaerythritol fatty acid ester, sorbitan monopalmitate, sorbitan monostearate, diglycerin fatty acid. Esters, alkyl diethanolamines, alkyl diethanolamine fatty acid monoesters, alkyl diethanolamides, polyoxyethylene dodecyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol monolaurates, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyether block copolymers , Cetylbetaine, hydroxyethyl imidazoline sulfate ester and the like. These may be used by mixing two or more kinds.

As the filler, talc, calcium carbonate, barium sulfate, carbon fiber, mica, wallastnite, whiskers and the like can be used.

In addition to the above-mentioned additives and processing aids, the flame-retardant styrene-based resin composition in the present embodiment includes anti-blocking agents, colorants, anti-blooming agents, surface treatment agents, antibacterial agents, and anti-eye tars (specifically). Prevention of eye shavings such as silicone oils described in Kai 2009-120717, monoamide compounds of higher aliphatic carboxylic acids, and monoester compounds formed by reacting higher aliphatic carboxylic acids with monovalent to trivalent alcohol compounds. Agent) and other optional additives may be contained.

In the present embodiment, the total content of the additive, the processing aid, and the optional additive component may be 0.05 to 5% by mass in the flame-retardant styrene resin composition.

The flame-retardant styrene resin composition of the present embodiment may be substantially composed of only the components (A) to (C) and the optional additive components. Further, it may consist of only the components (A) to (C), or only the components (A) to (C) and the optional additive component.
"Substantially composed of only the components (A) to (C) and optional additives" means that 95 to 100% by mass (preferably 98 to 100% by mass) of the flame-retardant styrene resin composition is (A). ) To (C) component, or (A) to (C) component and an optional additive component.
The flame-retardant styrene resin composition of the present embodiment may contain unavoidable impurities in addition to the components (A) to (C) and optional additives as long as the effects of the present invention are not impaired.

[Physical characteristics of flame-retardant styrene resin composition]
<Flame retardant>
The flame retardancy of the flame-retardant styrene resin composition of the present embodiment is within the standard in the UL94 vertical combustion test (UL94-V test), that is, in the flame-retardant class of V-0 to V-2. It is preferable to have.
In the present disclosure, the flame retardancy can be evaluated by the method described in the section [Examples] described later.

<Melt flow rate (MFR)>
The melt flow rate of the flame-retardant styrene resin composition of the present embodiment is preferably 1 gram / 10 minutes or more, and more preferably 2 grams / 10 minutes or more. If it is less than 1 gram / 10 minutes, the fluidity is low and there is a risk that large products and thin-walled products cannot be molded.
In the present disclosure, the melt flow rate is a value measured under the conditions of a temperature of 200 ° C. and a load of 49N in accordance with ISO1133.

<Charpy impact strength>
The Charpy impact strength of the flame-retardant styrene resin composition of the present embodiment is preferably 1.2 kJ / m ² or more, and more preferably 6 kJ / m ² or more. If it is less than 1.2 kJ / m ² , there is a concern that it will be damaged during use in applications such as internal parts of OA products.
In the present disclosure, the Charpy impact strength is a value measured in accordance with ISO 179.

<Light resistance>
The light resistance of the flame-retardant styrene resin composition of the present embodiment is preferably 10 or less, more preferably 5 or less in color difference ΔE. If it is larger than 10, it may not be usable outdoors due to a decrease in strength, discoloration may occur even indoors, and design and recyclability may be impaired.
In the present disclosure, the color difference ΔE is the color difference (ΔE) after 300 hours by maintaining the temperature of the black panel at 63 ° C. using a xenon lamp type weather meter in accordance with JIS K7103 and JIS K7105. It is a value measured by the value of.

[Manufacturing method of flame-retardant styrene resin composition]
The flame-retardant styrene resin composition of the present embodiment can be produced by melt-kneading each component by an arbitrary method. For example, a method of using a high-speed stirrer represented by a Henschel mixer, a batch type kneader represented by a Banbury mixer, a single-screw or biaxial continuous kneader, a roll mixer, or the like alone or in combination can be mentioned. The heating temperature during kneading is usually selected in the range of 180 to 260 ° C.

[Molding]
The flame-retardant styrene-based resin composition of the present embodiment can be obtained by an injection molding method, an injection compression molding method, or by using the above-mentioned melt-kneading molding machine or using the obtained pellets of the flame-retardant styrene-based resin composition as a raw material. A molded product can be manufactured by an extrusion molding method, a blow molding method, a press molding method, a vacuum molding method, a foam molding method, or the like.
Molded products containing the flame-retardant styrene resin composition of the present embodiment, particularly injection molded products (including injection compression), copiers, fax machines, televisions, radios, tape recorders, video decks, personal computers, printers, telephones, It is suitably used for information terminals, refrigerators, OA equipment such as microwave ovens, household electric appliances, housings and various parts of electric / electronic equipment, foam insulation materials, insulating films and the like.

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

<Measurement and evaluation method>
The measurement and evaluation of the physical properties of the resin compositions obtained in each Example and Comparative Example were carried out based on the following methods.

(1) Content of rubber-like polymer (a1) contained in rubber-modified styrene resin (A) The amount of butadiene segment was measured using a pyrolysis gas chromatographie based on the bonding mode of butadiene segment. , The content of the rubber-like polymer (a1) was calculated from the amount of butadiene segment. The unit is mass%.

(2) Average particle size of the rubber-like polymer (a1) contained in the rubber-modified styrene resin (A) An ultrathin section having a thickness of 75 nm was prepared from the rubber-modified styrene resin (A) dyed with osmium tetroxide. Then, a photograph with a magnification of 10000 times was taken using an electron microscope. In the photograph, the black-stained particles are the rubber-like polymer (a1). From the photo, the following formula (N1):
Average particle size = ΣniDri ³ / ΣniDri ² (N1)
(In the formula, ni is the number of rubber-like polymer (a1) particles having a particle size Dri, and the particle size Dri is a particle size calculated as a circle-equivalent diameter from the area of the particles in the photograph.)
The area average particle size was calculated and used as the average particle size of the rubber-like polymer (a1). In this measurement, a photograph was taken into a scanner at a resolution of 200 dpi and measured using particle analysis software of an image analysis device IP-1000 (manufactured by Asahi Kasei Corporation).

(3) Reduced Viscosity of Rubber-Modified Styrene Resin (A) The reduced viscosity is an index of the molecular weight of the rubber-modified styrene resin (A). 1 g of the rubber-modified styrene resin (A) was added to 20 mL of a mixed solvent of methyl ethyl ketone / methanol (mixed mass ratio 90/10) and dissolved in a shaker for 60 minutes. Next, using a himacCR20 centrifuge manufactured by Hitachi, Ltd. equipped with an R20A2 type rotor, the centrifuge was centrifuged at 0 ° C. and 20,000 rpm for 60 minutes, and then methanol was added to the supernatant to add a rubber-modified styrene resin (A). ), Which is the matrix phase, was precipitated with a styrene resin. After filtering the precipitate, it was dried to prepare a sample, and the reduced viscosity (dL / g) was measured in a toluene solution at 30 ° C. and a concentration of 0.5 g / dL.

(4) Content of styrene-based monomer unit (b1), methacrylic acid monomer unit, and methyl methacrylate monomer unit of the copolymer resin (B) Proton nuclear magnetic resonance ( ¹ H-NMR) measuring machine The resin composition was quantified from the integral ratio of the spectra measured in 1.
-Sample preparation: 30 mg of the resin pellet was dissolved in 0.75 mL of d6-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 times, repetition time 11 seconds.
(Spectral attribution)
For spectral assignments measured in dimethylsulfoxide heavy solvent, peaks of 0.5-1.5 ppm are hydrogen methacrylic acid, methyl methacrylate, and the α-methyl group hydrogen of the six-membered cyclic acid anhydride, 1.6. The peak of ~ 2.1ppm is the hydrogen of the methylene group of the polymer main chain, the peak of 3.5ppm is the hydrogen of the carboxylic acid ester of methyl methacrylate (-COOCH ₃ ), and the peak of 12.4ppm is the hydrogen of the carboxylic acid of the methacrylate. Is. The peak of 6.5 to 7.5 ppm is hydrogen in the aromatic ring of styrene. In addition, since the content of 6-membered cyclic acid anhydride is small in the resins of this example and the comparative example, it is usually difficult to quantify by this measuring method.

(5) Weight average molecular weight of the copolymer resin (B) The weight average molecular weight of the copolymer resin (B) was measured under the following conditions and procedures.
-Sample preparation: The resin was dissolved in tetrahydrofuran in an amount of about 0.05% by mass.
-Measurement conditions Equipment: TOSOH HLC-8220GPC (gel permeation chromatography)
Column: super HZM-H
Temperature: 40 ° C
Carrier: THF 0.35 mL / min
Detector: RI, UV: 254nm
Calibration curve: Created using standard PS made by TOSOH.

(6) Flame retardancy UL94 vertical combustion test using a 50W test flame using a test piece (b) (size: 127 mm × 12.7 mm, thickness: 1.5 mm or 0.8 mm) produced by the method described below (. The flame retardancy was evaluated by a method according to the UL94-V test).
The flame of the gas burner was applied to the test piece (b), and the degree of combustion was evaluated.
In addition, the flame-retardant class shown as the flame-retardant class classified by the UL94-V test. Five tests were performed on all the test pieces and the judgment was made. The outline of the classification method is as follows.
V-0: 5 pieces total burning time 50 seconds or less, maximum burning time 10 seconds or less, no dripping cotton ignition V-1: 5 pieces total burning time 250 seconds or less, maximum burning time 30 seconds or less, no dripping cotton ignition V-2: Total burning time of 5 pieces is 250 seconds or less, maximum burning time is 30 seconds or less, with dripping cotton ignition Not V: Non-standard of UL94

(7) Melt flow rate (MFR)
The melt mass flow rate (g / 10 min) of the copolymerized resin (B) was measured according to ISO 1133 (200 ° C., load 49N).

(8) Charpy impact strength With respect to the test piece (b) prepared by the method described later, the Charpy impact strength (kJ / m ² ) was measured with a notch in accordance with ISO 179.

(9) Light resistance The test piece (a) prepared by the method described later was used and evaluated according to JIS K7103 and JIS K7105. That is, using a xenon lamp type weather meter [Atlas Co., Ltd .; Ci65], the temperature of the black panel is maintained at 63 ° C., and the evaluation is based on the value of the color difference (ΔE) between the start of measurement and 300 hours after the start of measurement. did. This ΔE was measured under the following conditions using a spectroscopic colorimeter [manufactured by Nippon Denshoku Kogyo Co., Ltd.].
(A) Lamp: Halogen lamp; 12V, 50W [manufactured by NARVA]
(B) Wavelength of light: 400-700 nm
(C) Light source: C light source 2 degree field of view (d) Measurement hole: Diameter 30 mm
(E) Measurement target: Reflected light

(10) Surface appearance As for the surface appearance, observe one surface of the test piece prepared by the method described later, and if there are less than 20 dents with an opening of 0.1 mm or more, 20 pieces are regarded as "OK". The case where the above exists was evaluated as "NG".

The materials used in the examples are as follows.
[(A) component]
-Rubber-modified styrene resin (HIPS):
A rubber-modified styrene resin, which is high-impact polystyrene (HIPS), was used. The HIPS uses polybutadiene as a rubber-like polymer, and the analytical value of the HIPS by the above analysis method is that the content of the rubber-like polymer (a1) is 8.6% by mass, and the rubber-like polymer (a1). The average particle size of the particles was 1.9 μm and the reduction viscosity was 0.64 dL / g.

[(B) component]
[Resin a]
71.3 parts by mass of styrene (ST), 7.3 parts by mass of methacrylic acid (MAA), 6.4 parts by mass of methyl methacrylate (MMA), 15.0 parts by mass of ethylbenzene, 1,1-bis (t-butylper). Oxy) Cyclohexane A polymerization raw material composition consisting of 0.025 parts by mass, at a rate of 1.1 liters / hour, consisting of a fully mixed reactor with a capacity of 4 liters, and then a laminar flow reactor of 2 liters. A resin was prepared by continuously supplying the polymerization apparatus to a devolatilization apparatus in which a uniaxial extruder for removing volatile components such as unreacted monomers and polymerization solvent was connected.
The polymerization reaction conditions in the polymerization step were a polymerization temperature of 122 ° C. for the complete mixing reactor and a polymerization temperature of 120 to 142 ° C. for the laminar flow reactor. The devolatile unreacted gas was condensed in a condenser through which a refrigerant at −5 ° C. was passed, and recovered as an unreacted liquid.
The polymer content in the final polymerization solution was measured by the formula [(sample mass after drying / sample mass before drying) × 100%] after drying the polymerization solution at 215 ° C. under a reduced pressure of 2.5 kPa for 30 minutes. , 65.6% by mass, and the weight average molecular weight was 214,000.
Table 1 shows the composition ratio and physical properties of the obtained resin a.
[Resin b to d]
The composition, polymerization temperature conditions, and the like were adjusted so as to have the properties of the resin shown in Table 1 below, and the resins b to e were obtained in the same manner as the resin a.
Table 1 shows the composition ratios and physical properties of the obtained resins b to e.

[GPPS]
-MFR 2.2 polystyrene (GPPS, PS Japan Corporation, G9401) was used.

[Polyphenylene ether]
-Polyphenylene ether "Zylon S202A manufactured by Asahi Kasei Corporation) was used.
The following polyphenylene ether-based resins were used.
-Zylon S202A [manufactured by Asahi Kasei Corporation] (Mz molecular weight 6.0 x 10 ⁴ )

[(C) component]
Aluminum diethylphosphinate (hereinafter referred to as DEP) was produced with reference to the production method described in JP-A-08-73720.
The DEP mass was wet-pulverized in water and then classified to obtain a DEP having the following average particle size.
DEP-1: Aluminum diethylphosphinate Average particle size (d50%) 3.1 μm
DEP-2: Aluminum diethylphosphinate Average particle size (d50%) 20 μm
DEP-3: Aluminum diethylphosphinate Average particle size (d50%) 15 μm
DEP-4: Aluminum diethylphosphinate Average particle size (d50%) 0.8 μm
DEP-5: Calcium diethylphosphinate Average particle size (d50%) 3 μm
The average particle size of the granular phosphinates is calculated based on the volume-based particle size measured by using a laser diffraction / scattering type particle size distribution measuring device. The average particle size is a value measured by using a 3% isopropanol aqueous solution as a dispersion medium for phosphinates. Specifically, a blank measurement is performed with a dispersion medium of a 3% isopropanol aqueous solution using a laser diffraction / scattering particle size distribution measuring device LA-910 (manufactured by HORIBA, Ltd.), and then the measurement sample is transmitted through the specified value. It can be obtained by putting it in a rate (95% to 70%) and measuring it. The sample was dispersed in the dispersion medium by irradiating it with ultrasonic waves for 1 minute.

[PTFE]
PS-coated PTFE "SN3300 manufactured by Shine polymer" containing 50% polytetrafluoroethylene.

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

[Examples 1 to 12]
For each component and 100 parts by mass of the components (A) to (C) in the composition ratios shown in Tables 2 and 3 below, 0.5 part by mass of PTFE, 0.2 parts by mass of Irganox 1076 and Irgafos 168 were added and then premixed. .. The obtained premixture is mixed in a batch and melt-extruded in the range of 180 ° C to 260 ° C using a twin-screw extruder (TEM-26SS manufactured by Toshiba Machine Co., Ltd.) to form a flame-retardant styrene resin composition as a kneaded product. Obtained pellets of material. At this time, the screw rotation speed was 150 rpm and the discharge amount was 10 kg / hr.
The pellet-shaped flame-retardant styrene resin composition thus obtained was molded at a cylinder temperature of 220 ° C. using an injection molding machine manufactured by Japan Steel Works, Ltd. equipped with an ISO standard test piece type A mold. A test piece (a) was prepared by molding at a temperature of 50 ° C., an injection pressure (gauge pressure 40-60 MPa), an injection speed (panel set value) of 50%, and an injection time / cooling time = 5 sec / 20 sec. Using the obtained test pieces, the Charpy impact strength, the Vicat softening temperature, and the light resistance were measured, and the surface appearance of the molded product was evaluated. For flame retardancy evaluation, an injection molding machine manufactured by Japan Steel Works, Ltd. equipped with a pingate flat plate mold having dimensions of 127 mm × 12.7 mm × thickness of 1.5 mm was used, and the cylinder temperature was 220 ° C. and the mold temperature was 50 ° C. A test piece (b) was prepared and evaluated by molding at an injection pressure (gauge pressure 40-60 MPa), an injection speed (panel set value) 50%, and an injection time / cooling time = 5 sec / 20 sec. The results are shown in Table 2.

[Comparative Examples 1 to 6]
In Comparative Examples 1 to 6, pellets of the resin composition were obtained in the same manner as in Examples except that the compositions were changed as shown in Table 3. Table 3 shows the results of measurement and evaluation of each physical property.

As shown in Table 2, Examples 1 to 12 have high flame retardancy (V-0 or V-1 at a thickness of 1.5 mm) and are excellent in impact resistance, heat resistance, light resistance, and molded appearance. You can see that. In addition, the good dispersion makes the material highly elastic and rigid.

As shown in Table 3, with respect to Comparative Examples 1 and 2, the dispersibility is poor, the flame retardancy cannot be obtained, and the impact strength and the molded appearance are poor without the specific copolymer resin (B).
As shown in Table 3, in Comparative Example 3, when polyphenylene ether is used instead of the specific copolymer resin (B), the light resistance, impact strength, and molded appearance are deteriorated.
As shown in Table 3, in Comparative Example 4, when the amount of the component (B) is large, the fluidity and the impact strength decrease.
As shown in Table 3, with respect to Comparative Example 5, when the amount of the component (C) is large, the fluidity and the impact strength decrease. On the other hand, if the amount of the component (C) is small as in Comparative Example 6, flame retardancy cannot be obtained.

The molded product containing the flame-retardant styrene resin composition of the present invention includes computer parts such as desktop personal computers and notebook personal computers, mobile phone parts, electric / electronic devices, personal digital assistants, home electric appliances parts, automobile parts, and industrial materials. , And thin products such as building materials, sheets, films, etc. can be suitably used.

Claims (4)

The rubber-modified styrene resin (A) is 40 to 85% by mass,
The copolymer resin (B) containing the styrene-based monomer unit (b1), the unsaturated carboxylic acid-based monomer unit, and the unsaturated carboxylic acid ester-based monomer unit is 5.0 to 30% by mass.
The following general formula (1):

[In the above formula (1), R ¹¹ and R ¹² are linear or branched alkyl groups having 1 to 6 carbon atoms or aryl groups having 6 to 10 carbon atoms, respectively; M. ¹ is at least one selected from the group consisting of calcium ion, magnesium ion, aluminum ion, zinc ion, bismuth ion, manganese ion, sodium ion, potassium ion and protonated nitrogen base; a is M ¹ . Representing the ionic value, it is an integer of 1 to 3; m ¹ is an integer of 1 to 3; a = m ¹ . When a plurality of R ¹¹ and R ¹² are present, the respective R ¹¹ and R ¹² may be the same or different. ], And the following formula (2):

[In the formula, R ²¹ and R ²² are each independently a linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms; L ²³ is an integer. A chain or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkyl arylene group having 6 to 10 carbon atoms, or an arylalkylene group having 6 to 10 carbon atoms; M ² is at least one selected from the group consisting of calcium ion, magnesium ion, aluminum ion, zinc ion, bismuth ion, manganese ion, sodium ion, potassium ion and protonated nitrogen base; b is M ² Represents the ionic value of 1 to 3; m ² is an integer of 1 to 3; i is an integer of 1 or 2; b × i = 2 m ² . When a plurality of R ²¹ and R ²² are present, the respective R ²¹ and R ²² may be the same or different. ], The flame retardant (C) containing at least one phosphinate salt selected from the group consisting of diphosphane salt salts is 10 to 30% by mass.
A flame-retardant styrene-based resin composition comprising. The total content of the styrene-based monomer unit (b1), the unsaturated carboxylic acid-based monomer unit, and the unsaturated carboxylic acid ester-based monomer unit of the copolymer resin (B) was set to 100% by mass. When, the styrene-based monomer unit (b1) is contained in an amount of 67.0 to 96.0% by mass, the unsaturated carboxylic acid-based monomer unit is contained in an amount of 4.0 to 18.0% by mass, and The flame-retardant styrene-based resin composition according to claim 1, which contains 0.0 to 15.0% by mass of the unsaturated carboxylic acid ester-based monomer unit. The flame-retardant styrene resin composition according to claim 1 or 2, wherein the flame retardant (C) is granular and the average particle size of the flame retardant (C) is more than 0.5 μm and 10 μm or less. A molded product comprising the flame-retardant styrene resin composition according to any one of claims 1 to 3.