JP2010095731A - Flame retardant styrene resin composition and molded product formed from the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a styrene resin composition balanced in characteristics such as an industrially useful thermostability, color, fluidity and heat resistance while maintaining flame resistance, and to provide a molded product formed from the same with excellent appearance without silver streak. <P>SOLUTION: The resin composition includes (A) 100 pts.wt. of a styrene resin (component A) and (C) 1-100 pts.wt. of an organic phosphorus compound (component C) shown by formula (1), wherein the organic phosphorus compound (component C) satisfies (i) a heating residue at 500°C of 10% or less, (ii) an HPLC purity of 90% or over and (iii) an acid number of 0.5 mg-KOH/g or less, wherein Ar<SP>1</SP>and Ar<SP>2</SP>may be the same or different and are each a phenyl group optionally having a substituent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a flame retardant styrenic resin composition having flame retardancy, thermal stability, hue, fluidity and heat resistance, and a molded article excellent in appearance formed therefrom. More particularly, the present invention relates to a flame-free styrene resin composition containing a pentaerythritol diphosphonate compound having specific characteristics and substantially halogen-free, and a molded article therefrom.

  Styrenic resins have excellent impact resistance and excellent moldability, so they are used in a wide range of fields such as office automation equipment parts, home appliance parts, and automotive parts. Therefore, its use is limited. In particular, in order to increase product safety in recent years, flame retardant test regulations based on the subject 94 of Underwriters Laboratory (UL), an American standard, are becoming stricter for office automation equipment and molded products of household electrical appliances. Therefore, more advanced flame resistance is required.

  As a method for imparting flame retardancy to a flammable resin such as a styrene resin, a halogen flame retardant has been conventionally used. It is generally known that a halogen-based flame retardant can be used in combination with antimony oxide to achieve a high degree of flame retardancy. However, in recent years, halogen-based flame retardants have been used in many ways due to environmental problems such as the generation of toxic gases during combustion. Studies on flame retardants have been actively conducted.

  As such a method, many methods of adding a phosphorus flame retardant to a mixture of a styrene resin and a polyphenylene ether resin have been reported. Such a method is a method of improving thermal stability by adding a polyphenylene ether-based resin to a styrene-based resin and making it flame-retardant with a phosphorus-based flame retardant, and is disclosed in Patent Documents 1 to 6 and the like.

  However, all of the resin compositions in the above publications have a markedly reduced heat resistance compared to before the addition of the flame retardant. It has not reached. This is because the phosphorus-based flame retardant used in the resin composition of the above publication is derived from plasticity, and uses an aromatic phosphate ester monomer or an aromatic phosphate ester condensate. As long as phosphorus-based flame retardants are used, it has been unavoidable.

  Patent Document 7 discloses a two-component resin composition in which a pentaerythritol diphosphonate compound is added to high-impact polystyrene and a three-component resin composition in which polyphenylene ether is further added to the former. It is disclosed as an example. However, in this patent, it is presumed that the purity, acid value, and reduced viscosity of the high-impact polystyrene and the amount of rubber component of the pentaerythritol diphosphonate compound were not appropriate, and any practical flame-retardant composition was obtained. It is not done. That is, in the comparative example of this patent, an example in which 8% by weight of various pentaerythritol diphosphonate compounds are added to high-impact polystyrene is described. In the examples, polyphenylene ether is used to improve the flame retardancy. Further, although added, due to the disadvantages of the pentaerythritol diphosphonate compound, the flame retardancy was still insufficient and could not withstand practical use.

  Due to the above situation, the patent relates to the thermal stability, hue, and appearance of the resin composition, which is a practically important item, and the weight loss residue, purity, and acid value of the pentaerythritol diphosphonate-based compound There is also no mention about.

  Patent Document 8 describes an invention in which pentaerythritol diphosphate or diphosphonate is added to a resin component mainly composed of high impact polystyrene. Examples of using diphosphonates include HIPS / diphosphonate compositions as examples and achieving flame retardancy V-2, but the appearance and thermal stability of molded articles that are important in practice. Was still inadequate.

  In Patent Document 9, the ABS resin has a total number of carbon atoms in two hydrocarbyl substituents of 8 or less, and therefore, the two substituents cannot simultaneously contain an aromatic ring, which is different from that of the present invention. A flame retardant resin composition containing P, P'-dihydrocarbyl pentaerythritol diphosphonate is described. Specifically, dimethylpentaerythritol diphosphonate, which is a raw material for chemical weapons and is prohibited from industrial use, is used as diphosphonate, and achieves flame retardancy V-0 when blended in ABS resin by 25% by weight. However, it is clear that it is not practical. In addition, this publication does not include any description regarding the weight loss residue, purity, and acid value of the pentaerythritol diphosphonate compound related to appearance, thermal stability, and hue, which are important items for practical use.

  Patent Document 10 describes a resin composition excellent in flame retardancy in which pentaerythritol diphosphonate having an acid value of 0.7 mgKOH / g or less is blended with a resin component mainly composed of an aromatic polyester resin.

  As far as the present inventors know, it has been extremely difficult to achieve an effective flame retardant level by using a phosphorus compound alone and to achieve practical physical properties in the halogen-free flame retardant of conventional styrene resins. There were many problems in practical use. In order to achieve a practically effective flame retardant level using a phosphorus compound, it was necessary to use a large amount of the phosphorus compound. Furthermore, conventional phosphorus compounds are low boiling point compounds, and problems such as gas generation during extrusion and mold contamination during molding occur in the resin that is extruded and molded at a relatively high temperature. Further, it is generally known that when a normal phosphorus compound is added to a styrene resin, the heat resistance is extremely lowered and the original characteristics of the styrene resin are impaired.

JP 54-34848 A JP-A-5-287119 JP-A-5-339417 JP 7-316383 A JP-A-9-132893 JP-A-9-151315 U.S. Pat. No. 4,162,278 WO01 / 57134 specification WO00 / 17268 specification (Japanese translations of PCT publication No. 2002-526585) WO02 / 92690 specification

  An object of the present invention is to provide a styrenic resin composition having excellent thermal stability, hue, fluidity, and heat resistance, and also having flame retardancy, and a molded product excellent in appearance formed therefrom.

  The first object of the present invention is to provide a styrenic resin composition having a balance of industrially useful thermal stability, hue, fluidity, heat resistance, etc. while maintaining flame retardancy, and silver formed therefrom An object of the present invention is to provide a molded article having an excellent appearance without any defects.

  A second object of the present invention is to provide a styrenic resin composition that can achieve high flame retardancy of V94 level or higher of UL94 standard, and a molded article thereof, substantially free of halogen. There is to do.

  A third object of the present invention is to provide a flame-retardant styrene resin composition that can be advantageously used for office automation equipment parts, home appliance parts, electrical / electronic parts, automobile parts, and the like, and a molded product thereof. is there.

（式中、Ａｒ^１およびＡｒ^２は、同一又は異なっていても良く、置換基を有しても良いフェニル基である。）
により達成される。 According to the study by the present inventors, the object of the present invention is as follows.
(A) A resin composition comprising 100 parts by weight of a styrene-based resin (component A) and (C) 1 to 100 parts by weight of an organophosphorus compound (component C) represented by the following formula (1), wherein the organophosphorus compound (C component) is
(I) Heated weight reduction residue at 500 ° C. is 10% or less,
(Ii) a flame-retardant styrene-based resin composition characterized by satisfying an HPLC purity of 90% or more and (iii) an acid value of 0.5 mgKOH / g or less,

(In the formula, Ar ¹ and Ar ² may be the same or different and are phenyl groups which may have a substituent.)
Is achieved.

The flame retardant resin composition of the present invention and a molded product formed therefrom have the following advantages over the conventional flame retardant styrene resin composition.
(I) Due to the characteristics of the organophosphorus compound used as a flame retardant, a resin with excellent thermal stability that hardly causes thermal degradation of the styrene resin during molding of the styrene resin or when using the molded product A composition is obtained. In addition, a molded product excellent in appearance without burns or silver can be obtained. Therefore, a composition having a well-balanced thermal stability, appearance, hue, fluidity, heat resistance and flame retardancy can be obtained.
A styrenic resin composition having industrially useful flame retardancy, heat resistance, fluidity, and mechanical properties can be obtained without substantially using a halogen-containing flame retardant.
(Ii) Since the organophosphorus compound as a flame retardant has an excellent flame retardant effect with respect to the styrene resin, the V-2 level can be achieved even with a relatively small amount of use. That is, it is not necessary to add a large amount and component to achieve the target flame retardant level, and a composition having the target flame retardant level can be obtained with a relatively simple composition.
(Iii) Materials for molding various molded articles such as office automation equipment parts, home appliance parts, electrical / electronic parts, and automobile parts can be obtained without substantially containing halogen.

Hereinafter, the flame retardant styrene resin composition of the present invention will be described in detail.
The styrenic resin used as component A of the present invention is a homopolymer or copolymer of an aromatic vinyl monomer such as styrene, α-methylstyrene or vinyltoluene, these monomers and acrylonitrile, methyl methacrylate. Copolymers with vinyl monomers such as polybutadiene, diene rubbers such as polybutadiene, ethylene / propylene rubber, acrylic rubber, etc. with styrene and / or styrene derivatives, or styrene and / or styrene derivatives and other vinyl monomers Graft polymerized. Specific examples of the styrene resin include polystyrene, high impact polystyrene (HIPS), acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene. Copolymer (MBS resin), Methyl methacrylate / Acrylonitrile / Butadiene / Styrene copolymer (MABS resin), Acrylonitrile / Acrylic rubber / Styrene copolymer (AAS resin), Acrylonitrile / Ethylene propylene rubber / Styrene copolymer (ABS resin) AES resin) or a mixture thereof. From the viewpoint of impact resistance, a rubber-modified styrene resin is preferable, and the rubber-modified styrene resin refers to a polymer in which a rubber-like polymer is dispersed in a particle form in a matrix made of a vinyl aromatic polymer. Aromatic vinyl monomer in the presence of rubbery polymer, and optionally vinyl monomer are added to obtain a monomer mixture by known block polymerization, block suspension polymerization, solution polymerization or emulsion polymerization. It is done.

  Examples of the rubber-like polymer include diene rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), and saturated rubbers obtained by hydrogenating the diene rubber, isoprene rubber, chloroprene rubber, polybutyl acrylate. Examples thereof include acrylic rubbers such as ethylene-propylene-diene terpolymer (EPDM), and diene rubbers are particularly preferable.

The aromatic vinyl monomer as an essential component in the graft copolymerizable monomer mixture to be polymerized in the presence of the rubbery polymer is, for example, styrene, α-methylstyrene, paramethylstyrene, and the like. Styrene is most preferred.
Examples of vinyl monomers that can be added as needed include acrylonitrile and methyl methacrylate.

  The rubber-like polymer in the rubber-modified styrenic resin is 1 to 50% by weight, preferably 2 to 40% by weight. The monomer mixture capable of graft polymerization is 99 to 50% by weight, preferably 98 to 60% by weight. Within this range, the balance between impact resistance and rigidity of the intended resin composition is improved, and thermal stability is good.

  The reduced viscosity ηsp / C (0.5 g / dl, toluene solution, measured at 30 ° C.), which is a measure of the molecular weight of the styrene resin in the present invention, is 0.2 to 1.5 dl / g, preferably 0.3 to 1.4 dl / g. As means for satisfying the above-mentioned conditions concerning the reduced viscosity ηsp / C of the rubber-modified styrene resin, adjustment of the polymerization initiator amount, polymerization temperature, chain transfer agent amount, and the like can be raised. If the reduced viscosity is low, the heat resistance and impact resistance are also low.

  The styrenic resin used in the present invention is preferably high impact polystyrene (HIPS). The impact value of HIPS is preferably in the range of 20 J / m to 300 J / m in Izod impact strength (notched) measured by JIS K6871 test.

  Among the resin compositions of the present invention, the flame retardancy of a resin composition comprising (A) a styrene resin (A component) and (C) an organophosphorus compound (C component) is the content of the rubbery polymer of the A component. And susceptible to the reduced viscosity of component A. In order to obtain stable flame retardancy in the composition, the rubbery polymer content of the component A is 1 to 6%, preferably 1 to 5.5%. In order to obtain stable flame retardancy in the composition, the reduced viscosity of the component A is 0.2 to 0.9 dl / g, preferably 0.3 to 0.8 dl / g.

（式中、Ａｒ^１およびＡｒ^２は、同一又は異なっていても良く、置換基を有しても良いフェニル基である。） In the present invention, the organophosphorus compound used as component C is a pentaerythritol diphosphonate compound represented by the following formula (1) that satisfies the following properties (i) to (iii).
(I) Heated weight reduction residue at 500 ° C. is 10% or less,
(Ii) HPLC purity is 90% or more,
(Iii) Acid value of 0.5 mgKOH / g or less

(In the formula, Ar ¹ and Ar ² may be the same or different and are phenyl groups which may have a substituent.)

By using the organophosphorus compound of the formula (1) that satisfies the characteristics (i) to (iii), a resin composition excellent in thermal stability, hue, appearance, flame retardancy, and the like can be obtained.
The weight loss residue at 500 ° C. of the organophosphorus compound used as component C is measured by a thermogravimetric balance test (TGA method) under a nitrogen stream at a rate of temperature increase of 10 ° C./min. The remaining amount at 500 ° C. (%) Was defined as the weight loss residue after heating. The residual weight loss at 500 ° C. of the organophosphorus compound (component C) is 10% or less, preferably 8% or less, more preferably 5% or less, still more preferably 3% or less, and particularly preferably 1%. It is as follows. Those having a large residual weight after heating at 500 ° C. indicate that they contain a large amount of impurities, and these impurities adversely affect the thermal stability, hue, appearance, flame retardancy, etc. of the resin composition of the present invention.

  The C component organophosphorus compound has an HPLC purity of 90% or higher, preferably 95% or higher, particularly preferably 97% or higher. Such a high purity is preferable because of its excellent flame retardancy, hue and thermal stability. When the HPLC purity is less than 90%, the flame retardancy, hue and thermal stability are adversely affected by the impurities contained therein, resulting in mold contamination of the molding machine and defective appearance (silver) of the molded product. .

Here, the following method is used to measure the HPLC purity of the component C.
As the column, Develosil ODS-7 300 mm × 4 mmφ manufactured by Nomura Chemical Co., Ltd. was used, and the column temperature was 40 ° C. As a solvent, a mixed solution of acetonitrile and water of 6.5: 3.5 (volume ratio) was used, and 5 μl was injected. The detector used was UV-260 nm.

  The organic phosphorus compound of component C has an acid value of 0.5 mgKOH / g or less, preferably 0.4 mgKOH / g or less, more preferably 0.3 mgKOH / g or less, still more preferably 0.2 mgKOH / g or less, particularly preferably Is 0.1 mg KOH / g or less. By using the C component having an acid value in this range, a molded product excellent in hue, appearance and flame retardancy can be obtained, and a molded product having good thermal stability can be obtained. C component organophosphorus compounds having an acid value exceeding 0.5 mgKOH / g are not preferred because they can cause mold contamination of the molding machine and rusting of the extruder. Moreover, when an acid value is high, it will cause decomposition | disassembly of an organophosphorus compound itself, and the decomposition product of an organophosphorus compound will cause the appearance defect of a molded article, and silver will generate | occur | produce. Furthermore, since the resin composition of the present invention is also used for electric / electronic equipment, it is considered that the acid component adversely affects the electric / electronic equipment. Here, the acid value means the amount (mg) of KOH required to neutralize the acid component in 1 g of the sample (C component), and can be measured by the method defined in JIS-K-3504.

  The resin composition of the present invention has an HDT retention rate of 85% or more based on the base resin, and within the range of the retention rate, it cannot be a practically significant drawback, and maintains the high heat resistance inherent in the base resin. Features. The preferable range of the HDT retention is 90% or more, more preferably 95% or more.

  In the present invention, in addition to the organic phosphorus compound of component C, a phosphorus compound other than component C, a fluorine-containing resin, or other additives can be added. These additives are used for reducing the proportion of organophosphorus compounds that are component C, improving the flame retardancy of molded articles, improving the physical properties of molded articles, improving the chemical properties of molded articles, or other purposes. Therefore, it can be naturally blended. These other blending components will be specifically described later.

  A preferred example of the phosphorus compound used as the component C in the present invention is an organic phosphorus compound represented by the following formula (2).

  Next, a method for synthesizing the organophosphorus compound (C component) in the present invention will be described. The organic phosphorus compound of component C may be produced by a method other than the method described below as long as it satisfies the specific characteristics of the present invention.

  The organic phosphorus compound of component C is obtained, for example, by reacting pentaerythritol with phosphorus trichloride, subsequently treating the oxidized reaction product with an alkali metal compound such as sodium methoxide, and then reacting with aralkyl halide.

  It can also be obtained by reacting pentaerythritol with aralkyl phosphonic acid dichloride, or reacting pentaerythritol with phosphorus trichloride and reacting aralkyl alcohol with a compound obtained by reacting pentaerythritol with phosphorus trichloride, followed by Arbuzov transition at high temperature. . The latter reaction is disclosed, for example, in U.S. Pat. No. 3,141,032, JP-A-54-157156, and JP-A-53-39698.

  A specific method for synthesizing the organophosphorus compound of component C will be described below. However, this synthesis method is merely illustrative, and the organophosphorus compound of component C used in the present invention satisfies the specific characteristics. If it is a thing, what was synthesize | combined not only by these synthesis methods but the modification | change and the other synthesis method may be sufficient. A more specific synthesis method will be described in the preparation examples described later.

(I) Method 1 for producing organophosphorus compound (2) in component C;
A reaction product obtained by reacting pentaerythritol with phosphorus trichloride and then oxidizing with tertiary butanol can be obtained by treating with sodium methoxide and reacting with benzyl bromide.

(II) Production method 2 of organophosphorus compound of (2) in component C;
Pentaerythritol is reacted with phosphorus trichloride, and the resulting reaction product is reacted with benzyl alcohol. The obtained phosphite compound can be obtained by performing Arbuzov transition at high temperature in the presence of benzyl bromide.

  Furthermore, the organophosphorus compound obtained by the production method (I) or (II) is washed to satisfy the characteristics (i) to (iii). As a washing method, a reflux washing method with methanol is employed.

  This cleaning method is a method in which an organic phosphorus compound containing impurities and methanol are heated to reflux, and then cooled to room temperature and filtered. This cleaning method can remove impurities and reduce the acid value more effectively than repulp washing (washing with solvent and repeating filtration several times), and is advantageous in terms of cost.

  Specifically, 100-500 parts of xylene was added to 100 parts of the crude product of pentaerythritol diphosphonate produced by the production method of (I) or (II), and the mixture was added at 0.1-40 ° C. After stirring with a stirrer for 5 to 3 hours, filter. 100-500 parts of methanol is added to 100 parts of the resulting filtered product, and the mixture is heated to reflux for 0.5-6 hours. At this time, the solid component does not need to be completely dissolved. By cooling the slurry after heating to room temperature and filtering, pentaerythritol diphosphonate having the desired properties can be obtained.

  The organophosphorus compound of component C is 1 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 2 to 50 parts by weight, particularly preferably 5 to 50 parts by weight based on 100 parts by weight of the styrene resin (component A). It mix | blends in the range of a weight part.

  The suitable range of the blending ratio of component C is determined by the desired flame retardancy level, the type of resin component (component A), and the like. Furthermore, the compounding quantity of C component can be changed also by use of another flame retardant, a flame retardant adjuvant, and a fluorine-containing resin, and in many cases, the compounding ratio of C component can be reduced by using these.

The above-described flame-retardant styrene resin composition of the present invention is a composition that does not substantially contain halogen, and achieves flame retardancy of V-2 level or higher, which is very excellent in thermal stability and hue.
The flame retardant styrene resin composition of the present invention is a flame retardant styrene resin composition (I) comprising a styrene resin (component A) and an organic phosphorus compound (component C) represented by the formula (1). is there.

Flame retardant styrene resin composition (I)
(A) A resin composition comprising 100 parts by weight of a styrene resin (component A) and 1 to 100 parts by weight of an organophosphorus compound (component C) represented by the following formula (1), the organophosphorus compound (component C) )
(I) Heated weight reduction residue at 500 ° C. is 10% or less,
(Ii) A flame-retardant styrene resin composition characterized by satisfying an HPLC purity of 90% or more and (iii) an acid value of 0.5 mgKOH / g or less.

（式中、Ａｒ^１およびＡｒ^２は、同一又は異なっていても良く、置換基を有しても良いフェニル基である。）

(In the formula, Ar ¹ and Ar ² may be the same or different and are phenyl groups which may have a substituent.)

The above-described flame-retardant styrene resin composition (I) of the present invention is excellent in thermal stability, has no discoloration at the time of molding, has a good hue, has no appearance of silver and has an excellent appearance, fluidity and heat resistance. The property is also good. The flame retardancy is at least V-2 at the flame retardance level of UL94 standard, and preferably V-1. Even at the same flame retardancy level of V-2, the flame retardancy varies depending on the average number of seconds of combustion and the oxygen index (LOI). When the average burning time is small, the effect of preventing the spread of fire is high. With a test piece having a thickness of 1.6 mm, the average burning time is preferably 10 seconds or less, more preferably 8 seconds or less, and particularly preferably 6 seconds or less. Moreover, if LOI is 22.0 or more, it becomes difficult to combust in the air, and the applicable range is widened.
The range of 2-50 weight part is preferable with respect to 100 weight part of styrene resin (A component), and the range of 3-30 weight part is more preferable for an organophosphorus compound (C component).

  In the flame-retardant resin composition of the present invention, in addition to the organic phosphorus compound (C component), phosphorus or a phosphorus compound (D component) can be used in combination as another flame retardant. Examples of the D component include the following (D-1) to (D-5).

（Ｄ−３）；下記一般式（Ｄ−３）で表される縮合リン酸エステル

（Ｄ−４）；下記一般式（Ｄ−４）で表される縮合リン酸エステル

（Ｄ−５）；下記一般式（Ｄ−５）で表される有機リン化合物

(D-1); red phosphorus (D-2); triaryl phosphate represented by the following general formula (D-2)

(D-3); condensed phosphate represented by the following general formula (D-3)

(D-4); condensed phosphate represented by the following general formula (D-4)

(D-5); an organophosphorus compound represented by the following general formula (D-5)

In the formulas (D-2) to (D-4), Q ^{1 to} Q ⁴ may be the same or different and each is an aryl group having 6 to 15 carbon atoms, preferably an aryl group having 6 to 10 carbon atoms. is there. Specific examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group. These aryl groups may have 1 to 5, preferably 1 to 3 substituents. Examples of the substituents include (i) methyl group, ethyl group, propyl group, isopropyl group, and n-butyl. Group, sec-butyl group, tert-butyl group, neopentyl group and nonyl group, such as alkyl group having 1 to 12 carbon atoms, preferably alkyl group having 1 to 9 carbon atoms, (ii) methoxy group, ethoxy group, propoxy group An alkyloxy group having 1 to 12 carbon atoms such as butoxy group and pentoxy group, preferably an alkyloxy group having 1 to 9 carbon atoms, (iii) carbon such as methylthio group, ethylthio group, propylthio group, butylthio group and pentylthio group An alkylthio group having 1 to 12 carbon atoms, preferably an alkylthio group having 1 to 9 carbon atoms, and (iv) a group represented by the formula Ar ⁶ —W ¹ — (wherein W ¹ is — O-, -S- or an alkylene group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and Ar ⁶ represents an aryl group having 6 to 15 carbon atoms, preferably 6 to 10 carbon atoms). It is done.

In the formulas (D-3) and (D-4), Ar ⁴ and Ar ⁵ may be the same or different when both are present (in the case of D-4), and are arylene having 6 to 15 carbon atoms. Group, preferably an arylene group having 6 to 10 carbon atoms. Specific examples include a phenylene group or a naphthylene group. This arylene group may have 1 to 4, preferably 1 to 2 substituents. Examples of the substituent include (i) a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, and (ii) benzyl A group having 7 to 20 carbon atoms such as a group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and a cumyl group, and (iii) a group represented by the formula Q ⁵ —W ² — (wherein W ² is —O— or It indicates -S-, ^{Q 5} is 1 to 4 carbon atoms, preferably an alkyl group or 6 to 15 carbon atoms having 1 to 3 carbon atoms, preferably an aryl group having 6 to 10) and (iv) a phenyl group Examples thereof include aryl groups having 6 to 15 carbon atoms.

In formulas (D-3) and (D-4), m represents an integer of 1 to 5, preferably an integer of 1 to 3, and particularly preferably 1.
In the formula (D-4), Z is a single bond or group that bonds Ar ⁴ and Ar ⁵ , and —Ar ⁴ —Z—Ar ⁵ — is a residue usually derived from bisphenol. Thus, Z represents a single bond, —O—, —CO—, —S—, —SO ₂ — or an alkylene group having 1 to 3 carbon atoms, preferably a single bond, —O— or isopropylidene.

Even phosphorus compounds other than phosphorus or phosphorus compounds of (D-1) to (D-5) can be used in combination with the C component.
When the phosphorus or phosphorus compound (D component) of (D-1) to (D-5) is blended in the resin composition, the ratio is preferably 1 to 100 parts by weight of the organic phosphorus compound (C component). A range of 100 parts by weight, more preferably 5 to 80 parts by weight, particularly preferably 10 to 60 parts by weight is appropriate. Of the phosphorus or phosphorus compounds of (D-1) to (D-5), the phosphorus compounds of (D-2) to (D-5) are preferred.

The flame retardant resin composition of the present invention may further contain a biscumyl compound (E component) represented by the following formula.

The aromatic ring of this biscumyl compound may have 1 to 5, preferably 1 to 3 substituents, including (i) a methyl group, an ethyl group, a propyl group, an isopropyl group, an alkyl group having 1 to 12 carbon atoms such as n-butyl group, sec-butyl group, tert-butyl group, neopentyl group and nonyl group, preferably an alkyl group having 1 to 9 carbon atoms, (ii) methoxy group, ethoxy group Alkyloxy groups having 1 to 12 carbon atoms such as propoxy group, butoxy group and pentoxy group, preferably alkyloxy groups having 1 to 9 carbon atoms, (iii) methylthio group, ethylthio group, propylthio group, butylthio group and pentylthio group such alkylthio group having 1 to 12 carbon atoms, preferably alkylthio groups and (iv) ^Ar 6 -W ¹ of 1-9 carbon atoms - a group represented by the formula (this In ^{W 1} is -O -, - S-, or 1 to 8 carbon atoms, preferably an alkylene group having 1 to 4 carbon atoms, Ar ⁶ is 6 to 15 carbon atoms, preferably an aryl group having 6 to 10 carbon atoms Is shown).

  When this biscumyl compound (E component) is blended in the resin composition, the ratio is 0.01 to 3 parts by weight, preferably 0.02 to 2 parts by weight, based on 100 parts by weight of the styrene resin (component A). Particularly preferably, 0.03 to 1 part by weight is blended. It is presumed that the flame retardant effect by blending this biscumyl compound at the above ratio is due to radical generation, and as a result, the level of flame retardancy is improved.

  The flame retardant resin composition of the present invention may further contain a known flame retardant aid. Examples of the flame retardant aid include silicone oil. As such silicone oil, polydiorganosiloxane is used as a skeleton, preferably polydiphenylsiloxane, polymethylphenylsiloxane, polydimethylsiloxane, or an arbitrary copolymer or mixture thereof. Among them, polydimethylsiloxane is preferably used. . The viscosity is preferably 0.8 to 5,000 centipoise (25 ° C.), more preferably 10 to 1,000 centipoise (25 ° C.), and still more preferably 50 to 500 centipoise (25 ° C.). Those having excellent flame retardancy are preferred. The blending amount of the silicone oil is preferably in the range of 0.5 to 10 parts by weight with respect to 100 parts by weight of the styrene resin (component A).

  Furthermore, the flame retardant resin composition of the present invention may contain various flame retardant improvers. Examples of the flame retardant improving agent that can be blended in the flame retardant resin composition of the present invention include thermosetting resins represented by phenol resins and epoxy resins.

  The phenol resin used as the flame retardant modifier is arbitrary as long as it is a polymer having a plurality of phenolic hydroxyl groups, and examples thereof include novolak-type, resol-type and heat-reactive resins, or resins obtained by modifying these resins. It is done. These may be an uncured resin, a semi-cured resin, or a cured resin to which no curing agent is added. Among these, a phenol novolak resin that is non-reactive with no addition of a curing agent is preferred in terms of flame retardancy, impact resistance, and economy. Further, the shape is not particularly limited, and any of pulverized product, granular shape, flake shape, powder shape, needle shape, liquid state, and the like can be used. The said phenol resin can be used as a 1 type, or 2 or more types of mixture as needed.

  The phenol resin is not particularly limited, and commercially available products can be used. For example, in the case of a novolak-type phenol resin, the reaction vessel is charged with a molar ratio of phenols to aldehydes of 1: 0.7 to 1: 0.9, and oxalic acid, hydrochloric acid, sulfuric acid, toluenesulfonic acid, etc. After adding the catalyst, heating and refluxing reaction are performed. In order to remove the generated water, it is obtained by vacuum dehydration or standing dehydration, and further removing remaining water and unreacted phenols. By using a plurality of raw material components for these resins, a co-condensed phenol resin can be obtained, and this can also be used in the same manner.

  In the case of a resol-type phenol resin, a reaction vessel is prepared so that the molar ratio of phenols to aldehydes is 1: 1 to 1: 2, and further a catalyst such as sodium hydroxide, aqueous ammonia, and other basic substances. After adding, it can obtain by performing operation similar to a novolak-type phenol resin.

  Here, phenols are phenol, o-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, isoeugenol, o-methoxyphenol, 4,4′-dihydroxy. Examples include phenylpropane, isoamyl salicylate, benzyl salicylate, methyl salicylate, and 2,6-di-tert-butyl-p-cresol. These phenols can be used as one or a mixture of two or more as required. On the other hand, aldehydes include formaldehyde, paraformaldehyde, polyoxymethylene, trioxane and the like. These aldehydes can also be used as one or a mixture of two or more as required.

  The molecular weight of the phenolic resin is not particularly limited, but preferably has a number average molecular weight of 200 to 2,000, more preferably 400 to 1,500 in the range of mechanical properties, molding processability, and economic efficiency. Excellent and preferable.

  Examples of the epoxy resin used as a flame retardant improver include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, and cresol novolak type epoxy. Resins, naphthalene type epoxy resins, biphenol type epoxy resins and the like can be mentioned, but are not particularly limited thereto. These epoxy resins are not limited to one type in use, and two or more types of combined or various modified resins can be used.

  When blending the flame retardant improving resin, the proportion thereof is 0.01 to 45 parts by weight, preferably 0.1 to 40 parts by weight, particularly preferably 0.5 to 35 parts by weight based on 100 parts by weight of the component A. Part.

  The flame retardant resin composition of the present invention can further contain a fluorine-containing resin as an anti-dripping agent. The flame retardancy of the molded product is improved by blending the fluorine-containing resin. In particular, dripping in the combustion test of the molded product is suppressed.

  The fluorine-containing resin used as the anti-dripping agent is not particularly limited as long as it has a fibril-forming ability. For example, tetrafluoroethylene, trifluoroethylene, vinyl fluoride, vinylidene fluoride, hexafluoropropylene. Or a fluorine-containing monomer alone or a copolymer. In particular, polytetrafluoroethylene having fibril forming ability is preferred. Polytetrafluoroethylene having fibril-forming ability is a powder obtained by coagulating and drying latex obtained by emulsion polymerization of tetrafluoroethylene (so-called polytetrafluoroethylene fine powder, classified as type 3 in the ASTM standard) Thing). Alternatively, an aqueous dispersion (so-called polytetrafluoroethylene dispersion) produced by adding a surfactant to the latex and concentrating and stabilizing it may be mentioned.

  The molecular weight of the polytetrafluoroethylene having such fibril-forming ability is 1 million to 10 million, more preferably 2 million to 9 million in the number average molecular weight determined from the standard specific gravity.

  Further, the polytetrafluoroethylene having such fibril-forming ability preferably has a primary particle diameter in the range of 0.05 to 1.0 μm, more preferably 0.1 to 0.5 μm. In the case of using fine powder, the secondary particle diameter can be 1 to 1,000 μm, more preferably 10 to 500 μm.

  Such polytetrafluoroethylene has a melt-drip prevention performance during the combustion test of the test piece in the UL standard vertical combustion test. Specific examples of the polytetrafluoroethylene having such a fibril forming ability include Mitsui and DuPont. Teflon (registered trademark) 6J and Teflon (registered trademark) 30J manufactured by Fluorochemical Co., Ltd., Polyflon MPA FA-500, Polyflon F-201L and Polyflon D-1 manufactured by Daikin Chemical Industries, Ltd., and Asahi IC Fluorocarbon Examples thereof include CD076 manufactured by Polymers Co., Ltd.

  Such polytetrafluoroethylene is more preferably used in fin powder which has been subjected to various treatments to prevent secondary aggregation. Examples of such treatment include baking the surface of polytetrafluoroethylene. Moreover, as such a process, the surface of polytetrafluoroethylene having fibril-forming ability is coated with polytetrafluoroethylene having non-fibril-forming ability. In the present invention, polytetrafluoroethylene subjected to the latter treatment is more preferable. This is because, in the former case, the target fibril forming ability tends to be lowered. In such a case, it is preferable that the polytetrafluoroethylene having fibril forming ability is in the range of 70 to 95% by weight of the total amount. Further, the non-forming ability polytetrafluoroethylene has a molecular weight of 10,000 to 1,000,000, more preferably 10,000 to 800,000 in the number average molecular weight determined from the standard specific gravity.

Such polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) can be used in the form of an aqueous dispersion in addition to the solid form as described above.
Such polytetrafluoroethylene can be used in the form of an aqueous emulsion or dispersion in addition to the usual solid form, but the solid component is particularly preferred because the dispersant component tends to adversely affect the heat and moisture resistance. Can be used.

  In addition, polytetrafluoroethylene having such fibril-forming ability improves the dispersibility in the resin, and in order to obtain better appearance and mechanical properties, the polytetrafluoroethylene emulsion and the vinyl polymer emulsion are combined. An agglomerated mixture can also be mentioned as a preferred form.

  Here, as the vinyl polymer, a block copolymer composed of polypropylene, polyethylene, polystyrene, HIPS, AS resin, ABS resin, MBS resin, MABS resin, AAS resin, polymethyl (meth) acrylate, styrene and butadiene, and water thereof. Copolymer, block copolymer consisting of styrene and isoprene, and its hydrogenated copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene random copolymer and block copolymer, ethylene-butene random copolymer Polymers and block copolymers, copolymers of ethylene and α-olefin, copolymers of ethylene-unsaturated carboxylic acid esters such as ethylene-butyl acrylate, acrylic acid ester-butadiene copolymers such as butyl acrylate-butadiene , Rubber polymers such as polyalkyl (meth) acrylate, composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate, and vinyl monomers such as styrene, acrylonitrile, polyalkyl methacrylate, etc. And the like.

  In order to prepare such an agglomerated mixture, an aqueous emulsion of the above vinyl polymer having an average particle size of 0.01 to 1 μm, particularly 0.05 to 0.5 μm, is used. Mix with an aqueous emulsion of polytetrafluoroethylene having a diameter of 0.05 to 1.0 μm. Such an emulsion of polytetrafluoroethylene can be obtained by polymerizing polytetrafluoroethylene by emulsion polymerization using a fluorine-containing surfactant. In the emulsion polymerization, other copolymer components such as hexafluoropropylene can be copolymerized at 10% by weight or less of the whole polytetrafluoroethylene.

  In obtaining such an agglomerated mixture, an appropriate polytetrafluoroethylene emulsion usually has a solid content of 40 to 70% by weight, particularly 50 to 65% by weight, and a vinyl polymer emulsion has a content of 25 to 25%. Those having a solids content of 60% by weight, in particular 30-45% by weight, are used. Further, the proportion of polytetrafluoroethylene in the aggregated mixture is preferably 1 to 80% by weight, particularly 1 to 60% by weight, out of a total of 100% by weight with the vinyl polymer used in the aggregated mixture. A preferred example is a production method in which the above emulsion is mixed, stirred and mixed, poured into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, and separated and recovered by salting out and solidifying. In addition, a method of collecting the stirred mixed emulsion by a method such as spray drying or freeze drying can also be mentioned.

  Various forms of agglomerated mixture of an emulsion of polytetrafluoroethylene having a fibril-forming ability and an emulsion of vinyl polymer can be used. For example, a vinyl polymer is surrounded by polytetrafluoroethylene particles. Examples include a surrounded form, a form in which polytetrafluoroethylene is surrounded around a vinyl polymer, and a form in which several particles are aggregated with respect to one particle.

  Furthermore, the thing which graft-polymerized the same or another kind of vinyl polymer to the outer layer of the aggregation mixture can also be used. Preferred examples of the vinyl monomer include styrene, α-methylstyrene, methyl methacrylate, cyclohexyl acrylate, dodecyl methacrylate, dodecyl acrylate, acrylonitrile, and 2-ethylhexyl acrylate. May be copolymerized alone or copolymerized.

  Commercially available agglomerated mixtures of the above-mentioned polytetrafluoroethylene emulsion having a fibril-forming ability and a vinyl polymer emulsion are metablene “A3000” from Mitsubishi Rayon Co., Ltd., and “BLENDEX 449” from GE Specialty Chemicals. As a representative example.

  When the fluorine-containing resin is blended, the proportion is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of component A. If it is 0.01 parts by weight or more, sufficient melting and dropping prevention performance is easily obtained, and if it is 10 parts by weight or less, it is difficult to cause poor appearance and poor dispersion, and it is also economically advantageous.

  The flame retardant resin composition of the present invention includes various additives such as flame retardant aids, antioxidants, ultraviolet absorbers, light stabilizers and other deterioration inhibitors, lubricants, antistatic agents, and release agents. Further, reinforcing fibers such as plasticizers, glass fibers and carbon fibers, fillers such as talc, mica and wollastonite, and colorants such as pigments may be added. The amount of the additive used can be appropriately selected according to the type and purpose of the additive as long as the heat resistance, impact resistance, mechanical strength and the like are not impaired.

  The flame-retardant resin composition of the present invention is prepared by premixing components A to C and, if necessary, other components using a mixer such as a V-type blender, super mixer, super floater, Henschel mixer, etc. However, in many cases, the mixture is usually a mixture obtained by uniformly melt-mixing the preliminary mixture. Such a mixture can be obtained by kneading the preliminarily premixed mixture at a temperature of about 200 ° C. to 300 ° C., preferably about 210 ° C. to 280 ° C., and pelletizing the mixture. As the kneading means, various melt mixers such as a kneader, a single screw or a twin screw extruder can be used, but the resin composition is melted using a twin screw extruder and the liquid component is removed by a side feeder. It is often injected, extruded, and pelletized by a pelletizer.

  The flame-retardant resin composition of the present invention is useful as a material for molding various molded articles such as office automation equipment parts, home appliance parts, and automobile parts. Such a molded article can be produced by a conventional method, for example, by injection-molding a pellet-shaped flame-retardant resin composition using an injection molding machine, for example, at a cylinder temperature of about 200 to 280 ° C.

  EXAMPLES The present invention will be described below with reference to examples, but the scope of the present invention is not limited to these examples. The evaluation was performed by the following method.

(1) Colorability of resin composition 0.5 parts by weight of RTC-30 manufactured by Tyoxide as a colorant at the time of extrusion kneading of the resin composition is added to 100 parts by weight of the resin component, and the corner of the obtained resin composition A plate (length 50 mm × width 50 mm × thickness 5 mm) was injection molded. The resin composition is retained in the cylinder for 10 minutes at the time of injection molding, and then the hue of the square plate obtained in the third shot is measured with a spectroscopic colorimeter SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. The colorability was determined by ΔE with the composition to which no phosphorus compound was added. The judgment criteria were as follows.
ΔE less than 1.0: ○
ΔE of 1.0 or more: ×

(2) Hue of molded product From pellets obtained by extrusion kneading, a sample plate (the whole is 90 mm in length x 50 mm in width, 20 mm in thickness in the vertical direction is 3 mm, and 45 mm in length in the vertical direction). A plate having a step shape of 2 mm and a thickness of 25 mm in the longitudinal direction of 1 mm) was injection-molded, and the hue was visually determined. The judgment criteria were as follows.
Good hue: ○
Samples with slight burns: △
Samples with discoloration on the sample board: ×

(3) Appearance of molded product (with or without silver)
A sample plate was injection-molded from the pellets obtained by extrusion kneading, and the presence or absence of silver was visually determined for the appearance of the molded product. The judgment criteria were as follows.
Without silver: ○
Some silver can be seen on the sample board: △
Samples with silver on the sample board: ×

(4) Mold Contamination The mold contamination after the sample molding of the resin composition was performed for 500 shots was judged visually. The judgment criteria were as follows.
No mold contamination: ○
Small mold contamination: △
Large mold contamination: ×

(5) Heat resistance (deflection temperature under load; HDT)
The deflection temperature under load (HDT) was measured at a load of 18.5 kg using a 6.35 mm (1/4 inch) test piece by a method according to ASTM-D648. Also, the load deflection temperature retention ratio (M) is determined from the load deflection temperature x (° C.) of the molded product from the used base resin (component A) and the flame retardant resin composition (mixture of base resin and component C). The deflection temperature under load y (° C.) of the molded product was measured and calculated by the calculation formula of M = (y / x) × 100 (%).

(6) Fluidity (MVR)
This was performed in accordance with ISO-1133. The measurement conditions were 230 ° C. and 3.8 kg load.

(7) Flame retardancy (UL-94 evaluation)
Flame retardance is defined in US UL standard UL-94 as an evaluation measure of flame retardance using a test piece having a thickness of 3.2 mm (1/8 inch) and 1.6 mm (1/16 inch). Evaluation was performed according to the vertical combustion test. The table shows the total number of seconds for the UL standard and burning time.
In the UL-94 vertical combustion test, five test pieces are performed as a set of tests, and each test piece repeats flame for 10 seconds twice. However, this does not apply to specimens that are burned down by the first flame. After the first flame, the combustion time after removing the flame is measured, and after the flame is extinguished, the second flame is fired. After the second flame, the burning time after removing the flame is measured. In a set of five tests, a total of 10 burning times can be measured, all burning times are extinguished within 10 seconds, the total of 10 burning times is within 50 seconds, and the dripping material is cotton. V-0 is the one that does not ignite, extinguishes within 30 seconds of any combustion time, the sum of the 10 combustion times is within 250 seconds, and the drop does not cause cotton ignition. 1. All the combustion times are extinguished within 30 seconds, the total of the 10 combustion times is within 250 seconds, and the dripping material causes cotton ignition is V-2, and those below this evaluation standard It was set to notV.

(8) Flame retardancy (oxygen index; LOI evaluation)
This was carried out in accordance with a combustion test method for polymer materials according to the JIS-K-7201 oxygen index method.

(9) Reduced viscosity ηsp / C
A mixed solvent of 18 ml of methyl ethyl ketone and 2 ml of methanol is added to 1 g of rubber-modified styrenic resin, shaken at 25 ° C. for 2 hours, and centrifuged at 4000 rpm for 30 minutes. The supernatant liquid was taken out and the resin component was precipitated with methanol, followed by drying. 0.1 g of the resin thus obtained is dissolved in toluene to obtain a 0.5 g / dl solution, and 10 ml of this solution is placed in an Ostwald viscometer having a capillary diameter of about 0.3 mm, and this solution is added at 30 ° C. The flow down time t ₁ of the solution was measured. On the other hand, the falling number of seconds t ₀ of toluene was measured by the same viscometer, and calculated by the following equation. It is preferable that the falling time number t ₀ at this time toluene is more than 240 seconds.
ηsp / C = (t ₁ / t ₀ −1) / C (C: polymer concentration g / dl)

(10) Amount of rubber-like polymer component in the rubber-modified styrene resin The nuclear magnetic resonance of a hydrogen atom was measured by a nuclear magnetic resonance measuring apparatus (manufactured by Varian, UNITY300), and the rubbery state was determined from the molar ratio of the styrene unit to the butadiene unit. The amount of polymer component was calculated.

(11) Acid value of phosphorus compound Measurement was carried out according to JIS-K-3504.

(12) HPLC purity of phosphorus compound A sample was dissolved in a mixed solution of acetonitrile and water of 6.5: 3.5 (volume ratio), and 5 μl thereof was injected into the column. As the column, Develosil ODS-7 300 mm × 4 mmφ manufactured by Nomura Chemical Co., Ltd. was used, and the column temperature was 40 ° C. The detector used was UV-260 nm.

(13) ³¹ PNMR purity of phosphorus compound The nuclear magnetic resonance of a phosphorus atom was measured with a nuclear magnetic resonance measuring apparatus (manufactured by JEOL, JNM-AL400) (DMSO-d ₆ , 162 MHz, integration number 3072), and the integral area ratio Was the ³¹ PNMR purity of the phosphorus compound.
The ³¹ PNMR chart was expanded with respect to the following expansion range, and impurities were confirmed. As the magnification, the main peak is expanded in the vertical direction until the top of the main peak reaches the top edge of the computer screen, and the height of the main peak on that screen is 1/200 times the height of the computer screen. Enlarged to be at the top edge. In the horizontal direction, each of the following expansion ranges was expanded to the maximum width on the computer screen. If the expansion is insufficient, impurities cannot be confirmed, and the apparent ³¹ PNMR purity may be improved.
Expansion range 1: 219 ppm to 216 ppm
Expansion range 2: 180 ppm to 177 ppm
Expansion range 3: 149 ppm to 145 ppm
Expansion range 4: 124 ppm to 121 ppm
Expansion range 5: 93 ppm to 90 ppm
Expansion range 6: 27 ppm to 23 ppm
Expansion range 7: 23 ppm to 18 ppm
Expansion range 8: 9 ppm to -4 ppm
Expansion range 9: −6 ppm to −15 ppm

(14) Heated weight reduction residue It was measured using a thermogravimetric balance test (TGA method). Using a thermogravimetric measuring device TGA-50 manufactured by Shimadzu Corporation, the temperature was raised at 10 ° C./min in a nitrogen stream, and the remaining amount (%) at 500 ° C. was defined as the residual weight loss.

[Preparation Example 1]
Preparation of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dibenzyl-3,9-dioxide (FR-1) Thermometer, condenser, and dropping funnel The reaction vessel was charged with 816.9 g (6.0 mol) of pentaerythritol, 19.0 g (0.24 mol) of pyridine, and 2250.4 g (24.4 mol) of toluene and stirred. To the reaction vessel, 1651.8 g (12.0 mol) of phosphorus trichloride was added using the dropping funnel, and the mixture was heated and stirred at 60 ° C. after the addition was completed. After the reaction, the reaction mixture was cooled to room temperature, and 26.50 parts of methylene chloride was added to the resulting reaction product, and 889.4 g (12.0 moles) of tertiary butanol and 150.2 g (1.77 moles) of methylene chloride were cooled with ice. Mol) was added dropwise. The obtained crystals were washed with toluene and methylene chloride and filtered. The resulting braze Tobutsu 80 ° C., dried 12 hours at 1.33 × ¹⁰ 2 Pa, to give a white solid 1341.1g (5.88 moles). The obtained solid was found to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dihydro-3,9-dioxide according to ³¹ P, ¹ HNMR spectrum. confirmed.

2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dihydro-3,9-dioxide obtained in a reaction vessel equipped with a thermometer, condenser and dropping funnel 1341.0 g (5.88 mol) and DMF6534.2 g (89.39 mol) were charged and stirred. Sodium methoxide 648.7 g (12.01 mol) was added to the reaction vessel under ice cooling. After stirring for 2 hours under ice cooling, the mixture was stirred for 5 hours at room temperature. After further distilling off DMF, 2613.7 g (35.76 mol) of DMF was added, and 2037.79 g (11.91 mol) of benzyl bromide was added dropwise to the reaction mixture under ice cooling. After stirring for 3 hours under ice cooling, DMF was distilled off, 8 L of water was added, and the precipitated solid was collected by filtration and washed twice with 2 L of water. The obtained crude product and 4 L of methanol were put into a reaction vessel equipped with a condenser and a stirrer and refluxed for about 2 hours. After cooling to room temperature, the crystals were separated by filtration, washed with 2 L of methanol, and the obtained filtered product was dried at 120 ° C. and 1.33 × 10 ² Pa for 19 hours to obtain 1863.5 g of white scaly crystals ( 4.56 mol) was obtained. The crystals obtained are ³¹ P, ¹ HNMR spectrum and elemental analysis with 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dibenzyl-3,9-dioxide. I confirmed it. The yield was 76%, the residue from weight loss by heating was 0.85% (see FIG. 1), the acid value was 0.06 mgKOH / g, the HPLC purity was 99%, and the ³¹ PNMR purity was 99%.
¹ H-NMR (DMSO-d ₆ , 400 MHz): δ 7.2-7.4 (m, 10H), 4.1-4.5 (m, 8H), 3.5 (d, 4H), ³¹ P -NMR (DMSO-d ₆ , 162 MHz): δ 21.0 (S), melting point: 255-256 ° C, elemental analysis calculated: C, 55.89; H, 5.43, measured: C, 56.24 H, 5.35

[Preparation Example 2]
Preparation of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dibenzyl-3,9-dioxide (FR-2) Reaction with stirrer, thermometer, condenser In a container, 22,9-dibenzyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane 22.55 g (0.055 mol), benzyl bromide 19.01 g (0.11 mol) ) And 33.54 g (0.32 mol) of xylene, and dry nitrogen was allowed to flow while stirring at room temperature. Next, heating was started in an oil bath, and the mixture was heated and stirred at a reflux temperature (about 130 ° C.) for 4 hours. After heating, the mixture was allowed to cool to room temperature, 20 mL of xylene was added, and the mixture was further stirred for 30 minutes. The precipitated crystals were separated by filtration and washed twice with 20 mL of xylene. The obtained crude product and 100 mL of methanol were placed in a reaction vessel equipped with a condenser and a stirrer and refluxed for about 2 hours. After cooling to room temperature, the crystals were separated by filtration and washed with 20 mL of methanol, and the obtained filtered product was dried at 120 ° C. and 1.33 × 10 ² Pa for 19 hours to obtain white scaly crystals. The product was confirmed to be bisbenzylpentaerythritol diphosphonate by mass spectral analysis, ¹ H, ³¹ P nuclear magnetic resonance spectral analysis and elemental analysis. The yield was 20.60 g, the yield was 91%, the heating weight loss residue was 0.46% (see FIG. 2), the acid value was 0.05 mg KOH / g, the HPLC purity was 99%, and the ³¹ PNMR purity was 99%. It was.
¹ H-NMR (DMSO-d ₆ , 400 MHz): δ 7.2-7.4 (m, 10H), 4.1-4.5 (m, 8H), 3.5 (d, 4H), ³¹ P _{-NMR (DMSO-d 6, 162MHz} ): δ21.0 (S), melting point: 257 ° C.

[Preparation Example 3]
Preparation of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dibenzyl-3,9-dioxide (FR-3) Reaction with stirrer, thermometer, condenser In a container, 22,9-dibenzyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane 22.55 g (0.055 mol), benzyl bromide 19.01 g (0.11 mol) ) And 33.54 g (0.32 mol) of xylene, and dry nitrogen was allowed to flow while stirring at room temperature. Next, heating was started in an oil bath, and the mixture was heated and stirred at a reflux temperature (about 130 ° C.) for 4 hours. After heating, the mixture was allowed to cool to room temperature, 20 mL of xylene was added, and the mixture was further stirred for 30 minutes. The precipitated crystals were separated by filtration, and the obtained filtered product was dried under reduced pressure at 100 ° C. and 1.33 × 10 ² Pa. The white solid obtained was 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dibenzyl-3,9-dioxide by ¹ H, ³¹ P-NMR. I confirmed that there was. The residue from weight loss by heating was 10.1%, the acid value was 2.5 mgKOH / g, the HPLC purity was 84%, and the ³¹ PNMR purity was 85%.

The following were used for each component used in Examples and Comparative Examples.
(A) Styrenic resin (component A)
(I) Commercially available high impact polystyrene (A & M Styron 492R; reduced viscosity ηsp / C (0.5 g / dl, toluene solution, measured at 30 ° C.) is 0.96 dl / g, rubbery polymer is 6.5 % By weight) was used (hereinafter referred to as HIPS-1).
(Ii) Commercially available impact-resistant polystyrene (A & M Styron H9152; reduced viscosity ηsp / C (0.5 g / dl, toluene solution, measured at 30 ° C.) is 0.82 dl / g, rubbery polymer is 6.1 % By weight) was used (hereinafter referred to as HIPS-2).
(Iii) Commercially available high-impact polystyrene (A & M Styron 433; reduced viscosity ηsp / C (0.5 g / dl, toluene solution, measured at 30 ° C.) is 0.78 dl / g, rubbery polymer is 5.2 % By weight) was used (hereinafter referred to as HIPS-3).

(B) Organophosphorus compound (component C)
(I) 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-dibenzyl-3,9-dioxide synthesized in Preparation Example 1 In the general formula (4) The organophosphorus compound shown (hereinafter referred to as FR-1).
(Ii) 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-dibenzyl-3,9-dioxide synthesized in Preparation Example 2 In the general formula (4) Organophosphorus compound shown (hereinafter referred to as FR-2).
(Iii) 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-dibenzyl-3,9-dioxide synthesized in Preparation Example 3 In the general formula (4) Organophosphorus compound shown (hereinafter referred to as FR-3).

(C) Other organophosphorus compounds (component D)
(I) Triphenyl phosphate A commercially available aromatic phosphate (TPP manufactured by Daihachi Chemical Industry) was used (hereinafter referred to as FR-4).
(Ii) 1,3-phenylenebis [di (2,6-dimethylphenyl) phosphate]
In the general formula (D-3), Ar ⁴ is a phenylene group, Q ¹ , Q ² , Q ³ and Q ⁴ are 2,6-dimethylphenyl groups, and m is an organophosphate compound in which 1, A commercially available aromatic phosphate ester (Adeka Stub FP-500 manufactured by Asahi Denka Kogyo Co., Ltd.) was used (hereinafter referred to as FR-5).
(Iii) Resorcinol bis (diphenyl phosphate)
In the general formula (D-3), Ar ⁴ is a phenylene group, Q ¹ , Q ² , Q ³ and Q ⁴ are phenyl groups, and m is 0, 1, 2 (m = 1 is a main component). It is a phosphate ester compound, and a commercially available aromatic phosphate ester (CR-733S manufactured by Daihachi Chemical Industry) was used (hereinafter referred to as FR-6).
(Iv) Bisphenol A bis (diphenyl phosphate)
In the general formula (D-4), Ar ⁴ -Z-Ar ⁵ is an bisphenol A, Q ¹ , Q ² , Q ³ and Q ⁴ are phenyl groups, and m is an organic phosphate ester compound of 1. A commercially available aromatic phosphate ester (CR-741 manufactured by Daihachi Chemical Industry) was used (hereinafter referred to as FR-7).

[Examples 1 to 24 and Comparative Examples 1 to 26]
Each component shown in Tables 1 to 5 is blended in a tumbler in the amount (parts by weight) shown in Tables 1 to 5, and pelletized at a cylinder temperature of 220 ° C. with a 15 mmφ twin screw extruder (Technobel, KZW15). The obtained pellets were dried with a hot air dryer at 70 ° C. for 4 hours. Each test piece was molded from the pellets with an injection molding machine (manufactured by Nippon Steel Works, J75Si) at a molding temperature of 210 ° C and a mold temperature of 40 ° C. The results of evaluation using this test piece are shown in Tables 1 to 5.

  The flame-retardant resin composition of the present invention is useful as a material for molding various molded products such as office automation equipment parts, home appliance parts, electric / electronic parts, and automobile parts.

Claims (12)

(A) A resin composition comprising 100 parts by weight of a styrene-based resin (component A) and (C) 1 to 100 parts by weight of an organophosphorus compound (component C) represented by the following formula (1), wherein the organophosphorus compound (C component) is
(I) Heated weight reduction residue at 500 ° C. is 10% or less,
(Ii) A flame-retardant styrene resin composition characterized by satisfying an HPLC purity of 90% or more and (iii) an acid value of 0.5 mgKOH / g or less.

(In the formula, Ar ¹ and Ar ² may be the same or different and are phenyl groups which may have a substituent.) The flame retardant styrene resin composition according to claim 1, wherein the organic phosphorus compound of component C is an organic phosphorus compound represented by the following formula (2).

  The flame-retardant styrene resin composition according to claim 1, wherein the component A styrene resin is a rubber-modified styrene resin.   The flame-retardant styrene-based resin composition according to claim 1, wherein the component A styrene-based resin is high-impact polystyrene (HIPS).   The component A styrene-based resin has a reduced viscosity ηsp / C measured by the method described in the text of 0.2 to 1.5 dl / g, and the rubbery polymer component content measured by the method described in the text. The flame-retardant styrene resin composition according to claim 1, which is a rubber-modified styrene resin having a content of 1 to 50% by weight.   The flame-retardant styrene-based resin composition according to claim 1, wherein the weight loss residue after heating at 500 ° C of the organophosphorus compound of component C is 8% or less.   The flame-retardant styrene resin composition according to claim 1, wherein the HPLC purity of the organic phosphorus compound of component C is 95% or more.   The flame retardant styrenic resin composition according to claim 1, wherein the acid value of the organic phosphorus compound of component C is 0.4 mgKOH / g or less.   The flame-retardant styrene resin composition according to claim 1, wherein the C component is in a ratio of 2 to 50 parts by weight with respect to 100 parts by weight of the A component.   When the flame retardancy level of UL-94 is at least V-2 and the flame retardance level is V-2 with a test piece having a thickness of 1.6 mm, the average burning time is within 10 seconds and the oxygen index (LOI) ) Can achieve 22.0 or more. The flame-retardant styrene-based resin composition according to claim 1.   The flame-retardant styrenic resin composition according to claim 1, which contains substantially no halogen.   A molded article formed from the flame retardant resin composition according to claim 1.