JP2016011326A - Flame-retardant resin composition, flame-retardant master batch, molded body, and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant resin composition including a polycarbonate resin excellent in flame retardance with use of a non-halogen flame retardant, a flame-retardant master batch, a flame-retardant resin molding, and a manufacturing method thereof.SOLUTION: The method for manufacturing a flame-retardant resin composition includes melt-kneading a polycarbonate resin (A) and a phosphorus atom-containing oligomer (B). A flame-retardant resin excellent in flame retardance is obtained by the method. A flame-retardant master batch, a flame-retardant resin molding, and a manufacturing method thereof are also provided.

Description

  The present invention relates to a flame retardant resin composition, and more particularly to a flame retardant resin composition excellent in flame retardancy and moldability without impairing the original mechanical properties of the polycarbonate resin (A) and a molded product thereof.

  Polycarbonate resins are widely used as materials for OA equipment, electrical / electronic parts, household goods, building parts, automobile parts, etc. due to their excellent impact resistance, heat resistance, electrical characteristics, and the like. Polycarbonate resins have a high flame retardancy compared to polystyrene resins and the like, and are generally known to exhibit self-extinguishing properties (UL94 V-2) at an appropriate thickness without the addition of a flame retardant. It has been.

  However, the flame retardancy required for insulating materials in the OA field and the electric / electronic field is more severe and V-0 is required. As an existing method for achieving V-0, a method of making a flame retardant by blending a halogen-based flame retardant such as a bromine compound having high flame retardant efficiency and antimony oxide with a resin is employed. However, since the problem that halogen-based flame retardants generate dioxins during combustion has been highlighted, there has been a demand for dehalogenation of flame retardants used in the market. Therefore, as non-halogen flame retardants, flame retardants exhibiting excellent flame retardancy such as condensed phosphate esters, aluminum phosphinates, and melamine polyphosphates are commercially available. Proposed.

For example, a condensed phosphate ester is added to a polycarbonate resin (see Patent Document 1), an aluminum phosphinate is added (see Patent Document 2), and melamine polyphosphate is added (Patent Document 3). Have been proposed).
However, since the polycarbonate resin itself is extremely flammable, these flame retardants are insufficient in flame retardancy, and when trying to obtain excellent flame retardancy, the content ratio to the polycarbonate resin has to be increased. .

  Therefore, when the content ratio of the flame retardant increases, not only the mechanical properties tend to decrease, but also extrusion stability during melt-kneading, molding processability such as suppression of yarn breakage during molding and suppression of drawing There is a room for improvement because it tends to decrease, and further, the excellent transparency of the polycarbonate resin tends to decrease.

JP-A-8-302178 JP 2005-179360 A International Publication No. 03/46084 Pamphlet

  Accordingly, the first problem to be solved by the present invention is a polycarbonate resin composition using a non-halogen flame retardant, maintaining the mechanical properties inherent to the polycarbonate resin, and having excellent flame retardancy, and molded articles thereof Is to provide.

  Furthermore, the second problem to be solved by the present invention is to use a non-halogen flame retardant, not only the mechanical properties inherent in polycarbonate resin, but also the extrusion stability during melt-kneading and yarn breakage during molding. An object of the present invention is to provide a polycarbonate resin composition having excellent flame retardancy while maintaining molding processability such as suppression or suppression of drawing and a molded product thereof.

  Furthermore, the third problem to be solved by the present invention is to use a non-halogen flame retardant, not only the mechanical properties inherent in polycarbonate resin, but also the extrusion stability during melt-kneading and yarn breakage during molding. An object of the present invention is to provide a polycarbonate resin composition having excellent flame retardancy and transparency and a molded product thereof while maintaining molding processability such as suppression or suppression of drawing.

  As a result of various studies, the inventors of the present application have found that a polycarbonate resin composition obtained by blending a polycarbonate resin with a phosphorus atom-containing phenolic oligomer obtained by reacting HCA or a derivative thereof with an o-hydroxybenzaldehyde compound, and a polycarbonate resin composition thereof The present inventors have found that the molded product has excellent flame retardancy and have completed the present invention.

That is, the present invention
(1) A flame retardant resin composition containing a polycarbonate resin (A) and a phosphorus atom-containing oligomer (B) as essential components, wherein the phosphorus atom-containing oligomer (B) is added to 100 parts by mass of the polycarbonate resin (A). ) In the range of 3 to 25 parts by mass, and the phosphorus atom-containing oligomer (B) is represented by the following structural formula (1)

（式中、Ｒ^１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基を表し、ｎは繰り返し単位で１以上であり、Ｘは下記構造式（ｘ１）又は（ｘ２）

(Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, n is a repeating unit of 1 or more, and X is a structural formula shown below. (X1) or (x2)

で表される構造部位であり、Ｙは水素原子、水酸基又は前記構造式（ｘ１）若しくは（ｘ２）で表される構造部位であり、また、該構造式（ｘ１）又は（ｘ２）中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基を表す。）で表されることを特徴とする難燃性樹脂組成物に関する。

Y is a hydrogen atom, a hydroxyl group, or a structural moiety represented by the structural formula (x1) or (x2), and in the structural formula (x1) or (x2), R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group. It is related with the flame-retardant resin composition characterized by being represented by this.

The present invention also provides:
(2) A method for producing a flame-retardant resin composition in which a polycarbonate resin (A) and a phosphorus atom-containing oligomer (B) are melt-kneaded, and the phosphorus atom-containing oligomer (100 parts by mass) with respect to 100 parts by mass of the polycarbonate resin (A). B) is contained in the range of 3 to 25 parts by mass, and the phosphorus atom-containing oligomer (B) is represented by the following structural formula (1)

（式中、Ｒ^１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基を表し、ｎは繰り返し単位で１以上であり、Ｘは下記構造式（ｘ１）又は（ｘ２）

(Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, n is a repeating unit of 1 or more, and X is a structural formula shown below. (X1) or (x2)

で表される構造部位であり、Ｙは水素原子、水酸基又は前記構造式（ｘ１）若しくは（ｘ２）で表される構造部位であり、また、該構造式（ｘ１）又は（ｘ２）中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基を表す。）で表されることを特徴とする難燃性樹脂組成物の製造方法に関する。

Y is a hydrogen atom, a hydroxyl group, or a structural moiety represented by the structural formula (x1) or (x2), and in the structural formula (x1) or (x2), R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group. It is related with the manufacturing method of the flame-retardant resin composition characterized by these.

Furthermore, the present invention provides
(3) Step (1) for producing a flame-retardant masterbatch by melt-kneading the polycarbonate resin (A) and the phosphorus atom-containing oligomer (B) in advance, and the flame-retardant masterbatch obtained in the step (1) Furthermore, a method for producing a flame retardant resin composition comprising a step (2) of melt-kneading the thermoplastic resin (E),
The phosphorus atom-containing oligomer (B) is
The following structural formula (1)

（式中、Ｒ^１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基を表し、ｎは繰り返し単位で１以上であり、Ｘは下記構造式（ｘ１）又は（ｘ２）

(Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, n is a repeating unit of 1 or more, and X is a structural formula shown below. (X1) or (x2)

で表される構造部位であり、Ｙは水素原子、水酸基又は前記構造式（ｘ１）若しくは（ｘ２）で表される構造部位であり、また、該構造式（ｘ１）又は（ｘ２）中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基を表す。）で表されることを特徴とする難燃性樹脂組成物の製造方法に関する。

Y is a hydrogen atom, a hydroxyl group, or a structural moiety represented by the structural formula (x1) or (x2), and in the structural formula (x1) or (x2), R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group. It is related with the manufacturing method of the flame-retardant resin composition characterized by these.

Furthermore, the present invention provides
(4) A flame retardant masterbatch containing polycarbonate resin (A) and phosphorus atom-containing oligomer (B) as essential components,
The phosphorus atom-containing oligomer (B) is represented by the following structural formula (1)

（式中、Ｒ^１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基を表し、ｎは繰り返し単位で１以上であり、Ｘは下記構造式（ｘ１）又は（ｘ２）

(Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, n is a repeating unit of 1 or more, and X is a structural formula shown below. (X1) or (x2)

で表される構造部位であり、Ｙは水素原子、水酸基又は前記構造式（ｘ１）若しくは（ｘ２）で表される構造部位であり、また、該構造式（ｘ１）又は（ｘ２）中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基を表す。）で表されること、
ポリカーボネート樹脂（Ａ）１００質量部に対し、前記リン原子含有オリゴマー（Ｂ）を５〜３０質量部の範囲となる含有割合で含有する難燃性マスターバッチに関する。

Y is a hydrogen atom, a hydroxyl group, or a structural moiety represented by the structural formula (x1) or (x2), and in the structural formula (x1) or (x2), R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group. ),
It is related with the flame-retardant masterbatch which contains the said phosphorus atom containing oligomer (B) in the content rate used as the range of 5-30 mass parts with respect to 100 mass parts of polycarbonate resin (A).

  Furthermore, this invention relates to the molded object, fiber, film, or sheet | seat obtained by shape | molding the said flame-retardant resin composition.

According to the present invention, it is possible to provide a polycarbonate resin composition having excellent flame retardancy and a molded product thereof using a non-halogen flame retardant while maintaining the mechanical properties inherent to the polycarbonate resin.
In addition, according to the present invention, a non-halogen flame retardant is used and not only the mechanical properties inherent in polycarbonate resin, but also the extrusion stability during melt-kneading, the yarn breakage during molding or the suppression of drawing, etc. It is possible to provide a polycarbonate resin composition having excellent flame retardancy and a molded product thereof while maintaining the properties.
Further, according to the present invention, non-halogen flame retardant is used, and not only the mechanical properties inherent in polycarbonate resin, but also extrusion stability during melt-kneading, yarn breakage during molding, or suppression of drawing It is possible to provide a polycarbonate resin composition having excellent flame retardancy and transparency and a molded product thereof while maintaining the properties.

  The flame retardant resin composition of the present invention is a flame retardant resin composition containing a polycarbonate resin (A) and a phosphorus atom-containing oligomer (B) as essential components, wherein the phosphorus atom-containing oligomer (B) is: The following structural formula (1)

（式中、Ｒ^１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基を表し、ｎは繰り返し単位で１以上であり、Ｘは下記構造式（ｘ１）又は（ｘ２）

(Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, n is a repeating unit of 1 or more, and X is a structural formula shown below. (X1) or (x2)

で表される構造部位であり、Ｙは水素原子、水酸基又は前記構造式（ｘ１）若しくは（ｘ２）で表される構造部位であり、また、該構造式（ｘ１）又は（ｘ２）中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基を表す。）で表されることを特徴とする。

Y is a hydrogen atom, a hydroxyl group, or a structural moiety represented by the structural formula (x1) or (x2), and in the structural formula (x1) or (x2), R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group. ).

・ Polycarbonate resin (A)
There is no restriction | limiting in particular as polycarbonate resin used for this invention, A various thing is mentioned. Usually, an aromatic polycarbonate produced by a reaction between a dihydric phenol and a carbonate precursor can be used. That is, a product prepared by reacting a dihydric phenol and a carbonate precursor by a solution method or a melting method, that is, a reaction of a dihydric phenol and phosgene, a transesterification method of a dihydric phenol and diphenyl carbonate or the like is used. be able to.

  Various divalent phenols can be mentioned, and in particular, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxy). Phenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) oxide, Examples thereof include bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, and bis (4-hydroxyphenyl) ketone.

  Particularly preferred dihydric phenols are bis (hydroxyphenyl) alkanes, especially those using bisphenol A as the main raw material. The carbonate precursor is carbonyl halide, carbonyl ester, haloformate or the like, and specifically, phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, diethyl carbonate or the like. In addition, examples of the dihydric phenol include hydroquinone, resorcin, and catechol. These dihydric phenols may be used alone or in combination of two or more.

  The polycarbonate resin may have a branched structure. Examples of the branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-bidoxy Phenyl) -1,3,5-triisopropylbenzene, phloroglysin, trimellitic acid, isatin bis (o-cresol), etc. In order to adjust the molecular weight, phenol, pt-butylphenol, p- t-octylphenol, p-cumylphenol and the like are used.

The polycarbonate resin that can be used in the present invention may be a copolymer having a polycarbonate part and a polyorganosiloxane part, or a polycarbonate resin containing this copolymer. Further, it may be a polyester-polycarbonate resin obtained by polymerizing a polycarbonate in the presence of a bifunctional carboxylic acid such as terephthalic acid or an ester precursor such as an ester-forming derivative thereof. A mixture of various polycarbonate resins can also be used. The polycarbonate resin that can be used in the present invention is preferably substantially free of halogen in the structure. From the viewpoint of mechanical strength and moldability, the viscosity average molecular weight is preferably 10,000 to 100,000, and more preferably 14,000 to 40,000.
The viscosity average molecular weight of the component (A) in the present invention is calculated by inserting a specific viscosity (ηsp) obtained by measuring a solution of an aromatic polycarbonate resin at 20 ° C. in 100 cm ³ of methylene chloride at 20 ° C. into the following equation. It is what I asked for.
(Ηsp) / C = [η] + 0.45 × [η] ^2C
[Η] = 1.23 × 10 ⁻⁵ M ^0.83
(Where [η] is the intrinsic viscosity and C is the polymer concentration)

・ Phosphorus atom-containing oligomer (B)
Next, as described above, the phosphorus atom-containing oligomer (B) used in the present invention has the following structural formula (1).

（式中、Ｒ^１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基を表し、ｎは繰り返し単位で１以上であり、Ｘは下記構造式（ｘ１）又は（ｘ２）

(Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, n is a repeating unit of 1 or more, and X is a structural formula shown below. (X1) or (x2)

で表される構造部位であり、Ｙは水素原子、水酸基又は前記構造式（ｘ１）若しくは（ｘ２）で表される構造部位であり、また、該構造式（ｘ１）又は（ｘ２）中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基を表す。）で表され、かつ、前記構造式（１）においてｎが２以上の成分の含有率が、ＧＰＣ測定におけるピーク面積基準で５〜９０％の範囲にあることを特徴とするものである。本発明では、斯かるリン原子含有オリゴマー（Ｂ）を難燃剤成分として用いることにより、溶融混練時のブリードを抑えかつ金型からの離型性を良好に維持しながらも、薄肉成型品、成型品の薄肉部、薄膜部における難燃性能を飛躍的に高めることができるものである。

Y is a hydrogen atom, a hydroxyl group, or a structural moiety represented by the structural formula (x1) or (x2), and in the structural formula (x1) or (x2), R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group. In the structural formula (1), the content of components having n of 2 or more is in the range of 5 to 90% on the basis of the peak area in GPC measurement. In the present invention, by using such a phosphorus atom-containing oligomer (B) as a flame retardant component, a thin-walled molded product, a molded product can be obtained while suppressing bleeding at the time of melt-kneading and maintaining good releasability from the mold. The flame retardancy in the thin-walled part and the thin-film part of the product can be dramatically improved.

  The phosphorus atom-containing oligomer (B) thus has the following structural formula (2) in the structural formula (1).

（式中、Ｒ^１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基を表し、ｎは繰り返し単位で１以上であり、Ｘは下記構造式（ｘ１）又は（ｘ２）

(Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, n is a repeating unit of 1 or more, and X is a structural formula shown below. (X1) or (x2)

（前記構造式（ｘ１）又は（ｘ２）中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基を表す。）で表される構造部位である。）で表される構造部位を繰り返し単位として有することから、成型品における難燃性、特に薄肉部における難燃性が飛躍的に向上する。

(In the structural formula (x1) or (x2), R ² , R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group. It is a structural site represented by. ) As a repeating unit, the flame retardancy in the molded product, particularly the flame retardance in the thin-walled portion, is dramatically improved.

  Here, specific examples of the structural portion represented in the structural formula (2) include those represented by the following structural formulas (2-1) to (2-8).

  In the present invention, X in the structural formula (1) is selected from the structural formula (x1) and the structural formula (x2), and may be the structural formula (x1) particularly from the viewpoint of flame retardancy. Therefore, among the structural sites represented by the structural formula (2), the structural formulas (2-1), (2-2), (2-3) corresponding to the structural formula (x-1) are preferable. ) And (2-4) are preferred.

  In the structural formula (1), Y is a hydrogen atom, a hydroxyl group, or a structural site represented by the structural formula (x1) or (x2), and these coexist in the phosphorus atom-containing oligomer. May be. In the present invention, Y is preferably a hydrogen atom or a structural part represented by the structural formula (x1) or (x2) from the viewpoint of heat resistance or flame retardancy, and in particular from the viewpoint of flame retardancy. It is preferable that it is Formula (x1).

  Further, as described above, the phosphorus atom-containing oligomer has n in the range of 1 or more in the above structural formula (1), preferably in the range of 1 to 10. Furthermore, when the content of the component having n of 2 or more is in the range of 5 to 90% on the basis of the peak area in the GPC measurement, the compatibility with the resin (A) is excellent, and the flame retardancy of the thin-walled portion is excellent. It is more preferable because it is remarkably excellent.

  Here, the content of the component having n of 2 or more in the structural formula (1) refers to the ratio of the peak area of less than 36.0 minutes in the GPC chart measured under the following conditions.

<GPC measurement conditions>
GPC: Measurement conditions are as follows.
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation

Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”

Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation

Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate 1.0ml / min

  Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.

(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation

  Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

NMR: JEOL JNM-ECA500 nuclear magnetic resonance apparatus Magnetic field strength: 500 MHz
Pulse width: 3.25 μsec
Integration count: 8000 times Solvent: DMSO-d6
Sample concentration: 30 wt%

MS: Shimazu Biotech AXIMA-TOF2
Measurement mode: linear
Integration frequency: 50 times Sample composition: sample / DHBA / NaTFA / THF = 9.4 mg / 104.7 mg / 6.3 mg / 1 ml

  In the present invention, when the content of the component having n of 2 or more is 5% or more on the basis of the peak area in GPC measurement, the compatibility with the resin (A) is good and the bleed is less during melt kneading. On the other hand, when it is 90% or less, the fluidity at the time of melt-kneading is good and the impact strength is also excellent. Here, the other component is a component having n = 1, and therefore, in the phosphorus atom-containing oligomer of the present invention, the component having n = 1 is 95 to 10% on the basis of the peak area in GPC measurement. In the present invention, the content ratio of the component having n of 2 or more is such that the compatibility with the resin (A) and the workability are maintained at a high level, and the excellent flame retardancy can be further improved in the cured product. It is preferable that the content ratio of the component having n of 1 is 60 to 25%.

  More specifically, the content of the component with n = 1 is 95 to 10%, the content of the component with n = 2 is 3-50%, and the content of the component with n = 3 or more is 1-45. % Is preferable from the viewpoint of solvent solubility, in particular, the content of the component where n is 1 is 60 to 25%, the content of the component where n is 2 is 10 to 45%, and n is 3 or more. The content of the component is preferably 10 to 40% from the viewpoint that the balance between workability and flame retardancy is excellent.

  As described above, Y in the structural formula (1) is preferably the structural formula (x1). Therefore, in the structural formula (1), Y is the structural formula (x1), and n Is preferably a phosphorus atom-containing oligomer having a content of 2 or more components of 40 to 75% and a content of n of 1 of 60 to 25% from the viewpoint of flame retardancy and heat resistance. In (1), Y is the structural formula (x1), the content of the component in which n is 1 is 95 to 10%, the content of the component in which n is 2 is 3 to 50%, and n is 3 or more Is preferably from 1 to 45% from the viewpoint of preventing bleeding, improving flame retardancy, and being excellent in compatibility with the resin (A). In particular, Y is the structural formula (x1). And the content of the component with n = 1 is 60-25%, the content of the component with n = 2 is 10-45%, and Are particularly preferred from the viewpoint that the content of the three or more component is phosphorus atom-containing oligomer is 10 to 40% (B) excellent in these performance balance.

  In addition, the phosphorus atom-containing oligomer (B) described above preferably has a phosphorus atom content in the oligomer in the range of 9 to 12% by mass from the viewpoint of flame retardancy. The phosphorus atom content is a value measured according to “JIS standard K010246”.

  The phosphorus atom-containing oligomer (B) detailed above can be produced by the following production method.

  That is, the phosphorus atom-containing oligomer (B) has the following structural formula (b1-1) or (b1-2)

（式中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基を表す。）で表される化合物（ｂ１）と、下記構造式（ｂ２）

(Wherein R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group) b1) and the following structural formula (b2)

（式中、Ｒ^１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基を表す。）で表される化合物（ｂ２）とを、モル比［化合物（ｂ１）／化合物（ｂ２）］が０．０１／１．０〜０．９９／１．０となる割合で配合し、酸触媒の存在下、８０〜１８０℃で反応を行い、次いで、前記化合物（ｂ２）の仕込み量に対して、モル基準で合計１．０１〜３．０倍量となる前記化合物（ｂ１）を加え、１２０〜２００℃にて反応を行う方法により製造できる。

(Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group) and a molar ratio [ Compound (b1) / Compound (b2)] is blended at a ratio of 0.01 / 1.0 to 0.99 / 1.0, and reacted at 80 to 180 ° C. in the presence of an acid catalyst, It can manufacture by the method of adding the said compound (b1) used as a total 1.01-3.0 times amount on a molar basis with respect to the preparation amount of the said compound (b2), and reacting at 120-200 degreeC.

  In this invention, when manufacturing a phosphorus atom containing oligomer (B) by this method, precipitation of a reaction intermediate can be suppressed favorably and it becomes easy to make it high molecular weight.

Here, as the alkyl group having 1 to 5 carbon atoms constituting R ² , R ³ , R ⁴ and R ⁵ in the structural formula (b1-1) or (b1-2), a methyl group, ethyl Group, n-propyl group, i-propyl group, t-butyl group, and the compound (b1) used in the present invention is one in which all of R ² , R ³ , R ⁴ , and R ⁵ are hydrogen atoms. Is preferable from the viewpoint of flame retardancy. Further, the compound (b1) preferably has the structural formula (b1-1) from the viewpoint of excellent flame retardancy of the cured product. On the other hand, R ¹ in the structural formula (b2) in the compound (b2) includes a methyl group, an ethyl group, an n-propyl group, a methoxy group, etc., but the reactivity with the compound (b1) and the cured product From the viewpoint of excellent flame retardancy, R ¹ is preferably a hydrogen atom.

  Examples of the catalyst that can be used in the above method include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. And Lewis acid. The amount used is preferably in the range of 0.1 to 5.0% by mass with respect to the total weight of the charged raw materials from the viewpoint of preventing a decrease in electrical insulation of the cured product.

  In the reaction, since the compound (b2) is in a liquid state, it can be used as an organic solvent, but other organic solvents may be used from the viewpoint of improving workability and the like. Here, examples of the organic solvent used include non-ketone organic solvents such as alcohol-based organic solvents and hydrocarbon-based organic solvents. Specifically, examples of the alcohol-based organic solvent include propylene glycol monomethyl ether. Examples of the hydrocarbon organic solvent include toluene, xylene and the like.

  After completion of the reaction, the desired phosphorus atom-containing oligomer (B) can be obtained by drying under reduced pressure.

  The content ratio of the phosphorus atom-containing oligomer (B) used in the present invention in the flame-retardant resin composition is not particularly limited as long as the effects of the present invention are not impaired, but is excellent in mechanical properties and flame retardancy. From the point, it is preferably in the range of 3 to 25 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A), and more preferably in the range of 3 to 20 parts by mass from the viewpoint of excellent heat resistance. In addition, from the viewpoint of molding processability such as extrusion stability at the time of melt kneading and suppression of yarn breakage at the time of molding or suppression of drawing, the range of 3 to 15 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). It is preferable that it is in the range of 5 to 10 parts by mass from the viewpoint of excellent molding processability while maintaining excellent transparency of the polycarbonate resin, and excellent mechanical properties, heat resistance and flame retardancy. Most preferred.

・ Flame retardant aid (C)
The flame-retardant resin composition of the present invention improves various flame retardants and thermal stability, and accordingly, various flame retardant aids (for example, other flame retardants, antioxidants, stabilizers, drippings). An inhibitor, etc.).

(C1 other flame retardants)
In addition, the flame retardant resin composition of the present invention further imparts flame retardancy, so other flame retardants such as phosphorus-containing compounds, nitrogen-containing flame retardants, sulfur-containing flame retardants, silicon-containing flame retardants, alcohol-based Flame retardants, inorganic flame retardants (metal oxides, metal hydroxides, etc.) (hereinafter sometimes referred to as other flame retardants) and the like may be included as long as the effects of the present invention are not impaired.

(C1-1) Phosphorus-containing compound Phosphorus-containing compound Examples of phosphorus-containing compounds include organic phosphorus compounds (monomer-type, dimer-type and trimer-type oligomer-type organic phosphorus compounds, polymer-type organic phosphorus compounds, etc.), inorganic phosphorus compounds, and the like. It is done.

(C1-1-1) Organophosphorus compound Among the organophosphorus compounds, oligomeric organophosphorus compounds include phosphate esters, phosphate ester amides, phosphonitrile compounds, organic phosphonate compounds (esters, metal salts, etc.), Organic phosphinic acid compounds (esters, metal salts, etc.), polymeric organic phosphorus compounds, phosphine oxides and the like are included.

(C1-1-1-1) Phosphate ester As the phosphate ester, aliphatic phosphate ester [trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, triisobutyl phosphate And phosphoric acid tri-C _1-10 alkyl esters such as pentaerythritol phosphate (for example, NH-1197 manufactured by Great Lakes Chemical, bicyclophosphoric acid ester described in JP-A No. 2001-106889); Phosphoric acid di-C _1-10 alkyl ester and phosphoric acid mono-C _1-10 alkyl ester etc.], aromatic phosphoric acid ester [triphenyl phosphate, tricresyl phosphate, trixyl phosphate, diphenyl cresyl phosphate, phosphoric acid Tri (isopropylphenyl), Phosphoric acid tri C _6-20 aryl esters such as phosphate-diphenylethyl cresyl, aliphatic - aromatic phosphate [methyl diphenyl phosphate, phenyl diethyl phosphate, spirocyclic aromatic phosphoric acid ester (diphenyl pentaerythritol Diphosphate, dicresyl pentaerythritol diphosphate, dixylyl pentaerythritol diphosphate, etc.)] and the like.

(C1-1-1-2) Phosphoric ester amide The phosphoric ester amide includes a binding mode of phosphoric ester and phosphoric amide, and includes JP-A-2002-226547, JP-A-2001-354684, JP 2001-139823, JP 2000-327834, JP 2000-154277, JP 10-175985, JP 8-59888, JP 63-235363, JP The phosphoric ester amides described in JP 54-19919 can be used.

  Phosphoric ester amide is available under the trade name “Phosphate ester amide flame retardant SP series (for example, SP-601, SP-670, SP-703, etc.)” (manufactured by Shikoku Kasei Kogyo Co., Ltd.).

(C1-1-1-3) Phosphononitrile compound As the phosphonitrile compound, linear and cyclic phenoxyphosphazenes can be used.

(C1-1-1-4) Examples of the organic phosphonic acid compound organic phosphonic acid (phosphorous acid) compound, for example, aromatic phosphite (aryl is phenyl, cresyl phosphite and the like xylyl tri C _{6 -20} aryl esters), aliphatic phosphites (phosphorus tri-C _1-10 alkyl esters where alkyl is the alkyl etc.); di- or mono-C ₁ phosphites corresponding to the trialkyl phosphites _-10 and alkyl esters), organic phosphites [e.g., spiro cyclic alkylphosphonic such alkyl wherein is an illustration of alkyl C _1-6 alkylphosphonic di C _1-6 alkyl (pentaerythritol bis (methylphosphonate) Acid ester, etc.), alkyl is the alkyl exemplified above, aryl is phenyl, The alkyl phosphonic acid diester; Jill, _{C 1-6} alkylphosphonic di _{C 6-10} alkyl phosphonic acid diester, such as aryl and _{C 1-6} alkyl phosphonic acid _{C 1-6} alkyl _{C 6-10} aryl which is xylyl Corresponding C _6-10 aryl-phosphonic acid diesters (such as spirocyclic C _6-10 arylphosphonic acid esters such as pentaerythritol diphenylphosphonate); C _6-10 arylphosphonic acid monoesters (eg 10-hydroxy-9,10 - such as dihydro-9-oxa-10-phospha-phenanthrene-10-oxide); corresponding to the phosphonocarboxylic acid esters (the alkyl phosphonic acid diester, such as dimethyl methoxycarbonylmethyl acid C _1-4 alkoxycarbonyl Oki C _1-4 alkyl phosphonic acid diester) includes various phosphonates, such as phosphonocarboxylic acid triester], such as. Also included are phosphorous acid, phosphorous acid monoester, or phosphonocarboxylic acid metal salts (Ca, Mg, Zn, Ba, Al salts, etc.) that may be substituted with alkyl or aryl groups.

(C1-1-1-5) Organic Phosphinic Acid Compound In the organic phosphinic acid compound, an alkyl group (such as a C _1-4 alkyl group) or an aryl group (such as a C _6-10 aryl group) is substituted (monosubstituted or disubstituted). Optionally substituted phosphinic acid esters (C _1-6 alkyl phosphinates such as methyl phosphinate), C _6-10 aryl phosphinic acids such as phenyl phosphinate, 9,10-dihydro-9-oxa-10-phos Cyclic phosphinic acid esters such as phaphenanthrene-10-oxide, 10-C _1-30 alkyl or C _6-20 aryl substituted-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) Is included. In addition, metal salts (Ca, Mg, Zn, Ba, Al salts, etc.) of phosphinic acid (for example, dimethylphosphinic acid, diethylphosphinic acid, methylethylphosphinic acid, etc.) that may be substituted by alkyl groups or aryl groups, Also included are phosphinicocarboxylic acid esters (for example, 3-methylphosphinicopropionic acid ester, 3-phenylphosphinicopropionic acid ester, etc.), and homopolymers and copolymers thereof.

(C1-1-1-6) Polymer type organic phosphorus compound As the polymer type organic phosphorus compound, a condensate of a monomer type organic phosphorus compound other than the polymer type phosphate ester (B), for example, polyphosphinicocarboxylic acid ester Also included are polyphosphonic acid amides.

(C1-1-1-7) Phosphine oxide Examples of the phosphine oxide include triphenylphosphine oxide and tricresylphosphine oxide.

(C1-1-2) Inorganic phosphorus compound Examples of the inorganic phosphorus compound include red phosphorus and (poly) phosphate.

(C1-1-2-1) Red phosphorus Red phosphorus has a high flame retardant effect and can impart flame retardancy to the resin even in a small amount. In addition, since the effect can be obtained in a small amount, flame retardancy can be achieved without impairing the resin properties (for example, mechanical properties and electrical properties). As red phosphorus, usually red phosphorus subjected to stabilization treatment (stabilized red phosphorus) is preferably used. In particular, red phosphorus obtained by the method of making fine particles without pulverizing red phosphorus without forming a crushed surface having high reactivity with water and oxygen on the surface of red phosphorus, and further, the surface of red phosphorus, Red phosphorus coated with a resin (for example, a thermosetting resin, a thermoplastic resin), a metal, a metal compound (for example, a metal hydroxide, a metal oxide, or the like) alone or in combination of two or more types can be used. .

  As red phosphorus, stabilized red phosphorus can usually be used in powder form. The particle diameter of the stabilized red phosphorus is, for example, 0.01 to 100 μm, preferably 0.1 to 70 μm, and more preferably about 0.1 to 50 μm.

(C1-2-2) Inorganic salt of (poly) phosphoric acid As (poly) phosphate, inorganic salt of non-condensed or condensed phosphoric acid such as phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid ( Ammonium, Ca, Mg, Zn, Ba, and Al salts).

(C1-2) Nitrogen-containing flame retardant Nitrogen-containing flame retardant As a nitrogen-containing flame retardant, a salt of a triazine and cyanuric acid or a derivative thereof, for example, a melamine salt of cyanuric acid such as melamine cyanurate; Melem salts, melam salts, melon salts, guanamine salts (for example, guanamine cyanurate, acetoguanamine cyanurate, benzoguanamine cyanurate, etc.) are included. These salts can be used alone or in combination of two or more.

(C1-3) Sulfur-containing flame retardant Sulfur-containing flame retardant As the sulfur-containing flame retardant, organic sulfonic acid (alkanesulfonic acid, perfluorosulfonic acid, arylsulfonic acid, sulfonated polystyrene, etc.), sulfamic acid, organic sulfamic acid, And salts such as organic sulfonic acid amides (ammonium salts, alkali metal salts, alkaline earth metal salts, etc.).

(C1-4) Silicon-containing flame retardant The silicon-containing flame retardant includes (poly) organosiloxane. As the (poly) organosiloxane, homopolymers (for example, polydimethylsiloxane, polyphenylmethylsiloxane) such as dialkylsiloxane (for example, dimethylsiloxane), alkylarylsiloxane (for example, phenylmethylsiloxane), diarylsiloxane, monoorganosiloxane, etc. Etc.), or a copolymer. Further, as the (poly) organosiloxane, branched organosiloxane [trade name “XC99-B5664” of Toshiba Silicone Co., Ltd., trade names “X-40-9243”, “X-40-9244” of Shin-Etsu Chemical Co., Ltd.] , “X-40-9805”, compounds described in JP-A-10-139964, etc.], modified having a substituent such as an epoxy group, a hydroxyl group, a carboxyl group, an amino group or an ether group at the molecular end or main chain ( Poly) organosiloxane (for example, modified silicone) can also be used.

(C1-5) Alcohol Flame Retardant Examples of alcohol flame retardants include polyhydric alcohols (such as pentaerythritol), oligomeric polyhydric alcohols (such as dipentaerythritol and tripentaerythritol), esterified polyhydric alcohols, and substitution. Alcohols, celluloses (cellulose, hemicellulose, lignocellulose, pectocellulose, adipocellulose, etc.), saccharides (monosaccharides, polysaccharides, etc.) and the like.

(C1-6) Inorganic flame retardant Among inorganic flame retardants, examples of the metal oxide include molybdenum oxide, tungsten oxide, titanium oxide, zirconium oxide, tin oxide, copper oxide, zinc oxide, aluminum oxide, and nickel oxide. Iron oxide, manganese oxide, antimony trioxide, antimony tetroxide, antimony pentoxide and the like. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, tin hydroxide, and zirconium hydroxide. Examples of the metal sulfide include zinc sulfide, molybdenum sulfide, and tungsten sulfide. The inorganic flame retardant also includes expansive graphite.

  These other flame retardants can be used singly or in combination of two or more. The content of the other flame retardant is not particularly limited as long as it does not impair the effects of the present invention, but when used, for example, 0.01 to 50 parts by mass with respect to 100 parts by mass of the resin (A). The range is preferable, more preferably in the range of 0.05 to 30 parts by mass, and still more preferably in the range of 0.1 to 20 parts by mass.

(C2 antioxidant or stabilizer)
In addition, the flame retardant resin composition of the present invention may contain an antioxidant or a stabilizer in a range that does not impair the effects of the present invention in order to stably maintain heat resistance for a long period of time. Antioxidants or stabilizers include, for example, phenolic (such as hindered phenols), amine (such as hindered amines), phosphorus, sulfur, hydroquinone, quinoline antioxidants (or stabilizers), inorganic System stabilizers, compounds having reactive functional groups with respect to active hydrogen atoms (reactive stabilizers) and the like are included.

(C2-2) Phenol-based antioxidants Phenol-based antioxidants include hindered phenols (hindered phenol-based antioxidants) such as 1,6-hexanediol-bis [3- (3,5- C _2-10 alkylenediol-bis [3- (3,5-di-branched C _3-6 alkyl-4-hydroxyphenyl) propionate], such as di-t-butyl-4-hydroxyphenyl) propionate]; Di- or trioxy C _2-4 alkylenediol-bis [3- (3,5-di-branched) such as triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] C _3-6 alkyl-4-hydroxyphenyl) propionate]; for example, glycerol tris [3- (3,5-di -t- butyl - - _{C 3-8} alkylene triol such as hydroxyphenyl) propionate] - bis [3- (3,5-di - branched _{C 3-6} alkyl-4-hydroxyphenyl) propionate]; for example, pentaerythritol tetrakis [3- ( C _4-8 alkylenetetraol tetrakis [3- (3,5-di-branched C _3-6 alkyl-4-hydroxyphenyl) propionate] such as 3,5-di-t-butyl-4-hydroxyphenyl) propionate] ] Is preferable.

(C2-3) Amine-based antioxidant amine antioxidant, a hindered amine, for example, tri- or tetra-C _1-3 alkyl piperidine or methoxy derivative thereof (4-position, benzoyloxy, phenoxy and substituted 2,2,6,6-tetramethylpiperidine etc.), bis (tri, tetra or penta C _1-3 alkylpiperidine) C _2-20 alkylene dicarboxylic acid ester [eg bis (2,2,6 , 6-tetramethyl-4-piperidyl) oxalate, malonate corresponding to oxalate, adipate, sebacate, terephthalate, etc .; bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate], 1,2- Bis (2,2,6,6-tetramethyl-4-piperidyloxy) ethane, phenylnaphthyla Emissions, N, N'-diphenyl-1,4-phenylenediamine, and the like N- phenyl -N'- cyclohexyl-1,4-phenylenediamine.

(C2-4) (Organic) phosphorus stabilizers or antioxidants Phosphorus (organic phosphorus) stabilizers or antioxidants include, for example, triisodecyl phosphite, trisnonylphenyl phosphite, diphenylisodecylphos. Phyto, phenyl diisodecyl phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4'-butylidenebis (3-methyl-6-t-butylphenyl) ditridecyl phosphite , Tris (branched C _3-6 alkylphenyl) phosphite [e.g., tris (2,4-di-t-butylphenyl) phosphite, tris (2-t-butyl-4-methylphenyl) phosphite, tris ( 2,4-di -t- amyl phenyl) phosphite, etc.], (branched _{C 3-6} alkyl phenyl) Feniruho Fight [e.g., bis (2-t-butylphenyl) phenyl phosphite, etc. 2-t-butylphenyl diphenyl phosphite, tris (2-phenyl) phosphite, bis _{(C 1-9} alkylaryl) pentaerythritol Diphosphite [e.g., bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, etc.], triphenyl phosphate stabilizers (for example, 4-phenoxy-9-α -(4-Hydroxyphenyl) -p-cumenyl -3,5,8,10-tetraoxa-4,9-diphosphapyro [5.5] undecane, tris (2,4-di-t-butylphenyl) phosphate, etc.), diphosphonite stabilizers (for example, tetrakis ( 2,4-di-t-butyl) -4,4′-biphenylenediphosphonite and the like. The phosphorus stabilizer usually has a branched C _3-6 alkylphenyl group (particularly a t-butylphenyl group). In the flame-retardant resin composition of the present invention, it is preferable to use a phosphorus stabilizer or an antioxidant together, and the phosphorus antioxidant (C2-4) is reduced to 0 with respect to 100 parts by mass of the polycarbonate resin (A). The light resistance can be drastically improved by blending 0.01 to 10 parts by mass. This is because the phosphorus atom-containing oligomer (B) has a structure in which bulky HCA is reacted in the vicinity of the phenolic hydroxyl group, and when the hydrogen is donated to the peroxide radical generated by auto-oxidation, the phenolic hydroxyl group itself is This is thought to be due to phenoxy radicals having low activity due to steric hindrance.

(C2-5) Hydroquinone antioxidant The hydroquinone antioxidant includes, for example, 2,5-di-t-butylhydroquinone, and the quinoline antioxidant includes, for example, 6-ethoxy-2. 2,4-trimethyl-1,2-dihydroquinoline and the like, and examples of the sulfur-based antioxidant include dilauryl thiodipropionate and distearyl thiodipropionate.

(C2-6) Inorganic stabilizer (inorganic metal or mineral stabilizer)
Inorganic stabilizers (inorganic metal or mineral stabilizers) include hydrotalcite, zeolite, alkaline earth metal compounds, and the like.

(C2-6-1) Hydrotalcite Examples of the hydrotalcite include hydrotalcites described in JP-A-60-1241 and JP-A-9-59475, for example, the following formula [M ²⁺ _1-X M ³⁺ _X (OH) ₂ ] ^{X +} [A ^N− _{X / n} · mH ₂ O] ^X− (wherein M ²⁺ is a divalent metal such as Mg ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺⁾ indicates ^{ion, M 3+} is ^{Al 3+,} Fe ^{3+, .A} showing a trivalent metal ion such as ^{Cr 3+ n-it} is _{^{CO 3 2-, OH -, HPO}} 4 2-, SO 4 2- n -valent (such as A monovalent or divalent anion, where x is 0 <x <0.5, and m is 0 ≦ m <1). Hydrotalcite is available from Kyowa Chemical Industry Co., Ltd. as “DHT-4A”, “DHT-4A-2”, “Alkamizer”, and the like.

(C2-6-2) Zeolite The zeolite is not particularly limited. For example, zeolite described in JP-A-7-62142 [crystalline aluminosilicate having a minimum unit cell of alkali and / or alkaline earth metal] Zeolite (A-type, X-type, Y-type, L-type and ZSM-type zeolite, mordenite zeolite; natural zeolite such as chabazite, mordenite, faujasite, etc.) that is an acid salt can be used. The A-type zeolite is “Zeoram series (A-3, A-4, A-5)”, “Zeostar series (KA100P, NA-100P, CA-100P)”, etc., and X-type zeolite. "Zeoram Series (F-9)", "Zeostar Series (NX-100P)", etc. Y-type zeolite is "HSZ Series (320NAA)" etc. from Tosoh Corporation and Nippon Chemical Industry Co., Ltd. It is available.

(C2-6-3) Alkaline earth metal compound Examples of the alkaline earth metal compound include oxides (such as magnesium oxide), hydroxides (such as magnesium hydroxide and calcium hydroxide), and carbonates [magnesium carbonate]. , (Soft / colloid / heavy) calcium carbonate, etc.], organic carboxylates (magnesium acetate, calcium acetate, magnesium stearate, calcium stearate, calcium 12-hydroxystearate, etc.) and the like can be used.

  These inorganic stabilizers can be used alone or in combination of two or more.

(C2-7) Reactive Stabilizer The reactive stabilizer includes a compound having a functional group reactive with an active hydrogen atom. The compound having a functional group reactive with an active hydrogen atom is selected from a cyclic ether group, an oxetane group, an acid anhydride group, an isocyanate group, an oxazoline group (ring), an oxazine group (ring), a carbodiimide group, and the like. Examples thereof include compounds having at least one functional group.

(C2-7-1) Compound having cyclic ether group The compound having a cyclic ether group includes a compound having an epoxy group or an oxetane group. Examples of the compound having an epoxy group include alicyclic compounds such as vinylcyclohexene dioxide, glycidyl ester compounds such as versatic acid glycidyl ester, glycidyl ether compounds (hydroquinone diglycidyl ether, biphenol diglycidyl ether, bisphenol-A diester). Glycidyl ether, etc.), glycidylamine compounds, epoxy group-containing vinyl copolymers, epoxidized polybutadiene, epoxidized diene monomer-styrene copolymers, triglycidyl isocyanurate, epoxy-modified (poly) organosiloxane, and the like.

(C2-7-2) Compound having oxetane group Examples of the compound having an oxetane group include isophthalic acid di [1-ethyl (3-oxetanyl)] methyl ester and terephthalic acid di [1-ethyl (3-oxetanyl)]. ] Oxetanyl ester compounds such as methyl esters, oxetanyl ether compounds {for example, alkyl oxetanyl compounds such as di [1-ethyl (3-oxetanyl)] methyl ether and 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, Aryl oxetanyl compounds such as 3-ethyl-3- (phenoxymethyl) oxetane, aralkyl oxetanyl ether compounds such as 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bisphenol-A di [ 1-ethyl (3-o Bisphenol-type oxetane resins such as cetanyl)] methyl ether, mono to poly [1-ethyl (3-oxetanyl)] methyl etherified phenol novolak, mono to poly [1-ethyl (3-oxetanyl)] methyl etherified cresol novolak, etc. Novolak-type oxetane resin, etc.}, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyloxetane-modified oxetane-modified (poly) organosiloxane, and derivatives having the oxetanyl unit {for example, [1- And an alkyl oxetanylmethyl derivative {for example, [1-methyl (3-oxetanyl)] methyl derivative} corresponding to ethyl (3-oxetanyl)] methyl derivative}.

(C2-7-3) Compound having an acid anhydride group Examples of the compound having an acid anhydride group include an olefin resin having a maleic anhydride group (for example, ethylene-maleic anhydride copolymer, maleic anhydride). Modified polypropylene, etc.).

(C2-7-4) Compound having isocyanate group Examples of the compound having an isocyanate group include aliphatic isocyanates such as hexamethylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, aromatic isocyanates such as diphenylmethane isocyanate, and the like. Examples thereof include modified isocyanates (eg, isophorone diisocyanate trimer).

(C2-7-5) Compound having oxazoline group Examples of the compound having an oxazoline group include 2,2 '-(1,3-phenylene) -bis (2-oxazoline) and 2,2'-(1, Examples thereof include bisoxazoline compounds such as 4-phenylene) -bis (2-oxazoline), and vinyl resins having an oxazoline group (for example, vinyloxazoline-modified styrene resin).

(C2-7-6) Compound having an oxazine group Examples of the compound having an oxazine group include bisoxazine compounds such as 2,2'-bis (5,6-dihydro-4H-1,3-oxazine). Can be mentioned.

(C2-7-7) Compound having carbodiimide group Examples of the compound having a carbodiimide group include polyarylcarbodiimides such as poly (phenylcarbodiimide) and poly (naphthylcarbodiimide), poly (2-methyldiphenylcarbodiimide), poly ( 2,6-diethyldiphenylcarbodiimide), poly (2,6-diisopropyldiphenylcarbodiimide), poly (2,4,6-triisopropyldiphenylcarbodiimide), poly (2,4,6-trit-butyldiphenylcarbodiimide), etc. A polyalkylarylcarbodiimide, poly [4,4′-methylenebis (2,6-diethylphenyl) carbodiimide], poly [4,4′-methylenebis (2-ethyl-6-methylphenyl) carbodiimide], poly [4, 4 ' -[Alkylenebis (alkyl or cycloalkylaryl) carbodiimide] such as -methylenebis (2,6-diisopropylphenyl) carbodiimide], poly [4,4'-methylenebis (2-ethyl-6-methylcyclohexylphenyl) carbodiimide], etc. Is mentioned.

  These reactive stabilizers can be used alone or in combination of two or more.

  These antioxidants and / or stabilizers can be used alone or in combination of two or more. The content of the antioxidant and / or stabilizer is not particularly limited as long as the effect of the present invention is not impaired, but when used, for example, 0.01% with respect to 100 parts by mass of the polycarbonate resin (A). The range of -15 mass parts is preferable, The range of 0.05-10 mass parts is more preferable, Furthermore, the range of 0.1-10 mass parts is the most preferable.

  Of these antioxidants and stabilizers, it is preferable to combine an inorganic stabilizer and a reactive stabilizer from the viewpoint of hydrolysis resistance, and the ratio (mass ratio) of both is an inorganic stabilizer / reaction. Stability stabilizer = 95/5 to 10/90, preferably 90/10 to 30/70, more preferably 80/20 to 50/50.

  Phosphoric acids exemplified in the above-mentioned specific flame retardant aid (for example, inorganic phosphoric acid such as phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, polyphosphoric acid; phosphonocarboxylic acid, Addition of organic phosphoric acid such as nitrogen phosphoric acid) further improves thermal stability.

(C3 anti-dripping agent)
Furthermore, the flame retardant resin composition of the present invention may contain an anti-dripping agent such as a fluororesin within a range not impairing the effects of the present invention. The dripping prevention agent can suppress dripping (drip) of fire types and melt during combustion. Fluorine-based resins include tetrafluorethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, perfluoroalkyl vinyl ether and other fluorine-containing monomers, or copolymers; the fluorine-containing monomers and ethylene, propylene, acrylate And copolymers with copolymerizable monomers such as Examples of such fluorine-based resins (fluorine-containing resins) include homopolymers such as polytetrafluoroethylene, polychlorotrifluoroethylene, and polyvinylidene fluoride; tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoro Examples of the copolymer include an ethylene-perfluoroalkyl vinyl ether copolymer, an ethylene-tetrafluoroethylene copolymer, and an ethylene-chlorotrifluoroethylene copolymer. These fluororesins can be used alone or in combination of two or more.

  The fluororesin may be used in the form of particles, and the average particle size may be, for example, about 10 to 5000 μm, preferably about 100 to 1000 μm, and more preferably about 100 to 700 μm.

  Content of fluororesin is 0.01-10 mass parts with respect to 100 mass parts of polycarbonate resin (A), for example, Preferably it is 0.1-5 mass parts, More preferably, it is 0.1-3 mass parts It is.

・ Additive (D1) / Filler (D2)
Furthermore, the flame retardant resin composition of the present invention may contain an additive (D1) and a filler (D2) as other components depending on the purpose. Examples of other additives (D1) include UV absorbers, heat stabilizers, weather stabilizers and other stabilizers, lubricants, mold release agents, colorants, plasticizers, nucleating agents, impact modifiers, and sliding agents. It is done. Furthermore, the flame retardant resin composition of the present invention may be modified with a filler (D2) in order to further improve mechanical strength, rigidity, heat resistance, electrical properties and the like. The filler (D2) includes fibrous fillers and non-fibrous fillers (such as plate-like fillers and granular fillers). When using these additives (D1) and fillers (D2), the proportion of the additives (D1) or fillers (D2) in the flame retardant resin composition is within a range that does not impair the effects of the present invention. Although not particularly limited, when used, for example, the range of 1 to 60% by mass is preferable in the flame retardant resin composition of the present invention, the range of 1 to 50% by mass is more preferable, and further 1 to 45% by mass. The range of is most preferable.

(D2-1 fibrous filler)
Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, potassium titanate fiber, metal fiber, high melting point organic fiber (for example, aliphatic or aromatic polyamide, aromatic Group polyester, fluororesin, acrylic resin such as polyacrylonitrile, etc.). Preferred fiber fillers include glass fibers and carbon fibers.

(D2-2 Fibrous filler)
Among the non-fibrous fillers, examples of the plate-like filler include glass flakes, mica, graphite, and various metal foils. The granular fillers include carbon black, silicon carbide, silica, quartz powder, glass beads, glass powder, milled fiber (eg, milled glass fiber), calcium silicate, aluminum silicate, kaolin, talc, clay, silica Silicates such as algae and wollastonite; metal oxides such as iron oxide, titanium oxide, zinc oxide and alumina; carbonates of metals such as calcium carbonate and magnesium carbonate; sulfuric acid of metals such as calcium sulfate and barium sulfate Salt, metal powder, etc. are included. Preferred non-fibrous fillers include granular or plate-like fillers, particularly glass beads, milled fibers, kaolin, talc, mica, and glass flakes.

  Particularly preferred fillers (D2) include glass fibers, for example, glass fibers (such as chopped strands) having high strength and rigidity.

  In using these fillers (D2), it is desirable to use a sizing agent or a surface treatment agent if necessary. Such sizing agents or surface treatment agents include functional compounds. Examples of the functional compound include epoxy compounds, silane compounds, titanate compounds, preferably epoxy compounds, particularly bisphenol A type epoxy resins and novolak type epoxy resins.

  The filler (D2) may be subjected to a convergence treatment or a surface treatment with the convergence agent or the surface treatment agent. About the time of a process, you may process simultaneously with addition of a filler, and you may process previously before addition. Moreover, the usage-amount of the functional surface treating agent or sizing agent used together is 5 mass% or less with respect to a filler, Preferably it is about 0.05-2 mass%.

  The phosphorus atom-containing oligomer (B) of the present invention can make the resin highly flame-retardant because it promotes carbonization of the resin surface during combustion. In addition, by using in combination with polymer-type phosphoric acid ester, aromatic resin, etc., it is possible to impart further flame retardancy to the polycarbonate resin (A) even in a small amount, resulting in bleed out and reduced heat resistance. It is preferable because it does not cause

(D3 polymer compound)

(D3-1 resin)
The flame-retardant resin composition of the present invention is a polyester resin, a polyether ketone resin, a polyether resin, a polyimide resin, with respect to 100 parts by mass of the polycarbonate resin (A), within a range not impairing the effects of the present invention. It is preferable to further blend 1 to 100 parts by mass of a polyamide resin, a polyarylene sulfide resin typified by a polyphenylene sulfide resin, and a polyarylene ether resin typified by a polyphenylene ether resin, further improving flame retardancy and heat resistance. From the standpoint that it can be used, a polyarylene ether resin is a preferred resin.
The polyphenylene ether resin that can be used in the present invention includes the following general formula (p-1)

（但し、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４は、それぞれ水素、炭化水素、または置換炭化水素基からなる群から選択されるものであり、互いに同一でも異なっていてもよい。）で示される結合単位からなる単独重合体及び／又は共重合体である。このポリフェニレンエーテル樹脂の具体的な例としては、ポリ（２，６−ジメチル−１，４−フェニレンエーテル、２，６−ジメチルフェノールと２，３，６−トリメチルフェノールとの共重合体等が好ましく、中でもポリ（２，６−ジメチル−１，４−フェニレンエーテル）が好ましい。かかるポリフェニレンエーテル樹脂の製造方法は特に限定されるものではなく、例えば米国特許第３，３０６，８７４号明細書記載の方法による第一銅塩とアミンのコンプレックスを触媒として用い、例えば、２，６−キシレノールを酸化重合することにより容易に製造でき、そのほかにも米国特許第３，３０６，８７５号明細書、米国特許第３，２５７，３５７号明細書、米国特許第３，２５７，３５８号明細書及び特公昭５２−１７８８０号公報、特開昭５０−５１１９７号公報に記載された方法で容易に製造できる。本発明にて用いる上記ＰＰＥの還元粘度ηSP/C（０．５ｇ／ｄｌ、クロロフォルム溶液、３０℃測定）は、０．２０〜０．７０ｄｌ／ｇの範囲にあることが好ましく、０．３０〜０．６０ｄｌ／ｇの範囲にあることがより好ましい。ポリフェニレンエーテル樹脂の還元粘度に関する上記要件を満たすための手段としては、前記ポリフェニレンエーテル樹脂の製造の際の触媒量の調整などを挙げることができる。

(However, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each selected from the group consisting of hydrogen, hydrocarbon, or substituted hydrocarbon group, and may be the same or different from each other.) Homopolymers and / or copolymers composed of bonded units. Specific examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene ether, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and the like. Of these, poly (2,6-dimethyl-1,4-phenylene ether) is preferable, and the method for producing such a polyphenylene ether resin is not particularly limited, and is described in, for example, US Patent No. 3,306,874. It can be easily produced by oxidative polymerization of 2,6-xylenol using, for example, a complex of cuprous salt and amine prepared by the method, and in addition, US Pat. No. 3,306,875, US Pat. No. 3,257,357, US Pat. No. 3,257,358 and Japanese Patent Publication No. 52-17880, The PPE used in the present invention has a reduced viscosity ηSP / C (0.5 g / dl, chloroform solution, measured at 30 ° C.) of 0.20. It is preferably in the range of ˜0.70 dl / g, more preferably in the range of 0.30 to 0.60 dl / g, as a means for satisfying the above requirements regarding the reduced viscosity of the polyphenylene ether resin, Examples include adjustment of the amount of catalyst in the production of polyphenylene ether resin.

(D3-2 silicone compound)
In addition, the flame retardant resin composition of the present invention is a composition that does not easily drop (drip) droplets during combustion by itself, but if a silicone compound is further added within a range that does not impair the effects of the present invention. In addition, it is preferable because it can further enhance the effects of suppressing the drop (drip) of droplets during combustion, suppressing the spread of flames during combustion, and improving impact resistance. The silicone compound that can be used in the present invention refers to a silicone resin and / or silicone oil.

  The silicone resins that can be used in the present invention include the following general formulas (s-1) to (s-4).

（ここで、Ｒ^２１はそれぞれ飽和または不飽和一価炭化水素基、水素原子、ヒドロキシル基、アルコキシル基、アリール基、ビニルまたはアリル基から選ばれる基を表す。）で表される単位およびこれらの混合物から選ばれる化学的に結合されたシロキサン単位からなるポリオルガノシロキサンを挙げることができ、さらに、室温（２３℃）で約２００〜３００，０００，０００センチポイズの粘度のものが好ましいが、上記のシリコーン樹脂である限り、それに限定されるものではない。

(Wherein R ²¹ represents a group selected from a saturated or unsaturated monovalent hydrocarbon group, a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryl group, a vinyl group or an allyl group) and these units. Mention may be made of polyorganosiloxanes consisting of chemically bonded siloxane units selected from a mixture, more preferably those having a viscosity of about 200 to 300,000,000 centipoise at room temperature (23 ° C.). As long as it is a silicone resin, it is not limited thereto.

  As the silicone oil that can be used in the present invention, the following general formula (s-5)

（ここで、Ｒ^２２はアルキル基またはフェニル基を表し、ｉは１以上の整数である。）で表されるものをあげることができる。使用することができるシリコーンオイルは、０．６５〜１００，０００センチトークスの粘度のものが好ましいが、上記のシリコーンオイルである限り、それに限定されるものではない。

(Wherein R ²² represents an alkyl group or a phenyl group, and i is an integer of 1 or more). The silicone oil that can be used preferably has a viscosity of 0.65 to 100,000 centistokes, but is not limited thereto as long as it is the silicone oil described above.

  As the silicone compound that can be used in the present invention, a silicone resin and / or a silicone oil can be used, and a silicone oil is preferable from the viewpoint of improving flame retardancy and impact resistance.

  The addition amount of the silicone compound is preferably in the range of 0.01 to 10 parts by mass and more preferably in the range of 0.05 to 8 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). The range is more preferably 0.1 to 5 parts by mass.

-Production method of flame retardant resin composition The flame retardant resin composition of the present invention includes a polycarbonate resin (A), a phosphorus atom-containing oligomer (B), and, if necessary, a range that does not impair the effects of the present invention. The flame retardant aid (C), additive (D1), filler (D2), and polymer compound (D3) were premixed in advance using various mixers such as a tumbler or a Henschel mixer. Thereafter, melt kneading can be carried out using a Banbury mixer, roll, brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, or the like at a resin set temperature or higher. In addition, each component may be preliminarily mixed, or only a part of the components may be mixed in advance and supplied to an extruder using a feeder to be melt kneaded. Further, when the components (C), (D1), (D2), and (D3) are added, when these components are brittle members such as being easily broken by melt kneading, the components (A) to (B) The method of adding the components (C), (D1), (D2), and (D3) after the middle stream and melting and kneading them with the resin component is also a point of mechanical strength of the resulting resin composition To preferred. The resin composition after melt-kneading is subjected to a molding process to be described later, but may be once made into a pellet or powder form for storage and distribution. As long as the effect of the present invention is not impaired, the form in that case may be a known form such as a pellet or powder, and is not particularly limited, but is preferably a pellet from the viewpoint of handleability. The pellets can be produced according to a conventional method. For example, the pellets are preferably extruded into strands from the apparatus used for the melt-kneading and then cooled with water and cut to form pellets.

-Flame-retardant masterbatch and its manufacturing method As above-mentioned, the flame-retardant resin composition of this invention melt-kneads the flame-retardant resin composition containing a polycarbonate resin (A) and a phosphorus atom containing oligomer (B) directly. The flame retardant masterbatch containing the polycarbonate resin (A) and the phosphorus atom-containing oligomer (B) at a high concentration is produced by melt kneading, and the obtained flame retardant masterbatch is Further, a thermoplastic resin (E) such as a polycarbonate resin can be diluted and blended and melt kneaded. Details will be described below.

  More specifically, the components (A) and (B) described above are premixed by a mixer such as a V-type blender, a ribbon blender, and a Henschel mixer as necessary, and then a single-screw extrusion kneader, open Using a known mixer such as a roll mixer, a pressure kneader, a Banbury mixer, a twin-screw extrusion kneader or the like, the resin is set at a melting point or higher and melt-kneaded. Among these, the twin screw extrusion type kneader is preferable in terms of kneading properties and productivity. After melt-kneading, the flame-retardant masterbatch of the present invention is obtained by processing into pellets or the like according to a conventional method. Although the content rate of the phosphorus atom containing oligomer (B) in a flame-retardant masterbatch will not be specifically limited if it is a range which does not impair the effect of this invention, It contains the said phosphorus atom with respect to 100 mass parts of polycarbonate resin (A). It is preferable to melt-knead so that an oligomer (B) may be contained in 5-30 mass parts, and it is more preferable to melt-knead so that it may contain in 7-25 mass parts.

  The flame retardant resin composition of the present invention is obtained by further adding a thermoplastic resin (E) as a dilution resin to the flame retardant master batch thus obtained and melt-kneading. Thus, by obtaining a flame retardant resin composition via a masterbatch, the phosphorus atom-containing oligomer (B), which is a flame retardant component, can be stably and uniformly dispersed, and can also be added at a high concentration. An excellent flame retardant effect can be imparted to the molded body.

  Here, the thermoplastic resin for dilution resin (E) that can be used in the present invention is not particularly limited as long as the effects of the present invention are not impaired. For example, polycarbonate resin (A), polymer compound (D3), That is, polycarbonate resin, polyester resin, polyether ketone resin, polyether resin, polyimide resin, polyamide resin, polyarylene sulfide resin, polyarylene ether resin, silicone compound, etc., among these, polycarbonate resin, polyarylene ether resin Is preferable. When the flame retardant masterbatch containing the polycarbonate resin (A) and the thermoplastic resin (E) are melt-kneaded, the polycarbonate resin (A) and the thermoplastic resin (E) are the same type of resin depending on the purpose. Although different types of resins may be used, it is preferable to use the same type of resin from the viewpoint of compatibility.

  In order to produce a flame retardant resin composition from the flame retardant master batch of the present invention, the phosphorus atom-containing content is 100 parts by mass of the polycarbonate resin (A) in the finally obtained flame retardant resin composition. There is no particular limitation as long as the thermoplastic resin (E) for dilution resin is added and melt-kneaded so as to contain the oligomer (B) in a proportion of 3 to 25 parts by mass. For example, when the thermoplastic resin (E) is a polycarbonate resin, the phosphorus atoms are added to 100 parts by mass of the polycarbonate resin (A) and the thermoplastic resin for dilution resin (E) in the flame-retardant masterbatch. It is preferable to add the thermoplastic resin (E) so that the content oligomer (B) is 3 to 25 parts by mass. When the thermoplastic resin (E) is a resin other than the polycarbonate resin, the thermoplastic resin (E) for the dilution resin is 1 to 100 with respect to 100 parts of the polycarbonate resin (A) in the flame retardant masterbatch. It is preferable to add a thermoplastic resin (E) so that a mass part and the said phosphorus atom containing oligomer (B) may be 3-25 mass parts. The method for melt kneading is not particularly limited, and for example, a method similar to the method for producing the master batch can be employed.

  In addition, when manufacturing the said flame-retardant masterbatch, with said resin (A) and a phosphorus atom containing oligomer (B), or when diluting to the said flame-retardant masterbatch, a thermoplastic resin (E) In addition, the above-mentioned flame retardant aid (C), additive (D1), filler (D2), and polymer compound (D3) can be blended within a range that does not impair the effects of the present invention.

-Molded article / use The flame-retardant resin of the present invention containing 3 to 25 parts by mass of a phosphorus atom-containing oligomer (B) with respect to 100 parts by mass of the polycarbonate resin (A) obtained as described above. The composition can be melt-kneaded in a molding machine to produce a flame-retardant resin molding by various known molding methods such as extrusion molding, injection molding, calender molding, hollow molding, vacuum molding, and pressure molding. it can.

  As a specific example of the flame-retardant resin molded product obtained by molding the flame-retardant resin composition of the present invention, it can be used in various applications where high flame retardancy is required. It can be suitably used for applications such as films, sheets and fibers. Specifically, for example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, Represented by plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, etc. Electric / electronic parts: VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / compact discs, lighting parts, refrigerator parts, air conditioners Houses represented by parts, typewriter parts, word processor parts, office electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copying machine related parts, cleaning jigs, oilless bearings, stern bearings, underwater Various bearings such as bearings, machine-related parts represented by motor parts, lighters, typewriters, etc., optical equipment represented by microscopes, binoculars, cameras, watches, etc .; precision machine-related parts; alternator terminals, alternator connectors, ICs Various valves such as regulators, exhaust gas valves, fuel-related / exhaust / intake system pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, Air gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump Impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, fuel related solenoid valve coil, fuse connector, horn terminal, electrical equipment Parts insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake pin Storage devices such as ston, solenoid bobbin, engine oil filter, ignition device case, personal computer, printer, display, CRT display, fax, copy, word processor, notebook computer, mobile phone, PHS, DVD drive, PD drive, flexible disk drive It is useful for electrical / electronic equipment parts such as housings, chassis, relays, switches, case members, transformer members, coil bobbins, automobile parts, machine parts, and other various applications.

  The thickness of the sheet or film obtained by molding the flame retardant resin composition of the present invention into a sheet or film varies depending on the application and can be any thickness, but is usually 5 to 200 μm, Preferably it is 10-150 micrometers, More preferably, it is 20-100 micrometers, Most preferably, it is 30-70 micrometers.

  A molded body formed by molding the flame retardant resin composition of the present invention, particularly a film, sheet or fiber formed into a sheet, film, or fiber, is a resin (A) originally having mechanical strength and transparency. While maintaining the physical properties of the above, it is possible to suppress the bleeding out of the phosphorus atom-containing oligomer (B), which is a flame retardant component, and to exhibit excellent flame resistance and heat resistance satisfying UL-94 / VTM-0. .

  The term “sheet” or “film” in the present invention is not particularly used for strictly distinguishing between a sheet and a film, but is used to clarify that both are included, as long as it has the characteristics of the present invention. Sheets and films can be interpreted as widely as possible, and the term sheet includes what is called a plate or plate as long as it has the characteristics of the present invention. When it is necessary to distinguish between a sheet and a film, the sheet is usually used when the thickness is about 0.5 to 5 mm, and the film is usually used when the thickness is about 5 to 500 μm. used.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

(Synthesis Example 1) Synthesis of Phosphorus Atom-Containing Oligomer (B-1) A flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas introduction tube, and a stirrer, 1220 g (10.0 mol) of 2-hydroxybenzaldehyde And 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as “HCA”) 1512 g (7.0 mol), oxalic acid 22.3 g (0.19 mol) Was heated to 120 ° C. and reacted for 1 hour. Next, 1728 g (8.0 mol) of HCA was added, the temperature was raised to 180 ° C., and the reaction was carried out for 3 hours. Next, water is removed under reduced pressure by heating, and the following structural formula

で表される構造単位を有するリン原子含有オリゴマー（Ｂ−１）４１００ｇを得た。得られたリン原子含有オリゴマーの軟化点は１３８℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１８０℃）は６６ｄＰａ・ｓ、水酸基当量は４２８ｇ／ｅｑ．リン含有量１０．５％であり、ｎ＝２以上の成分比率は４９．０％であった。

4100 g of a phosphorus atom-containing oligomer (B-1) having a structural unit represented by The resulting phosphorus atom-containing oligomer had a softening point of 138 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 180 ° C.) of 66 dPa · s, and a hydroxyl group equivalent of 428 g / eq. The phosphorus content was 10.5%, and the component ratio of n = 2 or more was 49.0%.

(Examples 1-3, Comparative Examples 1-7) Manufacture of a flame-retardant masterbatch The raw materials were premixed with a Henschel mixer so that the composition ratios shown in Tables 1 and 2 were obtained, and sintered with an opening of 25 µm. The mixture was melt-kneaded in a 30 mmφ twin-screw vent type extruder (set temperature: 280 ° C.) equipped with a filter. After that, a strand-like product was obtained and cut into pellets to produce a master batch. The resin pressure rise value at that time was measured. The results are shown in Table 1. Moreover, when manufacturing the master batch using the above twin screw extruder, the extrusion stability when continuously operated for 1 hour was evaluated according to the following criteria.

(Extrusion stability)
○: The state of the kneaded discharge was stable and could be extruded without problems.
Δ: Viscosity drop and pulsation phenomenon and foaming slightly occurred in the kneaded discharge, but the strand could be drawn and sampling was possible.
X: Viscosity drop and pulsation phenomenon and foaming of the kneaded discharge were remarkable, and strands could not be drawn and sampling was impossible.

(Example of master batch measurement: Intrinsic viscosity)
About the polycarbonate resin composition pellets (master batch) (B1-1) to (B4-1) that could be sampled, a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (mass ratio 1/1) And dissolved at 110 ° C. to a concentration of 1.00 × 10 ⁻² kg / L, cooled to 30 ° C., and using a fully automatic solution viscometer (“2CH type DJ504” manufactured by Sentec Co., Ltd.) The intrinsic viscosity was measured. The measurement was performed by measuring the number of seconds of dropping only the sample solution having a concentration of 1.00 × 10 ⁻² kg / L and the solvent, and calculating by the following formula.

IV = [(1 + 4KH · ηsp) 0.5−1] / (200KH · C)
(Where ηsp = η / η0−1, η is the sample solution drop seconds, η0 is the solvent drop seconds, C is the polymer solution concentration (kg / L), and KH is the Huggins constant. KH adopted 0.33.)

However, the numbers of the composition ratios in the table represent parts by mass, and the following materials were used.
A: Polycarbonate ("Iupilon E-2000F" manufactured by Mitsubishi Engineering Plastics Co., Ltd.)
B2: condensed phosphate ester (“PX-202” manufactured by Daihachi Chemical Industry Co., Ltd.)
B3: Aluminum phosphate (“EXOLIT OP-930” manufactured by Clariant Co., Ltd.)
B4: Melamine polyphosphate (“MELAPUR 200/70” manufactured by Ciba Specialty Chemicals Co., Ltd.)

(Examples 4 to 11 and Comparative Examples 8 to 19)
Using polycarbonate resin composition pellets (master batch) (B1-1) to (B4-1) that could be sampled, diluted so that the composition ratios (flame retardant concentration) shown in Tables 3 to 6 were obtained. After dry blending using polycarbonate ("Iupilon E-2000F" manufactured by Mitsubishi Engineering Plastics Co., Ltd.) as the polymer (E) for the coating, a bar-shaped test piece having a thickness of 2 mm and a plate having a thickness of 2 mm are used. A test specimen was prepared.

The molding by the injection molding machine was performed under the following conditions.
Molding machine: FANUC ROBOSHOT S-2000i
Molding conditions: cylinder temperature 280 ° C., mold temperature 70 ° C., injection speed 50 mm / sec, screw rotation speed 80 rpm, back pressure 3 MPa, holding pressure 50 MPa, holding pressure 5 sec, cooling time 10 sec.
Mold: Mold 1 (Bar-shaped specimen) Width 13 mm x Length 135 mm x Thickness 2 mm Mold for bar-shaped specimen 2 (Plate-shaped specimen) Width 50 mm x Length 50 mm x Thickness 2 mm Mold for plate specimen

(Measurement example of molded products: flame retardancy)
The obtained bar-shaped test piece having a thickness of 2 mm was evaluated by a method based on the UL94 vertical flammability test standard.

(Measurement example of molded products: Transparency)
The obtained plate-shaped test piece was measured by a method based on JIS-K7136 test method 3 using a haze meter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.

(Measurement example of molded product: Intrinsic viscosity)
Instead of the polycarbonate resin composition pellet (masterbatch), except that the obtained 2 mm thick bar-shaped test piece was pulverized, it was a method based on (Measurement Example of Masterbatch: Intrinsic Viscosity), Intrinsic viscosity was measured.

(Measurement example of molded products: molding processability)
When injection molding of 10 bar-shaped test pieces, the drawing at the time of resin weighing in the injection molding machine and the obtained bar-shaped test pieces were observed and evaluated according to the following criteria.
○: The molten resin did not leak from the nozzle during resin weighing, and no drawing occurred. In addition, the sprue portion of the bar-shaped test piece did not show any stringing, and was completely sprue-breaked and could be continuously formed.
Δ: The resin melted from the nozzle did not leak during resin weighing, and no drawing occurred. In addition, stringing was observed at the sprue portion of the bar-shaped test piece, and no sprue break occurred, and continuous molding was impossible.
X: The resin melted from the nozzle leaked during resin weighing, and drawing occurred. In addition, stringing was observed at the sprue portion of the bar-shaped test piece, and no sprue break occurred, and continuous molding was impossible.

Claims (15)

A flame-retardant resin composition containing a polycarbonate resin (A) and a phosphorus atom-containing oligomer (B) as essential components, wherein 3 parts of the phosphorus atom-containing oligomer (B) is added to 100 parts by mass of the polycarbonate resin (A). It contains in the range of -25 mass parts, and the said phosphorus atom containing oligomer (B) is following Structural formula (1).

(Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, n is a repeating unit of 1 or more, and X is a structural formula shown below. (X1) or (x2)

Y is a hydrogen atom, a hydroxyl group, or a structural moiety represented by the structural formula (x1) or (x2), and in the structural formula (x1) or (x2), R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group. The flame-retardant resin composition characterized by being represented by this.   In addition to the polycarbonate resin (A) and the phosphorus atom-containing oligomer (B), 0.01 to 10 parts by mass of a phosphorus stabilizer or an antioxidant (C2-3) is added to 100 parts by mass of the polycarbonate resin (A). The flame-retardant resin composition according to claim 1, which is contained in the range of A method for producing a flame retardant resin composition in which a polycarbonate resin (A) and a phosphorus atom-containing oligomer (B) are melt-kneaded, wherein the phosphorus atom-containing oligomer (B) is added to 100 parts by mass of the polycarbonate resin (A). It contains in 3-25 mass parts, and the said phosphorus atom containing oligomer (B) is following Structural formula (1).

(Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, n is a repeating unit of 1 or more, and X is a structural formula shown below. (X1) or (x2)

Y is a hydrogen atom, a hydroxyl group, or a structural moiety represented by the structural formula (x1) or (x2), and in the structural formula (x1) or (x2), R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group. The method for producing a flame retardant resin composition, which is represented by:   In addition to the polycarbonate resin (A) and the phosphorus atom-containing oligomer (B), 0.01 to 10 parts by mass of a phosphorus stabilizer or an antioxidant (C2-4) is added to 100 parts by mass of the polycarbonate resin (A). The method for producing a flame retardant resin composition according to claim 3, wherein the mixture is melt kneaded in the range described above. Step (1) for producing a flame-retardant masterbatch by melt-kneading the polycarbonate resin (A) and the phosphorus atom-containing oligomer (B) in advance, the flame-retardant masterbatch obtained in the step (1), A method for producing a flame retardant resin composition comprising a step (2) of melt-kneading a thermoplastic resin (E),
The phosphorus atom-containing oligomer (B) is
The following structural formula (1)

(Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, n is a repeating unit of 1 or more, and X is a structural formula shown below. (X1) or (x2)

Y is a hydrogen atom, a hydroxyl group, or a structural moiety represented by the structural formula (x1) or (x2), and in the structural formula (x1) or (x2), R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group. The method for producing a flame retardant resin composition, which is represented by: The flame-retardant resin composition according to claim 5, wherein in the step (1), the phosphorus atom-containing oligomer (B) is melt-kneaded in the range of 5 to 30 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). Method. In the step (2), the thermoplastic resin (E) is at least one selected from the group consisting of a polycarbonate resin, a polyester resin, a polyether ketone resin, a polyether resin, a polyimide resin, a polyamide resin, and a polyarylene ether resin. The manufacturing method of the flame-retardant resin composition of Claim 5 or 6. In addition to the polycarbonate resin (A) and the phosphorus atom-containing oligomer (B), 0.01 to 10 parts by mass of a phosphorus stabilizer or an antioxidant (C2-4) is added to 100 parts by mass of the polycarbonate resin (A). The method for producing a flame retardant resin composition according to any one of claims 5 to 7, wherein the flame retardant resin composition is melt kneaded in addition to the range described above. A flame retardant masterbatch containing polycarbonate resin (A) and phosphorus atom-containing oligomer (B) as essential components,
The phosphorus atom-containing oligomer (B) is represented by the following structural formula (1)

(Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, n is a repeating unit of 1 or more, and X is a structural formula shown below. (X1) or (x2)

Y is a hydrogen atom, a hydroxyl group, or a structural moiety represented by the structural formula (x1) or (x2), and in the structural formula (x1) or (x2), R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group. ),
The flame-retardant masterbatch which contains the said phosphorus atom containing oligomer (B) with the content rate used as the range of 5-30 mass parts with respect to 100 mass parts of polycarbonate resin (A). A flame retardant resin composition obtained by melting and kneading a thermoplastic resin (E) to the flame retardant master batch according to claim 9. The thermoplastic resin (E) is a polycarbonate resin, and the phosphorus atom-containing oligomer (B) is 3 with respect to 100 parts by mass in total of the polycarbonate resin (A) and the thermoplastic resin (E) in the flame retardant masterbatch. The flame-retardant resin composition according to claim 9 or 10, which is in the range of -25 parts by mass. The thermoplastic resin (E) is a thermoplastic resin other than a polycarbonate resin, and the thermoplastic resin (E) is 1 to 100 parts by mass with respect to 100 parts of the polycarbonate resin (A) in the flame retardant masterbatch, and The flame-retardant resin composition according to claim 9 or 10, wherein the phosphorus atom-containing oligomer (B) is in the range of 3 to 25 parts by mass. The molded object obtained by shape | molding the flame-retardant resin composition of Claim 2 or 9. A fiber obtained by molding the flame retardant resin composition according to claim 2 or 9. A film or sheet obtained by molding the flame retardant resin composition according to claim 2 or 9.