JP5881285B2 - Flame retardant resin composition and molded product therefrom - Google Patents

Description

  The present invention relates to a flame retardant resin composition using a plant-derived raw material having high flame retardancy, good heat resistance and physical properties, and a molded article therefrom. More particularly, the present invention relates to a flame retardant resin composition containing a specific organophosphorus compound and substantially free of halogen, and a molded article therefrom.

  Generally, polypropylene (PP), acrylonitrile-butadiene-styrene (ABS), polyamide (PA6, PA66), polyester (PET, PBT), polycarbonate (PC), etc. are used as raw materials for resin molded products. Is used. However, these resins are manufactured using raw materials obtained from petroleum resources. In recent years, there are concerns about problems such as depletion of petroleum resources and the global environment, and raw materials obtained from biological materials such as plants are used. There is a demand for the production of resin. Considering the problem of the global environment in particular, the resin that uses plant-derived materials is considered to be carbon neutral because it is neutral as a carbon balance, considering the amount of carbon dioxide absorbed during plant growth even if incinerated after use. It is considered to be a resin with a low impact on the global environment.

On the other hand, when resins using these plant-derived raw materials are used for industrial materials, particularly electrical / electronic parts, OA-related parts, or automobile parts, it is necessary to impart flame retardancy for safety reasons.
Until now, various attempts have been made for flame retarding of resins using plant-derived materials, particularly polylactic acid resins, and a certain degree of flame retarding has been achieved. However, these flame retardant formulations use a large amount of flame retardant, and further impair the original physical properties and heat resistance of the resin due to the properties of the flame retardant.

JP 2001-164014 A JP 2004-277552 A Japanese Patent Laying-Open No. 2005-023260 JP-A-2005-139441 JP 2007-246730 A JP 2008-019294 A

The first object of the present invention is to provide a flame retardant resin composition using a plant-derived raw material having high flame retardancy, good heat resistance and physical properties, and a molded product therefrom.
A second object of the present invention is to provide a flame retardant resin composition containing a specific organophosphorus compound and substantially halogen-free, and a molded article therefrom.

  According to the study by the present inventors, the object of the present invention is as follows: (A) 100 parts by weight of a resin component (component A) containing at least 50% by weight of stereocomplex polylactic acid (component A-1) (B) It is achieved by a flame retardant resin composition containing 1 to 100 parts by weight of an organophosphorus compound (B component) represented by the following formula (1) and a molded product therefrom.

（式中、Ｘ^１、Ｘ^２は同一もしくは異なり、下記式（２）で表される芳香族置換アルキル基である。）

（式中、ＡＬは炭素数１〜５の分岐状または直鎖状の脂肪族炭化水素基であり、Ａｒは置換基を有しても良いフェニル基、ナフチル基、またはアントリル基である。ｎは１〜３の整数を示し、ＡｒはＡＬ中の任意の炭素原子に結合することができる。）
２．Ａ−１成分のステレオコンプレックスポリ乳酸が、Ｌ−乳酸単位を９０モル％以上含有するポリＬ−乳酸（α−１成分）とＤ−乳酸単位を９０モル％以上含有するポリＤ−乳酸（β−１成分）を含有しα−１成分とβ−１成分の重量比が１０：９０〜９０：１０の範囲にある前項１記載の難燃性樹脂組成物、
３．Ａ−１成分のステレオコンプレックスポリ乳酸は、示差走査熱量計（ＤＳＣ）測定の昇温過程における融解ピークのうち１９５℃以上の割合が８０％以上である前項１記載の難燃性樹脂組成物、
４．樹脂成分（Ａ成分）中のステレオコンプレックスポリ乳酸（Ａ−１成分）以外の樹脂成分（Ａ−２成分）がＡ−１成分以外のポリエステル樹脂（ＰＥｓｔ）、ポリフェニレンエーテル樹脂（ＰＰＥ）、ポリカーボネート樹脂（ＰＣ）、ポリアミド樹脂（ＰＡ）、ポリオレフィン樹脂（ＰＯ）、スチレン系樹脂、ポリフェニレンサルファイド樹脂（ＰＰＳ）およびポリエーテルイミド樹脂（ＰＥＩ）からなる群から選択される少なくとも１種の樹脂成分である前項１記載の難燃性樹脂組成物、
５．樹脂成分（Ａ成分）１００重量部に対して、（Ｃ）充填剤（Ｃ成分）が５〜１５０重量部である前項１記載の難燃性樹脂組成物、
６．樹脂成分（Ａ成分）１００重量部に対して、耐衝撃改質剤（Ｄ成分）が３〜５０重量部である請求項１記載の難燃性樹脂組成物、
７．有機リン化合物（Ｂ成分）は、下記式（３）および下記式（４）で表される有機リン化合物よりなる群から選択される少なくとも１種の化合物である前項１記載の難燃性樹脂組成物、

（式中、Ｒ^２、Ｒ^５は同一または異なっていてもよく、置換基を有しても良いフェニル基、ナフチル基、またはアントリル基である。Ｒ^１、Ｒ^３、Ｒ^４、Ｒ^６は同一または異なっていてもよく、水素原子、炭素数１〜４の分岐状または直鎖状のアルキル基、置換基を有しても良いフェニル基、ナフチル基、またはアントリル基から選択される置換基である。）

（式中、Ａｒ^１およびＡｒ^２は、同一又は異なっていても良く、フェニル基、ナフチル基またはアントリル基であり、その芳香環に置換基を有していてもよい。Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４は、同一又は異なっていても良く、水素原子、炭素数１〜３の脂肪族炭化水素基またはフェニル基、ナフチル基もしくはアントリル基であり、その芳香環に置換基を有していてもよい。ＡＬ^１およびＡＬ^２は、同一又は異なっていても良く、炭素数１〜４の分岐状または直鎖状の脂肪族炭化水素基である。Ａｒ^３およびＡｒ^４は、同一又は異なっていても良く、フェニル基、ナフチル基またはアントリル基であり、その芳香環に置換基を有していてもよい。ｐおよびｑは０〜３の整数を示し、Ａｒ^３およびＡｒ^４はそれぞれＡＬ^１およびＡＬ^２の任意の炭素原子に結合することができる。）
８．有機リン化合物（Ｂ成分）が、下記式（５）で表される前項１記載の難燃性樹脂組成物、

（式中、Ｒ^２１、Ｒ^２２は同一もしくは異なり、フェニル基、ナフチル基またはアントリル基であり、その芳香環に置換基を有していてもよい。）
９．有機リン化合物（Ｂ成分）が、下記式（１−ａ）で示される化合物である前項１記載の難燃性樹脂組成物、

１０．有機リン化合物（Ｂ成分）が、下記式（６）で表される前項１記載の難燃性樹脂組成物、

（式中、Ｒ^３１およびＲ^３４は、同一又は異なっていても良く、水素原子または炭素数１〜３の脂肪族炭化水素基である。Ｒ^３３およびＲ^３６は、同一または異なっていても良く、炭素数１〜４の脂肪族炭化水素基である。Ｒ^３２およびＲ^３５は、同一または異なっていてもよく、フェニル基、ナフチル基またはアントリル基であり、その芳香環に置換基を有していてもよい。）
１１．有機リン化合物（Ｂ成分）が、下記式（１−ｂ）で示される化合物である前項１記載の難燃性樹脂組成物、

１２．有機リン化合物（Ｂ成分）が、下記式（７）で表される前項１記載の難燃性樹脂組成物、

（式中、Ａｒ^１およびＡｒ^２は、同一又は異なっていても良く、フェニル基、ナフチル基またはアントリル基であり、その芳香環に置換基を有していてもよい。Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４は、同一又は異なっていても良く、水素原子、炭素数１〜３の脂肪族炭化水素基またはフェニル基、ナフチル基もしくはアントリル基であり、その芳香環に置換基を有していてもよい。ＡＬ^１およびＡＬ^２は、同一又は異なっていても良く、炭素数１〜４の分岐状または直鎖状の脂肪族炭化水素基である。Ａｒ^３およびＡｒ^４は、同一又は異なっていても良く、フェニル基、ナフチル基またはアントリル基であり、その芳香環に置換基を有していてもよい。ｐおよびｑは０〜３の整数を示し、Ａｒ^３およびＡｒ^４はそれぞれＡＬ^１およびＡＬ^２の任意の炭素原子に結合することができる。）
１３．有機リン化合物（Ｂ成分）が、下記式（１−ｃ）で示される化合物である前項１記載の難燃性樹脂組成物、

１４．有機リン化合物（Ｂ成分）が、下記式（８）で表される前項１記載の難燃性樹脂組成物、

（式中、Ｒ^４１およびＲ^４４は、同一又は異なっていても良く、水素原子、炭素数１〜４の脂肪族炭化水素基またはフェニル基、ナフチル基もしくはアントリル基であり、その芳香環に置換基を有していてもよい。Ｒ^４２、Ｒ^４３、Ｒ^４５およびＲ^４６は、同一または異なっていても良く、フェニル基、ナフチル基またはアントリル基であり、その芳香環に置換基を有していてもよい。）
１５．有機リン化合物（Ｂ成分）が、下記式（１−ｄ）で示される化合物である前項１記載の難燃性樹脂組成物、

１６．有機リン化合物（Ｂ成分）の酸価が０．７ｍｇＫＯＨ／ｇ以下である前項１記載の難燃性樹脂組成物、
１７．有機リン化合物（Ｂ成分）のＨＰＬＣ純度が少なくとも９０％である前項１記載の難燃性樹脂組成物、
１８．ＵＬ−９４規格の難燃レベルにおいて、少なくともＶ−２を達成する前項１記載の難燃性樹脂組成物、
１９．前項１記載の難燃性樹脂組成物より形成された成形品、
が提供される。 That is, according to the present invention,
1. (A) With respect to 100 parts by weight of a resin component (component A) containing at least 50% by weight of stereocomplex polylactic acid (component A-1), (B) an organophosphorus compound (B) represented by the following formula (1) (Component) 5 to 90 parts by weight, (C) filler (component C) 1 to 200 parts by weight , (D) impact modifier (D component) 2 to 80 parts by weight, and (E) talc as a crystallization accelerator (E component) 0.01-30 parts by weight, impact modifier (D component) is styrene-ethylene-butylene-styrene terpolymer (SEBS), styrene-ethylene-propylene-styrene A flame retardant resin composition which is at least one hydrogenated styrene-based thermoplastic elastomer selected from a terpolymer (SEPS) and a styrene-ethylene-propylene-styrene terpolymer (SEEPS) ,

(In formula, X < ¹ >, X < ² > is the same or different, and is an aromatic substituted alkyl group represented by following formula (2).)

(In the formula, AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, and Ar is a phenyl group, a naphthyl group, or an anthryl group which may have a substituent. Represents an integer of 1 to 3, and Ar can be bonded to any carbon atom in AL.)
2. The stereocomplex polylactic acid of component A-1 is poly L-lactic acid (α-1 component) containing 90 mol% or more of L-lactic acid units and poly D-lactic acid (β containing 90 mol% or more of D-lactic acid units). -1 component), and the weight ratio of the α-1 component and the β-1 component is in the range of 10:90 to 90:10,
3. The flame retardant resin composition according to item 1 above, wherein the stereocomplex polylactic acid as component A-1 has a ratio of 195 ° C. or higher of the melting peak in the temperature rising process of differential scanning calorimeter (DSC) measurement being 80% or higher,
4). Polyester resin (PEst), polyphenylene ether resin (PPE), and polycarbonate resin other than the A-1 component as the resin component (A-2 component) other than the stereocomplex polylactic acid (A-1 component) in the resin component (A component) The above-mentioned item which is at least one resin component selected from the group consisting of (PC), polyamide resin (PA), polyolefin resin (PO), styrene resin, polyphenylene sulfide resin (PPS) and polyetherimide resin (PEI) The flame retardant resin composition according to 1,
5). The flame-retardant resin composition according to item 1 , wherein the filler (C component) is 5 to 150 parts by weight with respect to 100 parts by weight of the resin component (component A) ;
6). The flame retardant resin composition according to claim 1, wherein the impact resistance modifier (D component) is 3 to 50 parts by weight with respect to 100 parts by weight of the resin component (A component).
7). The flame retardant resin composition according to item 1, wherein the organophosphorus compound (component B) is at least one compound selected from the group consisting of organophosphorus compounds represented by the following formula (3) and the following formula (4): object,

(In the formula, R ² and R ⁵ may be the same or different, and may be a phenyl group, a naphthyl group, or an anthryl group that may have a substituent. R ¹ , R ³ , R ⁴ , R ⁶ are Substituents which may be the same or different and are selected from a hydrogen atom, a branched or straight chain alkyl group having 1 to 4 carbon atoms, an optionally substituted phenyl group, naphthyl group, or anthryl group .)

(In formula, Ar < ¹ > and Ar < ² > may be the same or different, and are a phenyl group, a naphthyl group, or an anthryl group, and may have a substituent in the aromatic ring. R < ¹¹ >, R < ¹² >, R ¹³ and R ¹⁴ may be the same or different, and are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a phenyl group, a naphthyl group or an anthryl group, and have a substituent in the aromatic ring. AL ¹ and AL ² may be the same or different and are branched or straight-chain aliphatic hydrocarbon groups having 1 to 4 carbon atoms, Ar ³ and Ar ⁴ may be the same or It may be different, and may be a phenyl group, a naphthyl group or an anthryl group, and may have a substituent on the aromatic ring, p and q each represent an integer of 0 to ^3, and Ar ³ and Ar ⁴ each represent AL ¹ Contact It can be attached to any carbon atom of the fine AL ^2.)
8). The flame retardant resin composition according to item 1, wherein the organic phosphorus compound (component B) is represented by the following formula (5):

(Wherein R ²¹ and R ²² are the same or different and are a phenyl group, a naphthyl group or an anthryl group, and the aromatic ring may have a substituent.)
9. The flame retardant resin composition according to item 1, wherein the organic phosphorus compound (component B) is a compound represented by the following formula (1-a):

10. The flame retardant resin composition according to item 1, wherein the organic phosphorus compound (component B) is represented by the following formula (6):

(In the formula, R ³¹ and R ³⁴ may be the same or different, and are a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. R ³³ and R ³⁶ may be the same or different. And an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R ³² and R ³⁵ may be the same or different and each is a phenyl group, a naphthyl group or an anthryl group, and has a substituent in the aromatic ring. May be.)
11. The flame retardant resin composition according to item 1, wherein the organic phosphorus compound (component B) is a compound represented by the following formula (1-b):

12 The flame retardant resin composition according to item 1, wherein the organic phosphorus compound (component B) is represented by the following formula (7):

(In formula, Ar < ¹ > and Ar < ² > may be the same or different, and are a phenyl group, a naphthyl group, or an anthryl group, and may have a substituent in the aromatic ring. R < ¹¹ >, R < ¹² >, R ¹³ and R ¹⁴ may be the same or different, and are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a phenyl group, a naphthyl group or an anthryl group, and have a substituent in the aromatic ring. AL ¹ and AL ² may be the same or different and are branched or straight-chain aliphatic hydrocarbon groups having 1 to 4 carbon atoms, Ar ³ and Ar ⁴ may be the same or It may be different, and may be a phenyl group, a naphthyl group or an anthryl group, and may have a substituent on the aromatic ring, p and q each represent an integer of 0 to ^3, and Ar ³ and Ar ⁴ each represent AL ¹ Contact It can be attached to any carbon atom of the fine AL ^2.)
13. The flame retardant resin composition according to item 1, wherein the organic phosphorus compound (component B) is a compound represented by the following formula (1-c):

14 The flame retardant resin composition according to item 1, wherein the organic phosphorus compound (component B) is represented by the following formula (8):

(In the formula, R ⁴¹ and R ⁴⁴ may be the same or different and are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group or an anthryl group, and substituted on the aromatic ring thereof. R ⁴² , R ⁴³ , R ⁴⁵ and R ⁴⁶ may be the same or different and are a phenyl group, a naphthyl group or an anthryl group, and have a substituent on the aromatic ring. May be.)
15. The flame retardant resin composition according to item 1, wherein the organophosphorus compound (component B) is a compound represented by the following formula (1-d):

16. The flame-retardant resin composition according to item 1, wherein the organic phosphorus compound (component B) has an acid value of 0.7 mgKOH / g or less,
17. The flame-retardant resin composition according to item 1, wherein the organophosphorus compound (component B) has an HPLC purity of at least 90%;
18. The flame retardant resin composition according to item 1 above, which achieves at least V-2 at a flame retardant level of UL-94 standard,
19. A molded product formed from the flame retardant resin composition according to the preceding item 1,
Is provided.

  According to this invention, the flame-retardant resin composition using the plant-derived raw material which achieves high flame retardance without impairing the original characteristic of resin is obtained.

The flame retardant resin composition of the present invention and a molded product formed therefrom have the following advantages compared to conventional resin compositions using plant-derived materials.
(I) A resin composition using a plant-derived raw material having high flame retardancy 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 a resin using a plant-derived raw material, the V-2 level, particularly preferably the V-0 level, even with a relatively small amount used. Achieved.
(Iii) Due to the structure and properties of the organophosphorus compound used as a flame retardant, thermal degradation of the resin using the plant-derived raw material hardly occurs during the molding of the resin using the plant-derived raw material or the molded product. In addition, a resin composition having excellent heat resistance can be obtained. Therefore, a composition having excellent balance of flame retardancy, mechanical strength and heat resistance can be obtained.

Hereinafter, the flame retardant resin composition of the present invention will be described in more detail.
Stereocomplex polylactic acid (A-1 component) having a content of at least 50% by weight in the resin component (A component) in the present invention is disclosed in JP-A-63-240142 and Macromolecules, 24, 5651 (1991). As described, a stereo complex is obtained by mixing poly-L-lactic acid (α-1 component) composed of L-lactic acid units and poly-D-lactic acid (β-1 component) composed of D-lactic acid units in a solution or in a molten state. It is known that polylactic acid is formed.

The poly-1 L-lactic acid as the α-1 component is preferably composed of 90 to 100 mol% of L-lactic acid units and 0 to 10 mol% of copolymerized units other than L-lactic acid.
The poly-D-lactic acid which is a β-1 component is preferably composed of 90 to 100 mol% of D-lactic acid units and 0 to 10 mol% of copolymerized units other than D-lactic acid. That is, the optical purity of the α-1 component or the β-1 component is preferably 90 to 100 mol%. When the optical purity is lower than 90 mol%, the crystallinity and the melting point are lowered, and the formation of a stereocomplex is caused. It becomes difficult. Therefore, the melting point of the α-1 component or the β-1 component is preferably 160 ° C. or higher, more preferably 170 ° C. or higher, and further preferably 175 ° C. or higher.

From this viewpoint, the optical purity of lactic acid and lactide which are polymer raw materials is preferably 96 to 100 mol%, more preferably 97.5 to 100 mol%, still more preferably 98.5 to 100 mol%, and most preferably 99. It is in the range of ˜100 mol%.
The copolymer unit is a D-lactic acid unit if it is an α-1 component, and an L-lactic acid unit if it is a β-1 component, and examples include units other than lactic acid.

  The copolymer unit other than the lactic acid unit is in the range of 0 to 10 mol%, preferably 0 to 5 mol%, more preferably 0 to 2 mol%, still more preferably 0 to 1 mol%. Copolymerized units include units derived from dicarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones and the like having functional groups capable of forming two or more ester bonds, and various polyesters, various polyethers, various types composed of these various components. Examples are units derived from polycarbonate and the like.

  Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid. Examples of the polyhydric alcohol include aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol. Or aromatic polyhydric alcohols, such as what added ethylene oxide to bisphenol, etc. are mentioned. Examples of the hydroxycarboxylic acid include glycolic acid and hydroxybutyric acid. Examples of the lactone include glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, and δ-valerolactone.

The weight average molecular weights of the α-1 component and the β-1 component are preferably 80,000 to 300,000, more preferably 100,000 to 250,000, more preferably, in order to achieve both the mechanical properties and moldability of the composition of the present invention. Is in the range of 1 to 230,000.
The weight average molecular weight and number average molecular weight of polylactic acid are values measured by gel permeation chromatography (GPC) and converted to standard polystyrene.

  The production method of α-1 component and β-1 component is not particularly limited, and can be produced by a conventionally known method. For example, L- or D-lactide melt ring-opening polymerization method, low molecular weight polylactic acid Examples of the solid phase polymerization method, and a direct polymerization method in which lactic acid is dehydrated and condensed can be exemplified.

  The polymerization reaction can be carried out in a conventionally known reaction apparatus. For example, a vertical reactor or a horizontal reactor equipped with a high-viscosity stirring blade such as a helical ribbon blade can be used alone or in parallel. Moreover, any of a batch type, a continuous type, a semibatch type may be sufficient, and these may be combined.

  In the solid-state polymerization method, it is preferable to crystallize the prepolymer in advance from the viewpoint of preventing fusion of pellets and production efficiency, and the container itself rotates like a fixed vertical or horizontal reaction vessel, or a tumbler or kiln. In a reaction vessel (such as a rotary kiln), the polymerization is carried out by raising the temperature gradually with the progress of the polymerization at a constant temperature in the temperature range from the glass transition temperature of the prepolymer to less than the melting point. For the purpose of efficiently removing generated water, a method of reducing the pressure inside the reaction vessels or circulating a heated inert gas stream is also preferably used.

  The composition of this invention contains the metal catalyst used when manufacturing polylactic acid. The metal catalyst is a compound containing at least one metal element selected from the group consisting of alkaline earth metals, rare earth metals, third-period transition metals, aluminum, germanium, tin, and antimony. Examples of the alkaline earth metal include magnesium, calcium, and strontium. Examples of rare earth elements include scandium, yttrium, lanthanum, and cerium. As the transition metal of the third period, iron, cobalt, nickel, and zinc can be cited. Metal catalysts are added to the composition, for example, as carboxylates, alkoxides, aryloxides or enolates of β-diketones of these metals. In view of polymerization activity and hue, tin octylate, titanium tetraisopropoxide, and aluminum triisopropoxide are particularly preferable.

  The content of the metal catalyst is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.1 part by weight with respect to 100 parts by weight of polylactic acid. When the content of the metal catalyst is too small, the polymerization rate is remarkably lowered. On the contrary, if the amount is too large, coloring due to reaction heat or depolymerization or transesterification reaction is accelerated, so that the hue and thermal stability of the resulting composition are deteriorated.

  Alcohol may be used as a polymerization initiator. Such alcohol is preferably non-volatile without inhibiting the polymerization of polylactic acid. For example, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol and the like can be suitably used.

  A stereocomplex crystal is formed by mixing an α-1 component and a β-1 component. In this case, the weight ratio of the α-1 component to the β-1 component is preferably 90:10 to 10:90, more preferably 75:25 to 25:75, and still more preferably 60:40 to 40:60. is there.

  Highly stereocomplexed stereocomplex polylactic acid (component A-1) has a ratio of 195 ° C. or higher of the melting peak in the temperature rising process of differential scanning calorimeter (DSC) measurement to 80% or higher. The proportion of the melting peak of the A-1 component at 195 ° C. or higher is preferably 80% or higher, more preferably 90% or higher, and most preferably 100%. If the ratio of the melting peak at 195 ° C. or higher is lower than 80%, the characteristics of homocrystals derived from poly L-lactic acid (α-1 component) and poly D-lactic acid (β-1 component) appear, and the heat resistance is high. It becomes insufficient.

  The melting peak of the component A-1 is preferably 200 ° C. or higher, more preferably 205 ° C. or higher, and further preferably 210 ° C. or higher. When the melting peak of the A-1 component is lower than 195 ° C., the heat resistance is insufficient due to its crystallinity and low melting point.

  Such a highly stereocomplexed A-1 component is poly-L-lactic acid (α-1 component and poly-D-lactic acid (β-1 component) are present in such a quantitative ratio. The obtained enantiomeric average chain length can be preferably in the range of 10 to 40, and only the crystal melting peak of the stereocomplex phase polylactic acid is observed without the crystal melting peak of the homophase polylactic acid. .

Here, the enantiomeric average chain length (Li) determined by 13C-NMR is the peak of the quadruple structure of CH carbon of polylactic acid in Makromol. Chem. , 191, 287 (1990), and the area ratio (Iiii, Iisi, Isi, Iiis, Isis, Issi, Iiss, Isss) is a value defined by the formula (IV). i represents isotactic (LL, DD), and s represents syndiotactic (LD, DL) linkage.
Li = (3Iiii + 2Iisi + 2Isi + 2Iii + Isis + Issi + Iiss) / (Iisi + Iis + Isi + 2Isis + 2Issi + 2Iiss + 3Isss) +1 (IV)

  In the present invention, the enantiomeric average chain length (Li) is preferably in the range of 10 to 40, and by satisfying such a condition, the heat resistance of the composition, particularly suitable release properties can be achieved. .

  If the average enantiomeric chain length is less than 10, even if a stereocomplex phase polylactic acid is highly formed in the DSC measurement, the composition may be inferior in heat resistance. This is because the formation of lactic acid is inferior and the heat resistance is inferior. In addition to this point of view, the enantiomeric average chain length is preferably selected from the range of 15 to 40, more preferably 18 to 39, from the viewpoint of the releasability of the composition.

  In the resin component (component A) in the present invention, as preferred examples of the resin component (component A-2) other than stereocomplex polylactic acid (component A-1), polyester resin (PEst) other than component A-1 and polyphenylene At least selected from the group consisting of ether resin (PPE), polycarbonate resin (PC), polyamide resin (PA), polyolefin resin (PO), styrene resin, polyphenylene sulfide resin (PPS) and polyetherimide resin (PEI). One type of resin component may be mentioned. Of these A-2 components, polyester resin (PEst), polyphenylene ether resin (PPE), polycarbonate resin (PC), polyamide resin (PA), polyolefin resin (PO), and styrenic resin are preferable.

Next, the thermoplastic resin as the component A-2 will be specifically described.
As polyester resin (PEst) as A-2 component, 1 type, or 2 or more types selected from polylactic acid and / or lactic acid copolymer other than A-1 component, aromatic polyester resin, or aliphatic polyester resin Of the mixture.

  Among the polylactic acid and / or lactic acid copolymer other than the component A-1, polylactic acid is L-lactic acid, D-lactic acid, DL-lactic acid or a mixture thereof, or L which is a cyclic dimer of L-lactic acid. -Polymers using lactide, D-lactide, which is a cyclic dimer of D-lactic acid, meso-lactide, which is a cyclic dimer from L-lactic acid and D-lactic acid, or a mixture thereof.

  The method for producing the polylactic acid used in the present invention is not particularly limited, but it is generally produced by using a known melt polymerization method or a solid phase polymerization method in combination. Specific examples are disclosed in U.S. Pat. No. 1,995,970, U.S. Pat. No. 2,362,511, U.S. Pat. No. 2,683,136, and a cyclic dimer of lactic acid generally called lactide. Is synthesized by ring-opening polymerization. US Pat. No. 2,758,987 discloses a ring-opening polymerization method in which a cyclic dimer (lactide) of lactic acid is melt-polymerized.

  Of the polylactic acid and / or lactic acid copolymer that is the component A-2, the lactic acid copolymer is a copolymer containing lactic acid as a main raw material, such as a lactic acid-hydroxycarboxylic acid copolymer. And lactic acid-aliphatic polyhydric alcohol-aliphatic polybasic acid copolymer.

  Specific examples of the hydroxycarboxylic acid used in the lactic acid copolymer used in the present invention include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 4-hydroxy Examples include valeric acid and 6-hydroxycaproic acid, which can be used alone or as a mixture of two or more. Furthermore, a cyclic ester intermediate of hydroxycarboxylic acid, for example, glycolide which is a dimer of glycolic acid or ε-caprolactone which is a cyclic ester of 6-hydroxycaproic acid can be used.

Specific examples of the aliphatic polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol,
Dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, decamethylene glycol Aliphatic diols such as 1,4-cyclohexanedimethanol and the like can be used alone or as a mixture of two or more.

  Specific examples of the aliphatic polybasic acid include aliphatic dibasic acids such as succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid. A basic acid is mentioned, It can use individually or in mixture of 2 or more types.

  A copolymer of lactic acid and hydroxycarboxylic acid is usually synthesized from a cyclic ester intermediate of lactide and hydroxycarboxylic acid by ring-opening polymerization, and the production method thereof is described in US Pat. No. 3,635,956, US Pat. 797,499. US Pat. No. 5,310,865 discloses a method in which dehydration polycondensation is directly performed using a mixture of lactic acid and hydroxycarboxylic acid as a raw material. US Pat. No. 4,057,537 discloses a ring-opening polymerization method in which a cyclic dimer of lactic acid and an aliphatic hydroxycarboxylic acid, for example, lactide or glycolide and ε-caprolactone is melt-polymerized in the presence of a catalyst. It is disclosed. In the case of producing a lactic acid copolymer by direct dehydration polycondensation without using ring-opening polymerization, lactic acid and other hydroxycarboxylic acid as necessary are preferably copolymerized in the presence of an organic solvent, particularly a phenyl ether solvent. Lactic acid co-condensation with a polymerization degree suitable for the present invention is carried out by polymerizing by a method in which water is removed from the solvent distilled off by azeotropic distillation and water is removed, and the solvent is brought into a substantially anhydrous state, and returned to the reaction system. A polymer is obtained.

US Pat. No. 5,428,126 discloses a method for directly dehydrating and condensing a mixture of lactic acid, an aliphatic dihydric alcohol and an aliphatic dibasic acid. European Patent Publication No. 071880A2 discloses a method of condensing a polymer of polylactic acid, an aliphatic dihydric alcohol and an aliphatic dibasic acid in the presence of an organic solvent.
In the present invention, when a polylactic acid or a lactic acid copolymer is produced, an appropriate molecular weight regulator, branching agent, other modifier, etc. may be added.

  The aromatic polyester resin as the component A-2 is a polyester having an aromatic dicarboxylic acid as a main dicarboxylic acid component and an aliphatic diol having 2 to 10 carbon atoms as a main glycol component. Preferably 80 mol% or more, more preferably 90 mol% or more of the dicarboxylic acid component is composed of an aromatic dicarboxylic acid component. On the other hand, the glycol component preferably comprises an aliphatic diol component having 2 to 10 carbon atoms, more preferably 80 mol% or more, and more preferably 90 mol% or more.

  Preferable examples of the aromatic dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, methyl terephthalic acid, methyl isophthalic acid, 2,6-naphthalenedicarboxylic acid, and the like. These can use 1 type (s) or 2 or more types. Examples of secondary dicarboxylic acids other than aromatic dicarboxylic acids include aliphatic dicarboxylic acids such as adipic acid, sebacic acid, decanedicarboxylic acid, azelaic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, and alicyclic dicarboxylic acids. it can.

  Examples of the aliphatic diol having 2 to 10 carbon atoms include aliphatic diols such as ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol and neopentyl glycol, and alicyclic diols such as 1,4-cyclohexanedimethanol. Can be mentioned. Examples of glycols other than aliphatic diols having 2 to 10 carbon atoms include p, p'-dihydroxyethoxybisphenol A and polyoxyethylene glycol.

  Preferred examples of the aromatic polyester resin include at least one dicarboxylic acid selected from terephthalic acid and 2,6-naphthalenedicarboxylic acid as the main dicarboxylic acid component, and ethylene glycol, trimethylene glycol, and tetramethylene as the main diol component. A polyester having an ester unit composed of at least one diol selected from glycols.

  Specific aromatic polyester resins include polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, polycyclohexanedimethyl terephthalate resin, polytrimethylene terephthalate resin, and polytrimethylene naphthalate resin. It is preferably at least one selected from the group consisting of

Particularly preferred is at least one selected from the group consisting of a polyethylene terephthalate resin, a polybutylene terephthalate resin and a polyethylene naphthalate resin. In particular, polybutylene terephthalate resin is particularly preferable.
Moreover, the polyester elastomer which uses the said repeating unit as the main repeating unit of a hard segment can also be used as aromatic polyester resin of this invention.

As the soft segment of the polyester elastomer having tetramethylene terephthalate or tetramethylene-2,6-naphthalenedicarboxylate as the main repeating unit of the hard segment, for example, dicarboxylic acid is selected from terephthalic acid, isophthalic acid, sebacic acid and adipic acid From at least one dicarboxylic acid consisting of at least one dicarboxylic acid and having a diol component selected from the group consisting of a long-chain diol having 5 to 10 carbon atoms and H (OCH ₂ CH ₂ ) _i OH (i = 2 to 5) Further, a polyester or polycaprolactone having a melting point of 100 ° C. or lower or amorphous can be used.

  The main component is a component of 80 mol% or more, preferably 90 mol% or more of the total dicarboxylic acid component or the total glycol component, and the main repeating unit is 80 mol% or more of the total repeating unit, preferably 90 mol%. It is a repeating unit of mol% or more.

  The molecular weight of the aromatic polyester resin in the present invention may be any intrinsic viscosity that can be used as a normal molded article, and the intrinsic viscosity measured in orthochlorophenol at 35 ° C. is preferably 0.5 to 1.6 dl. / G, more preferably 0.6 to 1.5 dl / g.

  Moreover, it is advantageous that the aromatic polyester resin has a terminal carboxyl group (—COOH) amount of 1 to 60 equivalents / T (1 ton of polymer). The amount of the terminal carboxyl group can be determined, for example, by potentiometric titration of an m-cresol solution with an alkaline solution.

  As polyphenylene ether resin as A-2 component, what is generally known as PPE resin can be used. Specific examples of such PPE include (2,6-dimethyl-1,4-phenylene) ether, (2,6-diethyl-1,4-phenylene) ether, (2,6-dipropyl-1,4-phenylene). ) Ether, (2-methyl-6-ethyl-1,4-phenylene) ether, (2-methyl-6-propyl-1,4-phenylene) ether, (2,3,6-trimethyl-1,4- Homopolymers and / or copolymers such as (phenylene) ether are mentioned, and poly (2,6-dimethyl-1,4-phenylene) ether is particularly preferred. Moreover, the copolymer which the styrene compound graft-polymerized to these PPE may be sufficient. The method for producing such PPE is not particularly limited. For example, 2,6-xylenol is oxidized using a complex of cuprous salt and amines as a catalyst according to the method described in US Pat. No. 3,306,874. It can be easily produced by polymerization.

  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 PPE resin, is 0.2 to 0.7 dl / g, preferably 0.3 to 0.6 dl. / G. A PPE resin having a reduced viscosity in this range has a good balance between molding processability and mechanical properties, and the reduced viscosity can be easily adjusted by adjusting the amount of catalyst during the production of PPE.

  The polycarbonate resin (PC) as the component A-2 is obtained by an interfacial polymerization reaction of various dihydroxyaryl compounds and phosgene using a solvent such as methylene chloride, or an ester of a dihydroxyaryl compound and diphenyl carbonate. What is obtained by an exchange reaction is mentioned. A typical example is a polycarbonate obtained by the reaction of 2,2'-bis (4-hydroxyphenyl) propane and phosgene.

  Examples of the dihydroxyaryl compound used as a raw material for polycarbonate include bis (4-hydroxyphenyl) methane, 1,1′-bis (4-hydroxyphenyl) ethane, 2,2′-bis (4-hydroxyphenyl) propane, 2, 2'-bis (4-hydroxyphenyl) butane, 2,2'-bis (4-hydroxyphenyl) octane, 2,2'-bis (4-hydroxy-3-methylphenyl) propane, 2,2'-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2′-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2′-bis (4-hydroxy-3-cyclohexylphenyl) Propane, 2,2′-bis (4-hydroxy-3-methoxyphenyl) propane, 1,1′-bis (4-hydroxyphenyl) Cyclopentane, 1,1′-bis (4-hydroxyphenyl) cyclohexane, 1,1′-bis (4-hydroxyphenyl) cyclododecane, 4,4′-dihydroxyphenyl ether, 4,4′-dihydroxy-3, 3'-dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, Examples include bis (4-hydroxyphenyl) ketone. These dihydroxyaryl compounds can be used alone or in combination of two or more.

  Preferred dihydroxyaryl compounds include bisphenols that form highly heat-resistant aromatic polycarbonates, bis (hydroxyphenyl) alkanes such as 2,2′-bis (4-hydroxyphenyl) propane, and bis (4-hydroxyphenyl) cyclohexane. Bis (hydroxyphenyl) cycloalkane, dihydroxydiphenyl sulfide, dihydroxydiphenyl sulfone, dihydroxydiphenyl ketone and the like. A particularly preferred dihydroxyaryl compound is 2,2'-bis (4-hydroxyphenyl) propane which forms a bisphenol A type aromatic polycarbonate.

  In addition, if it is a range which does not impair heat resistance, mechanical strength, etc., when manufacturing bisphenol A type aromatic polycarbonate, you may substitute a part of bisphenol A with another dihydroxyaryl compound.

The molecular weight of the polycarbonate resin is not particularly limited, but if it is too low, the strength is not sufficient, and if it is too high, the melt viscosity becomes high and it becomes difficult to mold, so it is usually 10,000 to 50,000 in terms of viscosity average molecular weight. It is preferably 15,000 to 30,000. The viscosity average molecular weight (M) mentioned here is obtained by inserting the specific viscosity (η _sp ) obtained from a solution obtained by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20 ° C. into the following equation.
η _sp /C=[η]+0.45×[η] ² C
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
([Η] is the intrinsic viscosity, C is the polymer concentration of 0.7)

  The basic means for producing the polycarbonate resin will be briefly described. In the interfacial polymerization method (solution polymerization method) using phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and an organic solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, or amine compounds such as pyridine. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In addition, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used for promoting the reaction, and a terminal terminator such as an alkyl-substituted phenol such as phenol or p-tert-butylphenol is used as a molecular weight regulator. It is desirable to use it. The reaction temperature is preferably 0 to 40 ° C., the reaction time is several minutes to 5 hours, and the pH during the reaction is preferably maintained at 10 or more. It should be noted that not all of the resulting molecular chain ends need to have a structure derived from a terminal terminator.

  In a transesterification reaction (melt polymerization method) using a carbonic acid diester as a carbonate precursor, a predetermined proportion of dihydric phenol is stirred with the carbonic acid diester in the presence of an inert gas, and the resulting alcohol or phenol is distilled. It is done by the method. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 350 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. An end terminator is added simultaneously with the dihydric phenol or the like in the initial stage of the reaction or in the middle of the reaction. Moreover, in order to accelerate | stimulate reaction, the catalyst used for the transesterification reaction now well-known can be used. Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.

  Examples of the polyamide resin (PA) as the component A-2 include ring-opening polymer of cyclic lactam, polymer of aminocarboxylic acid, polycondensate of dibasic acid and diamine, and the like. Nylon 6, Nylon 66, Nylon 46, Nylon 610, Nylon 612, Nylon 11, Nylon 12, and other aliphatic polyamides and poly (metaxylene adipamide), poly (hexamethylene terephthalamide), poly (nonamethylene terephthalamide) And aliphatic-aromatic polyamides such as poly (hexamethylene isophthalamide) and poly (tetramethylene isophthalamide), and copolymers and mixtures thereof. The polyamide that can be used in the present invention is not particularly limited.

  The molecular weight of such a polyamide resin is not particularly limited, but a relative viscosity of 1.7 to 4.5 measured at 25% in 98% sulfuric acid at a concentration of 1% can be preferably used. Is 2.0 to 4.0, particularly preferably 2.0 to 3.5.

  The polyolefin resin as the component A-2 is a homopolymer or copolymer of olefins such as ethylene, propylene and butene, or a copolymer of monomer components copolymerizable with these olefins. . Specifically, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-α-olefin copolymer Examples thereof include a copolymer, an ethylene-propylene copolymer, and an ethylene-butene copolymer. The molecular weight of these polyolefin resins is not particularly limited, but the higher the molecular weight, the better the flame retardancy.

  The styrene resin as the component A-2 is a homopolymer or copolymer of an aromatic vinyl monomer such as styrene, α-methylstyrene or vinyltoluene, these monomers and acrylonitrile, methyl methacrylate or the like. Styrene and / or styrene derivatives, or styrene and / or styrene derivatives and other vinyl monomers are graft-polymerized onto copolymers with vinyl monomers, diene rubbers such as polybutadiene, ethylene / propylene rubber, acrylic rubber, etc. It has been made. Specific examples of the styrenic resin include, for example, 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 styrene resin is 1 to 80% by weight, preferably 2 to 70% by weight. The monomer mixture capable of graft polymerization is 99 to 20% by weight, preferably 98 to 30% by weight.

Styrene resin used as the component A-2 of the present invention, in particular high impact polystyrene, in accordance with the JIS-K-7210-1999, 200 ℃ , MVR value measured under the conditions of 5kg load 1 to 100 cm ³ / 10min preferably in the range ^of, more preferably in the range of 2~80cm 3 / ^10min, more preferably in the range of 3~60cm 3 / ^10min, a range of 5 to 50 cm 3 / 10min is particularly preferred.

In addition, the styrene resin used as the A-2 component of the present invention, particularly AS resin and ABS resin, has an MVR value of 1 to 100 cm measured at 220 ° C. under a load of 10 kg in accordance with JIS-K-7210-1999. ³ / range of 10min is ^preferred, more preferably in the range of 2～80Cm 3 / ^10min, more preferably in the range of 3～60Cm 3 / ^10min, a range of 5 to 50 cm 3 / 10min is particularly preferred.

It is less than the styrene-based resin MVR value ^{1 cm} 3 / 10min will be reduced workability during time and extrusion of the resin ^composition, greater than 100 cm 3 / 10min when lowering heat resistance and mechanical properties of the resin composition Will be.

  The styrene resin used as the component A-2 of the present invention preferably has a reduced viscosity ηsp / C, which is a measure of its molecular weight, of 0.2 to 1.5 dl / g, more preferably 0.3 to 1. 4 dl / g. Here, the reduced viscosity ηsp / C is a value obtained by measuring a toluene solution having a solution concentration of 0.5 g / 100 ml at 30 ° C.

When the reduced viscosity ηsp / C of the styrene resin is lower than 0.2 dl / g, the heat resistance and mechanical properties of the resulting resin composition are lowered. Moreover, when higher than 1.5 dl / g, the workability at the time of extrusion of a resin composition, a shaping | molding, etc. will fall.
Examples of means for satisfying the above conditions regarding the MVR value and the reduced viscosity ηsp / C of the styrene resin include adjustment of the polymerization initiator amount, the polymerization temperature, and the chain transfer agent amount.

式中、ｎは１以上の整数であり、５０〜５００の整数が好ましく１００〜４００の整数がより好ましく、直鎖状、架橋状いずれであってもよい。 The polyphenylene sulfide resin (PPS) as the component A-2 has a repeating unit represented by the following formula.

In the formula, n is an integer of 1 or more, preferably an integer of 50 to 500, more preferably an integer of 100 to 400, and may be linear or crosslinked.

  An example of a method for producing a polyphenylene sulfide resin is a method of reacting dichlorobenzene with sodium disulfide. Cross-linked polymers can be manufactured by polymerizing a polymer with a low polymerization degree in the presence of air and then partially crosslinking to increase the molecular weight. It can be manufactured by the method.

The polyetherimide resin (PEI) as the component A-2 has a repeating unit represented by the following formula.

Ar ¹ in the formula represents an aromatic dihydroxy compound residue, and Ar ² represents an aromatic diamine residue. As an aromatic dihydroxy compound, the aromatic dihydroxy compound shown by description of polycarbonate resin mentioned above is mentioned, Bisphenol A is especially preferable. As aromatic diamines, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenyl, 3,4′-diaminodiphenyl, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, diaminodiphenylmethane, Examples include diaminodiphenyl sulfone and diaminodiphenyl sulfide.
N in the above formula represents an integer of 5 to 1,000, and an integer of 10 to 500 is preferable.

  Examples of the method for producing the polyetherimide resin include US Pat. No. 3,847,867, US Pat. No. 3,847,869, US Pat. No. 3,850,885, US Pat. No. 3,852. 242 and U.S. Pat. No. 3,855,178.

  Of the various A-2 components described above, polyester resins (PEst), polyphenylene ether resins (PPE), polycarbonate resins (PC), polyamide resins (PA), polyolefin resins (PO), and styrenes other than the A-1 component Resins are preferred.

（式中、Ｘ^１、Ｘ^２は同一もしくは異なり、下記式（２）で表される芳香族置換アルキル基である。）

（式中、ＡＬは炭素数１〜５の分岐状または直鎖状の脂肪族炭化水素基であり、Ａｒは置換基を有しても良いフェニル基、ナフチル基、またはアントリル基である。ｎは１〜３の整数を示し、ＡｒはＡＬ中の任意の炭素原子に結合することができる。） In the present invention, the organophosphorus compound used as the component B is represented by the following formula (1).

(In formula, X < ¹ >, X < ² > is the same or different, and is an aromatic substituted alkyl group represented by following formula (2).)

(In the formula, AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, and Ar is a phenyl group, a naphthyl group, or an anthryl group which may have a substituent. Represents an integer of 1 to 3, and Ar can be bonded to any carbon atom in AL.)

  The organophosphorus compound is preferably at least one compound selected from the group consisting of organophosphorus compounds represented by the following formula (3) and the following formula (4).

（式中、Ｒ^２、Ｒ^５は同一または異なっていてもよく、置換基を有しても良いフェニル基、ナフチル基、またはアントリル基である。Ｒ^１、Ｒ^３、Ｒ^４、Ｒ^６は同一または異なっていてもよく、水素原子、炭素数１〜４の分岐状または直鎖状のアルキル基、置換基を有しても良いフェニル基、ナフチル基、またはアントリル基から選択される置換基である。）

(In the formula, R ² and R ⁵ may be the same or different, and may be a phenyl group, a naphthyl group, or an anthryl group that may have a substituent. R ¹ , R ³ , R ⁴ , R ⁶ are Substituents which may be the same or different and are selected from a hydrogen atom, a branched or straight chain alkyl group having 1 to 4 carbon atoms, an optionally substituted phenyl group, naphthyl group, or anthryl group .)

（式中、Ａｒ^１およびＡｒ^２は、同一又は異なっていても良く、フェニル基、ナフチル基またはアントリル基であり、その芳香環に置換基を有していてもよい。Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４は、同一又は異なっていても良く、水素原子、炭素数１〜３の脂肪族炭化水素基またはフェニル基、ナフチル基もしくはアントリル基であり、その芳香環に置換基を有していてもよい。ＡＬ^１およびＡＬ^２は、同一又は異なっていても良く、炭素数１〜４の分岐状または直鎖状の脂肪族炭化水素基である。Ａｒ^３およびＡｒ^４は、同一又は異なっていても良く、フェニル基、ナフチル基またはアントリル基であり、その芳香環に置換基を有していてもよい。ｐおよびｑは０〜３の整数を示し、Ａｒ^３およびＡｒ^４はそれぞれＡＬ^１およびＡＬ^２の任意の炭素原子に結合することができる。）

(In formula, Ar < ¹ > and Ar < ² > may be the same or different, and are a phenyl group, a naphthyl group, or an anthryl group, and may have a substituent in the aromatic ring. R < ¹¹ >, R < ¹² >, R ¹³ and R ¹⁴ may be the same or different, and are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a phenyl group, a naphthyl group or an anthryl group, and have a substituent in the aromatic ring. AL ¹ and AL ² may be the same or different and are branched or straight-chain aliphatic hydrocarbon groups having 1 to 4 carbon atoms, Ar ³ and Ar ⁴ may be the same or It may be different, and may be a phenyl group, a naphthyl group or an anthryl group, and may have a substituent on the aromatic ring, p and q each represent an integer of 0 to ^3, and Ar ³ and Ar ⁴ each represent AL ¹ Contact It can be attached to any carbon atom of the fine AL ^2.)

  The organophosphorus compound is more preferably an organophosphorus compound represented by the following formula (5), (6), (7) or (8).

In the above formula (5), R ²¹ and R ²² are the same or different and are a phenyl group, a naphthyl group or an anthryl group which may have a substituent on the aromatic ring, and among them, a phenyl group is preferred. The phenyl group, naphthyl group or anthryl group of R ²¹ and R ²² may be substituted with a hydrogen atom of the aromatic ring, and as a substituent, methyl, ethyl, propyl, butyl or a bonding group of the aromatic ring is Examples thereof include an aryl group having 6 to 14 carbon atoms via an oxygen atom, a sulfur atom, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

In the above formula (6), R ³¹ and R ³⁴ may be the same or different and are a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Preferred are a hydrogen atom, a methyl group, and an ethyl group, and particularly preferred is a hydrogen atom. R ³³ and R ³⁶ may be the same or different and are each an aliphatic hydrocarbon group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R ³² and R ³⁵ may be the same or different, and are a phenyl group, a naphthyl group or an anthryl group, and may have a substituent on the aromatic ring. Preferably, it represents a phenyl group, and may have a substituent in any part other than the part bonded to phosphorus via a carbon atom on the aromatic ring, and includes methyl, ethyl, propyl (including isomers) , Butyl (including isomers) or a group bonded to the aromatic ring thereof is an aryl group having 6 to 14 carbon atoms via oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

In the above formula (6), preferred specific examples of R ³² and R ³⁵ include phenyl group, cresyl group, xylyl group, trimethylphenyl group, 4-phenoxyphenyl group, cumyl group, naphthyl group, 4-benzylphenyl group and the like. In particular, a phenyl group is preferable.

In the above formula (7), Ar ¹ and Ar ² may be the same or different, and are a phenyl group, a naphthyl group, or an anthryl group, and may have a substituent on the aromatic ring. Preferable specific examples of Ar ¹ and Ar ² include a phenyl group, a cresyl group, a xylyl group, a trimethylphenyl group, a 4-phenoxyphenyl group, a cumyl group, a naphthyl group, and a 4-benzylphenyl group. Is preferred.

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may be the same or different and are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a phenyl group, a naphthyl group or an anthryl group, and its aromatic ring May have a substituent. Preferably, it represents a phenyl group, and may have a substituent in any part other than the part bonded to phosphorus via a carbon atom on the aromatic ring, and includes methyl, ethyl, propyl (including isomers) , Butyl (including isomers) or a group bonded to the aromatic ring thereof is an aryl group having 6 to 14 carbon atoms via oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

In the above formula (7), AL ¹ and AL ² may be the same or different and are branched or straight-chain aliphatic hydrocarbon groups having 1 to 4 carbon atoms. A branched or straight chain aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, and a branched or straight chain aliphatic hydrocarbon group having 1 to 2 carbon atoms is particularly preferable.

In the above formula (7), preferred specific examples of AL ¹ and AL ² include a methylene group, an ethylene group, an ethylidene group, a trimethylene group, a propylidene group, an isopropylidene group, and the like. In particular, a methylene group, an ethylene group, and Ethylidene groups are preferred.

In the above formula (7), Ar ³ and Ar ⁴ may be the same or different, and are a phenyl group, a naphthyl group or an anthryl group, and may have a substituent on the aromatic ring. Preferably, it represents a phenyl group, and may have a substituent in any part other than the part bonded to phosphorus via a carbon atom on the aromatic ring, and includes methyl, ethyl, propyl (including isomers) , Butyl (including isomers) or a group bonded to the aromatic ring thereof is an aryl group having 6 to 14 carbon atoms via oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

In the above formula (7), p and q is an integer of 0 to 3, Ar ³ and Ar ⁴ may be bonded to any carbon atoms of AL ¹ and AL ^2, respectively. p and q are preferably 0 or 1, particularly preferably 0.

In the above formula (8), R ⁴¹ and R ⁴⁴ may be the same or different and are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group or an anthryl group, The ring may have a substituent. Preferably they are a hydrogen atom, a C1-C3 aliphatic hydrocarbon group, or a phenyl group which may have a substituent. When R ⁴¹ and R ⁴⁴ are phenyl groups, they may have a substituent in any part other than the part bonded to phosphorus via a carbon atom on the aromatic ring, and methyl, ethyl, propyl (isomer The linking group to the aromatic ring is oxygen, sulfur or an aryl group having 6 to 14 carbon atoms via an aliphatic hydrocarbon group having 1 to 4 carbon atoms. .

In the above formula (8), preferred examples of R ⁴¹ and R ⁴⁴ include hydrogen atom, methyl group, ethyl group, propyl group (including isomers), phenyl group, cresyl group, xylyl group, trimethylphenyl group, A 4-phenoxyphenyl group, a cumyl group, a naphthyl group, a 4-benzylphenyl group and the like can be mentioned, and a hydrogen atom, a methyl group or a phenyl group is particularly preferable.

R ⁴² , R ⁴³ , R ⁴⁵ and R ⁴⁶ may be the same or different and are a phenyl group, a naphthyl group or an anthryl group, and may have a substituent on the aromatic ring. Preferably, it represents a phenyl group and may have a substituent in any part other than the part bonded to phosphorus via a carbon atom on the aromatic ring, and includes methyl, ethyl, propyl (including isomers) ), Butyl (including isomers) or a group bonded to the aromatic ring thereof is an aryl group having 6 to 14 carbon atoms via oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

In the above formula (8), preferred specific examples of R ⁴² , R ⁴³ , R ⁴⁵ and R ⁴⁶ include phenyl group, cresyl group, xylyl group, trimethylphenyl group, 4-phenoxyphenyl group, cumyl group, naphthyl group, 4-benzylphenyl group etc. are mentioned, A phenyl group is especially preferable.

  The organophosphorus compound (component B) represented by the formula (1) exhibits a very excellent flame retardant effect for the resin. As far as the present inventors know, in the conventional flame-retarding of the resin by halogen-free, it is difficult to flame-retardant with a small amount of flame retardant, and there are many problems in practical use.

  However, according to the present invention, the organophosphorus compound (component B) surprisingly achieves flame retardancy of the resin by itself in a small amount, and impairs the original properties of the resin, particularly heat resistance. There is no.

  However, in the present invention, in addition to the B component, a flame retardant other than the B component, a flame retardant aid, a fluorine-containing resin or other additive, a reduction in the use ratio of the B component, an improvement in flame retardancy of the molded product Naturally, it can be added to improve the physical properties of the molded article, to improve the chemical properties of the molded article, or for other purposes.

  The organophosphorus compound (component B) as a flame retardant in the flame retardant resin composition of the present invention is represented by the above formula (1), but the most preferred representative compounds are the following formulas (1-a), (1 -B), an organophosphorus compound represented by (1-c) or (1-d).

Next, a method for synthesizing the organophosphorus compound (component B) in the present invention will be described. The component B may be produced by a method other than the method described below.
The component B can be 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, reacting aralkyl alcohol with a compound obtained by reacting pentaerythritol with phosphorus trichloride, and then performing 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.

The specific synthesis method of the B component will be described below. This synthesis method is merely for the purpose of explanation, and the B component used in the present invention is not limited to these synthesis methods, but also its modifications and other synthesis methods. It may be synthesized. A more specific synthesis method will be described in the preparation examples described later.
(I) the organophosphorus compound of (1-a) in component B;
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) the organophosphorus compound of (1-b) in component B;
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 1-phenylethyl bromide.
(III) the organophosphorus compound of (1-c) in component B;
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 2-phenylethyl bromide.
(IV) the organophosphorus compound of (1-d) in component B;
It can be obtained by reacting pentaerythritol with diphenylmethylphosphonic acid dichloride.

  Alternatively, it can be obtained by reacting pentaerythritol with phosphorus trichloride and heat-treating the resulting product and the reaction product of diphenylmethyl alcohol in the presence of a catalyst.

  As the above-mentioned B component, those having an acid value of 0.7 mgKOH / g or less, preferably 0.5 mgKOH / g or less are used. By using the component B having an acid value in this range, a molded product having excellent flame retardancy and hue can be obtained, and a molded product having good thermal stability can be obtained. The component B most preferably has an acid value of 0.4 mgKOH / g or less. Here, the acid value means the amount (mg) of KOH necessary for neutralizing the acid component in 1 g of the sample (component B).

  Furthermore, as the component B, one whose HPLC purity is preferably at least 90%, more preferably at least 95% is used. Such a high-purity product is preferable because of excellent flame retardancy, hue, and thermal stability of the molded product. Here, the HPLC purity of the B component can be measured effectively by using the following method.

  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 6: 4 (volume ratio) was used, and 5 μl was injected. The detector used was UV-260 nm.

  The method for removing impurities in component B is not particularly limited, but a method of performing repulp washing with a solvent such as water or methanol (washing with a solvent, repeating filtration several times) is the most effective. It is also advantageous in terms of cost.

  The component B is 1 to 100 parts by weight, preferably 5 to 90 parts by weight, based on 100 parts by weight of a resin component (component A) containing at least 50% by weight of stereocomplex polylactic acid (A-1 component). More preferably 10 to 70 parts by weight, and particularly preferably 15 to 50 parts by weight. The preferred range of the blending ratio of the B component is determined by the desired flame retardancy level, the type of resin component (A component), the amount added, and the like. Even if it is other than the A component, B component, C component, and D component constituting these compositions, other components can be used as necessary as long as the purpose of the present invention is not impaired, and other flame retardants, The blending amount of the B component can also be changed by using a flame retardant aid and a fluorine-containing resin. In many cases, the blending ratio of the B component can be reduced by using these components.

  In the present invention, the filler used as the component C is not particularly limited as long as it is blended for the purpose of improving the physical properties, particularly mechanical properties, of the molded product, and may be either an inorganic or organic filler. A fibrous filler is preferable.

  Examples of the inorganic filler include glass fillers such as glass chopped fiber, glass milled fiber, glass roving strand, glass flake, glass beads, and glass powder; carbon such as carbon fiber, carbon milled fiber, carbon roving strand, and carbon flake. System fillers; inorganic fillers such as talc, mica, wollastonite, kaolin, montmorillonite, bentonite, sepiolite, zonotolite, clay, silica; inorganic pigments such as titanium oxide, carbon black, etc., selected from these Or a combination of these. For the purpose of reinforcing the resin composition, it is preferable to mix a fibrous filler, and it is preferable to mix glass fiber, carbon fiber, or a mixture thereof.

  Organic fillers include rice husk, wood chips, okara, waste paper pulverized material, clothing pulverized material chips, cotton fiber, hemp fiber, bamboo fiber, wood fiber, kenaf fiber, jute fiber, banana fiber, coconut Plant fibers such as fibers, or pulp and cellulose fibers processed from these plant fibers and fiber-like materials such as silk, wool, angora, cashmere, camel, etc., polyester fibers, nylon fibers, acrylic fibers, etc. Examples include fiber, paper powder, wood powder, cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein, starch and the like. From the viewpoint of moldability, powdery materials such as paper powder, wood powder, bamboo powder, cellulose powder, kenaf powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein powder, and starch are preferred. Powder, bamboo powder, cellulose powder and kenaf powder are preferred. Paper powder and wood powder are more preferable. Paper dust is particularly preferable.

  These organic fillers may be those directly collected from natural products, but may also be those obtained by recycling waste materials such as waste paper, waste wood and old clothes. The wood is preferably a softwood material such as pine, cedar, oak or fir, or a hardwood material such as beech, shii or eucalyptus.

  Paper powder is an adhesive from the viewpoint of moldability, especially emulsion-based adhesives such as vinyl acetate resin-based emulsions and acrylic resin-based emulsions when processing paper, polyvinyl alcohol-based adhesives, polyamide-based adhesives, etc. Preferred examples include those containing a hot melt adhesive.

  These fillers can use a sizing agent or a surface treatment agent as required. The type of the sizing agent or the surface treatment agent is not particularly limited, but generally includes functional compounds such as epoxy compounds, silane compounds, titanate compounds, and the like, and it is preferable to select those suitable for the resin. An epoxy compound is preferable, and a bisphenol A type and / or novolac type epoxy resin is more preferable.

  When the filler (component C) is blended, the proportion thereof is preferably 1 to 200 parts by weight, more preferably 5 to 150 parts by weight, and still more preferably 10 parts with respect to 100 parts by weight of the resin component (component A). ~ 100 parts by weight. If it is added in an amount of more than 200 parts by weight, it may cause the flame retardancy and physical properties of the resin composition to deteriorate, and the operability and moldability may be difficult, and may cause deterioration of the surface appearance.

In the present invention, the impact modifier used as the D component includes (i) one or more rubber layers therein, and the components include an acrylic component, a silicon component, a styrene component, and a nitrile. An impact modifier that is at least one selected from a system component, a conjugated diene component, a urethane component, and an ethylene propylene component, and a component other than the rubber layer is a vinyl monomer, and (ii) copolymerization Examples thereof include impact modifiers substantially free of rubber components such as polyethylene, polyester elastomer and polyamide elastomer.
Preferred is (i) an impact modifier containing one or more rubber layers therein, and particularly preferred is a hydrogenated styrene thermoplastic elastomer.

  The hydrogenated styrene thermoplastic elastomer can be obtained by hydrogenating a copolymer of an aromatic vinyl monomer and a conjugated diene monomer. The hydrogenated styrene-based thermoplastic elastomer is a terpolymer obtained by hydrogenating a polymer containing a conjugated diene as a repeating unit. Specific examples of the polymer containing a conjugated diene preferably used in the present invention as a repeating unit include a styrene-butadiene copolymer, a styrene-isoprene copolymer, a styrene-isopentadiene copolymer, and the like. The addition method is not particularly limited, and as a specific example, it can be carried out based on the prior art as disclosed in Japanese Patent Application Laid-Open No. 2007-301449. Specific examples of the hydrogenated styrene-based thermoplastic elastomer include styrene-ethylene-butylene-styrene terpolymer (SEBS) obtained by hydrogenating a styrene-butadiene copolymer, and styrene obtained by hydrogenating a styrene-isoprene copolymer. -Ethylene-propylene-styrene terpolymer (SEPS), styrene-ethylene-propylene-styrene terpolymer (SEEPS) obtained by hydrogenating a styrene-isopentadiene copolymer, and the like.

  When the impact modifier (component D) is blended, the proportion is preferably 1 to 100 parts by weight, more preferably 2 to 80 parts by weight, with respect to 100 parts by weight of the resin component (component A). Preferably it is 3-50 weight part. If it is added in an amount of more than 100 parts by weight, the resin composition will be deteriorated in heat resistance, releasability and dimensional stability, and if it is less than 1 part by weight, sufficient impact resistance cannot be obtained.

  A flame retardant, a flame retardant auxiliary, and the like that can be added in addition to the component C are not particularly limited, but a non-halogen compound is preferable in terms of the properties of the present invention. Preferred examples include red phosphorus, triaryl phosphate represented by the following general formula (E-1), condensed phosphate ester represented by the following general formula (E-2), and the following general formula (E-3). The condensed phosphoric acid ester represented, the organic phosphorus compound represented by the following general formula (E-4), ammonium polyphosphate, melamine polyphosphate, a phosphazene compound, a phosphinic acid metal salt, melamine cyanurate, etc. are mentioned.

In the formulas (E-1) to (E-3), Q ^{1 to} Q ⁴ may be the same or different, and are each 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 (E-2) and (E-3), Ar ⁴ and Ar ⁵ may be the same or different when both are present (in the case of E-3), and 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 the formulas (E-2) and (E-3), m represents an integer of 1 to 5, preferably an integer of 1 to 3, and particularly preferably 1.
In the formula (E-3), 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.

  Furthermore, the fluorine-containing resin that can be used in the present invention 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 products of agglomerated mixture of the above 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.

Furthermore, the composition of the present invention may contain a crystallization accelerator. By containing the crystallization accelerator, a molded product having excellent mechanical properties, heat resistance, and moldability can be obtained.
That is, by applying a crystallization accelerator, the moldability and crystallinity of the resin component (component A) are improved, and a molded product that is sufficiently crystallized even in normal injection molding and has excellent heat resistance and moist heat resistance is obtained. Can do. In addition, the manufacturing time for manufacturing the molded product can be greatly shortened, and the economic effect is great.

As the crystallization accelerator, either an inorganic crystallization nucleating agent or an organic crystallization nucleating agent can be used.
As inorganic crystallization nucleating agents, talc, kaolin, silica, synthetic mica, clay, zeolite, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium carbonate, calcium sulfate, barium sulfate, calcium sulfide, boron nitride , Montmorillonite, neodymium oxide, aluminum oxide, phenylphosphonate metal salt and the like. These inorganic crystallization nucleating agents are treated with various dispersing aids in order to enhance the dispersibility in the composition and the effect thereof, and are in a highly dispersed state with a primary particle size of about 0.01 to 0.5 μm. Are preferred.

  Organic crystallization nucleating agents include calcium benzoate, sodium benzoate, lithium benzoate, potassium benzoate, magnesium benzoate, barium benzoate, calcium oxalate, disodium terephthalate, dilithium terephthalate, dipotassium terephthalate, Sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, barium myristate, sodium octacolate, calcium octacolate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate , Barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, salicy Organic carboxylic acid metal salts such as zinc acid, aluminum dibenzoate, β-naphthoic acid sodium, β-naphthoic acid potassium, sodium cyclohexanecarboxylic acid and the like, and organic sulfonic acid metal salts such as sodium p-toluenesulfonate and sodium sulfoisophthalate. Can be mentioned.

  In addition, stearic acid amide, ethylene bislauric acid amide, palmitic acid amide, hydroxy stearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide) and other organic carboxylic acid amides, low density polyethylene, high density polyethylene, polyiso Propylene, polybutene, poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, high melting point polylactic acid, sodium salt of ethylene-acrylic acid copolymer, sodium of styrene-maleic anhydride copolymer Examples thereof include salts (so-called ionomers), benzylidene sorbitol and derivatives thereof such as dibenzylidene sorbitol.

Among these, at least one selected from talc and organic carboxylic acid metal salts is preferably used. Only one type of crystallization nucleating agent may be used in the present invention, or two or more types may be used in combination.
The content of the crystallization accelerator is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight per 100 parts by weight of the resin component (component A).

  Preparation of the flame retardant resin composition of the present invention involves resin component (component A), organophosphorus compound (component B), filler (component C), impact modifier (component D), and as required. A method in which other components are premixed using a mixer such as a V-type blender, a super mixer, a super floater, and a Henschel mixer, and the premix is supplied to a kneader and melt mixed is preferably employed. As the kneading machine, various melt mixers such as a kneader, a single screw or a twin screw extruder can be used, and among them, the resin composition is 200 to 300 ° C., preferably 210 to 280 ° C. using the twin screw extruder. A method is preferably used in which a liquid component is injected by a side feeder, extruded by a side feeder, extruded, and pelletized by a pelletizer.

  In addition, depending on the type of C component filler, particularly a high aspect ratio filler, the aspect ratio may decrease in the melt blending method by pre-blending, and the mechanical properties of the resulting resin composition may decrease. The addition method using a side feeder is preferably used.

  The flame retardant resin composition of the present invention is substantially free of halogen and has very high flame retardant performance, such as home appliance parts, electrical / electronic parts, automobile parts, mechanical / mechanical parts, cosmetic containers, etc. It is useful as a material for molding various molded articles. Specifically, breaker parts, switch parts, motor parts, ignition coil cases, power plugs, power outlets, coil bobbins, connectors, relay cases, fuse cases, flyback transformer parts, focus block parts, distributor caps, harness connectors, etc. Can be suitably used. Furthermore, thinning housings, casings or chassis, such as electronic and electrical products (such as telephones, personal computers, printers, fax machines, copiers, televisions, VCRs, audio equipment and other home appliances / OA equipment, or parts thereof) Useful for housings, casings or chassis. In particular, it is also useful as a printer casing, fixing unit parts, and other machine / mechanical parts of home appliances and OA products such as fax machines that require particularly excellent heat resistance and flame retardancy.

  The molding method is not particularly limited, such as injection molding, blow molding, press molding, and the like, but it is preferably manufactured by injection molding a pellet-shaped resin composition using an injection molding machine.

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

1. Manufacture of stereocomplex polylactic acid (A-1 component) Stereocomplex polylactic acid (A-1 component) was manufactured by the method shown in the following manufacture example. Moreover, each value in a manufacture example was calculated | required with the following method.

(1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer:
It was measured by gel permeation chromatography (GPC) and converted to standard polystyrene. The GPC measurement instrument used a differential refractometer Shimadzu RID-6A as a detector and Toso-TSKgel G3000HXL as a column. The measurement was performed by injecting 10 μl of a sample having a concentration of 1 mg / ml (chloroform containing 1% hexafluoroisopropanol) at a temperature of 40 ° C. and a flow rate of 1.0 ml / min using chloroform as an eluent.

(2) Carboxyl group concentration The sample was dissolved in purified o-cresol under a nitrogen stream, and then titrated with 0.05 N potassium hydroxide in ethanol using bromocresol blue as an indicator.

(3) Measurement with a differential scanning calorimeter (DSC) In the first heating process of the sample using DSC (TA-2920, manufactured by TA Instrument Co., Ltd.), a melting peak at 190 ° C. or higher was used as a melting peak derived from stereo crystals. The melting temperature was Tms and the melting enthalpy was Hms. In addition, the melting peak at 190 ° C. or less was defined as a homocrystalline melting peak, the melting temperature was Tmh, and the melting enthalpy was Hmh.
Stereogenicity = ΔHms / (ΔHms + ΔHmh) × 100

(4) Enantiomeric average chain length The sample was dissolved in HFIP / chloroform = 1/1 mixed solvent and then reprecipitated with methanol. The reprecipitated polymer component was ultrasonically washed with methanol and centrifuged 10 times to remove impurities and solvent components, followed by drying with a vacuum dryer for 1 day to extract a polylactic acid component that could be a measurement sample.
Using the sample thus extracted, the average enantiomeric chain length was measured as follows.
13-C NMR apparatus: BURKER ARX-500 manufactured by Nippon Bruker
Sample: 50mg / 0.7ml
Measurement solvent: 10% HFIP-containing deuterated chloroform Internal standard: Tetramethylsilane (TMS) 1% (v / v)
Measurement temperature: 27 ° C (300K)
Measurement frequency: 125 MHz
Of the carbon peaks attributed to carbonyl carbon (C═O), the peak (a) (around 170.1-170.3 MHz) is a homo sequence (LLLLLL or DDDDDDD) and the peak (b ) (Around 170.0-169.8 MHz) belongs to the racemic chain (LLLDDD...), And the average chain length was calculated from the integrated value of these peaks by the following formula.
v = integral value of peak (a) / integral value of peak (b)

In the examples and comparative examples of the present invention, the following materials were used.
[Reference Example: Synthesis of ethyl di-n-hexylphosphonoacetate (DHPA)]
100 parts by weight of trihexyl phosphite and 100 parts by weight of ethyl bromoacetate were placed in a reaction vessel, and the inside was replaced with nitrogen. Subsequently, the reaction vessel was heated to 170 ° C., and the reaction was carried out for 3 hours while heating to reflux. After excess ethyl bromoacetate was distilled off at 80 ° C. under reduced pressure, the reaction mixture was distilled under reduced pressure at 190 ° C. to obtain a colorless transparent liquid (yield 84%, boiling point 146 ° C./0.5 mmHg).

[Α-1 component: Production of poly L-lactic acid (PLLA)]
[Production Example 1]
100 parts by weight of L-lactide (manufactured by Musashino Chemical Laboratory, Inc., optical purity 100%) and 0.15 part by weight of stearyl alcohol are charged from a raw material charging port of a polymerization reaction vessel equipped with a cooling distillation pipe under a nitrogen stream. It is. Subsequently, the inside of the reaction vessel was replaced with nitrogen five times, and L-lactide was melted at 190 ° C. When L-lactide was completely melted, 0.005 part by weight of a toluene 500 μL solution of tin octylate was added and polymerized at 190 ° C. for 1 hour. After completion of the polymerization, 0.082 part by weight of ethyl di-n-hexylphosphonoacetate was added from the raw material charging port and kneaded for 15 minutes. Finally, excess L-lactide was devolatilized, and the polymer was discharged from the reaction vessel to form a chip to obtain poly L-lactic acid (PLLA).
The resulting poly L-lactic acid resin has a weight average molecular weight of 151,000, a glass transition point (Tg) of 55 ° C., a melting peak temperature (Tmh) of 177 ° C., a carboxyl group content of 15 eq / ton, and an enantiomer average chain length. The syndiotactic connecting part could not be measured and could not be calculated.

[Β-1 component: production of poly-D-lactic acid (PDLA)]
[Production Example 2]
Poly D-lactic acid (PDLA) was prepared in the same manner as in Production Example 1 except that D-lactide (manufactured by Musashino Chemical Laboratory, Inc., optical purity 100%) was used instead of L-lactide in Production Example 1. Obtained. The resulting poly-D-lactic acid resin has a weight average molecular weight of 152,000, a glass transition point (Tg) of 55 ° C., a melting peak temperature (Tmh) of 177 ° C., a carboxyl group content of 14 eq / ton, and an enantiomer average chain length. The syndiotactic connecting part could not be measured and could not be calculated.

[Component A-1: Production of stereocomplex polylactic acid (scPLA)]
[Production Example 3]
100 parts by weight of polylactic acid resin composed of 50 parts by weight of PLLA and PDLA obtained in Production Examples 1 and 2 and sodium 2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate (Adekastab) (NA-11: manufactured by ADEKA Co., Ltd.) 0.1 part by weight was mixed with a blender, dried at 110 ° C. for 5 hours, and supplied to a vent type twin-screw extruder having a diameter of 30 mmφ [TEX30XSST manufactured by Nippon Steel Works, Ltd.] Then, it was melt-extruded and pelletized at a cylinder temperature of 250 ° C., a screw rotation speed of 250 rpm, a discharge rate of 9 kg / h, and a vent vacuum of 3 kPa to obtain stereocomplex polylactic acid. The resulting stereocomplex polylactic acid has a weight average molecular weight of 130,000, a glass transition point (Tg) of 58 ° C., a complex phase polylactic acid crystal melting peak temperature (Tms) of 220 ° C., a carboxyl group content of 17 eq / ton, an enantiomeric average The chain length was 28, and the ratio of the melting peak at 195 ° C. or higher was 100% among the melting peaks in the temperature rising process of differential scanning calorimetry (DSC) measurement. The amount of NA-11 added is part by weight per 100 parts by weight of PLLA and PDLA.

2. Production of organophosphorus compound (component B) An organophosphorus compound (component B) was produced by the method shown in the production examples below. Moreover, each value in a manufacture example was calculated | required with the following method.

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

(6) HPLC purity of organophosphorus compound The sample was dissolved in a 6: 4 (volume ratio) mixed solution of acetonitrile and water, 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.

(7) ³¹ PNMR purity of organophosphorus compound The nuclear magnetic resonance of a phosphorus atom was measured with a nuclear magnetic resonance measuring apparatus (JNM-AL400, manufactured by JEOL) (DMSO-d ₆ , 162 MHz, integration number 3072), and the integration area The ratio was ³¹ PNMR purity of the phosphorus compound.

[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 obtained filtered product was dried at 80 ° C. and 1.33 × 10 ² Pa for 12 hours to obtain 1341.1 g (5.88 mol) of a white solid. 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% and ³¹ PNMR purity was 99%. The HPLC purity measured by the method described in the text was 99%. The acid value was 0.06 mgKOH / g.

¹ H-NMR (DMSO-d ₆ , 300 MHz): δ 7.2-7.4 (m, 10H), 4.1-4.5 (m, 8H), 3.5 (d, 4H), ³¹ P _{-NMR (DMSO-d 6, 120MHz} ): δ23.1 (S), melting point: 255-256 ° C., elemental analysis: calculated: C, 55.89; H, 5.43 , measurement values: 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 40 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%, and ³¹ PNMR purity was 99%. The HPLC purity measured by the method described in the text was 99%. The acid value was 0.05 mgKOH / g.

¹ H-NMR (DMSO-d ₆ , 300 MHz): δ 7.2-7.4 (m, 10H), 4.1-4.5 (m, 8H), 3.5 (d, 4H), ³¹ P _{-NMR (DMSO-d 6, 120MHz} ): δ23.1 (S), melting point: 257 ° C.

[Preparation Example 3]
Preparation of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-diα-methylbenzyl-3,9-dioxide (FR-3) Thermometer, condenser, A reaction vessel equipped with a dropping funnel 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 5180.7 g (61.0 mol) of methylene chloride was added to the obtained reaction product, and 889.4 g (12.0 mol) of tertiary butanol and 150. 2 g (1.77 mol) was added dropwise. The obtained crystals were washed with toluene and methylene chloride and filtered. The obtained filtered product was dried at 80 ° C. and 1.33 × 10 ² Pa for 12 hours to obtain 1341.1 g (5.88 mol) of a white solid. 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 2204.06 g (11.91 mol) of 1-phenylethyl 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 1845.9 g of white scaly crystals ( 4.23 mol) was obtained. The obtained solid was analyzed by ³¹ PNMR, ¹ HNMR spectrum and elemental analysis, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-diα-methylbenzyl-3,9. -Confirmed that it was a geoxide. ³¹ PNMR purity was 99%. The HPLC purity measured by the method described in the text was 99%. The acid value was 0.03 mgKOH / g.

¹ H-NMR (CDCl ₃ , 300 MHz): δ 7.2-7.4 (m, 10H), 4.0-4.2 (m, 4H), 3.4-3.8 (m, 4H), 3.3 (qd, 4H), 1.6 (ddd, 6H), ³¹ P-NMR (CDCl ₃ , 120 MHz): δ 28.7 (S), melting point: 190-210 ° C., elemental analysis calculated value: C, 57.80; H, 6.01, measured value: C, 57.83; H, 5.96

[Preparation Example 4]
Preparation of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-di (2-phenylethyl) -3,9-dioxide (FR-4) Thermometer A reaction vessel equipped with a condenser and a dropping funnel 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 5180.7 g (61.0 mol) of methylene chloride was added to the obtained reaction product, and 889.4 g (12.0 mol) of tertiary butanol and 150. 2 g (1.77 mol) was added dropwise. The obtained crystals were washed with toluene and methylene chloride and filtered. The obtained filtered product was dried at 80 ° C. and 1.33 × 10 ² Pa for 12 hours to obtain 1341.1 g (5.88 mol) of a white solid. 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 2183.8 g (11.8 mol) of (2-bromoethyl) benzene 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 and washed with 2 L of methanol, and the resulting filtered product was dried at 120 ° C. and 1.33 × 10 ² Pa for 19 hours to give 1924.4 g (4. 41 mol) was obtained. The obtained solid was found to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-di (2-phenylethyl) -3 by ³¹ PNMR, ¹ HNMR spectrum and elemental analysis. , 9-Dioxide was confirmed. ³¹ PNMR purity was 99%. The HPLC purity measured by the method described in the text was 99%. The acid value was 0.03 mgKOH / g.

¹ H-NMR (CDCl ₃ , 300 MHz): δ 7.1-7.4 (m, 10H), 3.85-4.65 (m, 8H), 2.90-3.05 (m, 4H), 2.1-2.3 (m, 4H), ³¹ P-NMR (CDCl ₃ , 120 MHz): δ 31.5 (S), melting point: 245-246 ° C., elemental analysis calculated: C, 57.80; H , 6.01, measured value: C, 58.00; H, 6.07

[Preparation Example 5]
Preparation of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (diphenylmethyl) -3,9-dioxide (FR-6) Stirrer, stirrer In a 10-liter three-necked flask equipped with a reflux condenser and a thermometer, 2058.5 g (7.22 mol) of diphenylmethylphosphonic dichloride, 468.3 g (3.44 mol) of pentaerythritol, 1169.4 g of pyridine ( 14.8 mol) and 8200 g of chloroform were charged, heated to 60 ° C. under a nitrogen stream, and stirred for 6 hours. After completion of the reaction, chloroform was replaced with methylene chloride, and 6 L of distilled water was added to the reaction mixture and stirred to precipitate a white powder. This was collected by suction filtration, and the obtained white product was washed with methanol and then dried at 100 ° C. and 1.33 × 10 ² Pa for 10 hours to obtain 1156.2 g of a white solid. The obtained solid was found to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (diphenylmethyl) by ³¹ P-NMR, ¹ H-NMR spectrum and elemental analysis. It was confirmed that it was −3,9-dioxide. ^{The 31} P-NMR purity was 99%. The HPLC purity measured by the method described in the text was 99%. The acid value was 0.3 mgKOH / g.

¹ H-NMR (DMSO-d6, 300 MHz): δ 7.20-7.60 (m, 20H), 5.25 (d, 2H), 4.15-4.55 (m, 8H), ³¹ P- NMR (DMSO-d6, 120 MHz): δ 20.9, melting point: 265 ° C., elemental analysis calculated: C, 66.43; H, 5.39, measured: C, 66.14; H, 5.41

The resin compositions prepared in Examples and Comparative Examples were evaluated by the following methods.
(8) Flame retardancy (UL-94 evaluation)
Flame retardancy is evaluated using a test piece with a thickness of 1/16 inch (1.6 mm) according to the vertical flame test defined in UL-94 of the US UL standard as a flame retardant evaluation scale. It was.
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.

(9) Heat resistance (deflection temperature under load; HDT)
The deflection temperature under load (HDT) was measured at a load of 1.8 MPa using a 6.35 mm (1/4 inch) test piece by a method according to ISO 75-2.

(10) Impact resistance (Charpy impact strength with notch)
Based on ISO179, the notched Charpy impact strength was measured.

The following were used for each component used in Examples and Comparative Examples.
(I) Stereocomplex polylactic acid resin (A-1 component)
(I) The stereocomplex PLA produced in Production Example 3 was used (hereinafter referred to as scPLA).
(II) Resin component other than A-1 component (A-2 component)
(I) Commercially available polylactic acid (manufactured by Nature Works 4032D; poly L-lactic acid resin) was used (hereinafter referred to as PLLA).
(Ii) A commercially available polybutylene terephthalate resin (TRB-H manufactured by Teijin Ltd.) was used (hereinafter referred to as PBT). 230 ° C., MVR value measured at 3.8kg load ^was 9.5cm 3 / 10min.
(Iii) A commercially available polycarbonate resin (Panlite L-1225 manufactured by Teijin Chemicals Ltd.) was used (hereinafter referred to as PC). Terminal OH group content = 14eq / ton, 300 ℃, MVR value measured at 1.2kg load ^was 10.1 cm 3 / 10min.
(Iv) Commercially available impact-resistant polystyrene (PSJ polystyrene H9152 manufactured by PS Japan Co., Ltd.) was used (hereinafter referred to as HIPS). 200 ° C., MVR value at 5kg load ^was 5.7 cm 3 / 10min.
(V) A commercially available ABS resin (Santac UT-61 manufactured by Nippon A & L Co., Ltd.) was used (hereinafter referred to as ABS). 220 ° C., MVR value at 10kg load ^was 35 cm 3 / 10min.
(Vi) A commercially available polyphenylene ether resin (Zylon P-402 manufactured by Asahi Kasei Kogyo Co., Ltd.) was used (hereinafter referred to as PPE).
(III) Organophosphorus compound (component B)
(I) 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-dibenzyl-3,9-dioxide synthesized in Preparation Example 1 {the above formula (1-a ) Was used (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 {the above formula (1-a ) Was used (hereinafter referred to as FR-2).
(Iii) 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-diα-methylbenzyl-3,9-dioxide synthesized in Preparation Example 3 (1-b) organophosphorus compound} was used (hereinafter referred to as FR-3).
(Iv) 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-di (2-phenylethyl) -3,9-dioxide synthesized in Preparation Example 4 The organophosphorus compound of formula (1-c)} was used (hereinafter referred to as FR-4).
(V) 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (diphenylmethyl) -3,9-dioxide synthesized in Preparation Example 5 (1-d) organophosphorus compound} was used (hereinafter referred to as FR-5).
(IV) Filler (component C)
(I) A commercially available milled fiber (PFE-301 manufactured by Nittobo Co., Ltd.) was used (hereinafter referred to as MF).
(Ii) A commercially available chopped strand (CS3PE-455 manufactured by Nittobo Co., Ltd.) was used (hereinafter referred to as CS).
(V) Impact resistance modifier (D component)
(I) A commercially available hydrogenated styrene-based thermoplastic elastomer (Septon 8006 manufactured by Kuraray Co., Ltd.) was used.
(VI) Other organophosphorus compounds (i) 1,3-phenylenebis [di (2,6-dimethylphenyl) phosphate] (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.) (hereinafter referred to as PX-) 200)
(VII) Talc (i) Commercially available talc (P-3 manufactured by Nippon Talc Co., Ltd.) was used.

[Examples 1-46 and Comparative Examples 1-29]
Each component of Tables 1-5 was mix | blended with the tumbler in the quantity (weight part) of Tables 1-5, and was pelletized with the 15 mmphi twin screw extruder (the Technobel make, KZW15). The obtained pellets were dried in a hot air dryer at 100 ° C. for 24 hours. The dried pellets were molded with an injection molding machine (J75EIII manufactured by Nippon Steel Works). The result evaluated using the shaping | molding board was shown to Tables 1-5.

  The flame-retardant resin composition of the present invention is useful as a material for molding various molded products such as home appliance parts, electric / electronic parts, automobile parts, machine / mechanical parts, cosmetic containers and the like.

Claims (19)

(A) With respect to 100 parts by weight of a resin component (component A) containing at least 50% by weight of stereocomplex polylactic acid (component A-1), (B) an organophosphorus compound (B) represented by the following formula (1) (Component) 5 to 90 parts by weight, (C) filler (component C) 1 to 200 parts by weight , (D) impact modifier (D component) 2 to 80 parts by weight, and (E) talc as a crystallization accelerator (E component) 0.01-30 parts by weight, impact modifier (D component) is styrene-ethylene-butylene-styrene terpolymer (SEBS), styrene-ethylene-propylene-styrene A flame retardant resin composition which is at least one hydrogenated styrene-based thermoplastic elastomer selected from a terpolymer (SEPS) and a styrene-ethylene-propylene-styrene terpolymer (SEEPS).

(In formula, X < ¹ >, X < ² > is the same or different, and is an aromatic substituted alkyl group represented by following formula (2).)

(In the formula, AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, and Ar is a phenyl group, a naphthyl group, or an anthryl group which may have a substituent. Represents an integer of 1 to 3, and Ar can be bonded to any carbon atom in AL.)   The stereocomplex polylactic acid of component A-1 is poly L-lactic acid (α-1 component) containing 90 mol% or more of L-lactic acid units and poly D-lactic acid (β containing 90 mol% or more of D-lactic acid units). The flame retardant resin composition according to claim 1, wherein the weight ratio of the α-1 component and the β-1 component is in the range of 10:90 to 90:10.   The flame retardant resin composition according to claim 1, wherein the stereocomplex polylactic acid of component A-1 has a ratio of 195 ° C or higher of the melting peak in the temperature rising process of differential scanning calorimetry (DSC) measurement being 80% or higher. .   Polyester resin (PEst), polyphenylene ether resin (PPE), and polycarbonate resin other than the A-1 component as the resin component (A-2 component) other than the stereocomplex polylactic acid (A-1 component) in the resin component (A component) (PC), a polyamide resin (PA), a polyolefin resin (PO), a styrene resin, a polyphenylene sulfide resin (PPS), and a polyetherimide resin (PEI). Item 2. A flame retardant resin composition according to Item 1. The flame retardant resin composition according to claim 1 , wherein the filler (C component) is 5 to 150 parts by weight with respect to 100 parts by weight of the resin component (A component) .   The flame retardant resin composition according to claim 1, wherein the impact resistance modifier (component D) is 3 to 50 parts by weight with respect to 100 parts by weight of the resin component (component A). The flame retardant resin according to claim 1, wherein the organophosphorus compound (component B) is at least one compound selected from the group consisting of the organophosphorus compounds represented by the following formula (3) and the following formula (4). Composition.

(In the formula, R ² and R ⁵ may be the same or different, and may be a phenyl group, a naphthyl group, or an anthryl group that may have a substituent. R ¹ , R ³ , R ⁴ , R ⁶ are Substituents which may be the same or different and are selected from a hydrogen atom, a branched or straight chain alkyl group having 1 to 4 carbon atoms, an optionally substituted phenyl group, naphthyl group, or anthryl group .)

(In formula, Ar < ¹ > and Ar < ² > may be the same or different, and are a phenyl group, a naphthyl group, or an anthryl group, and may have a substituent in the aromatic ring. R < ¹¹ >, R < ¹² >, R ¹³ and R ¹⁴ may be the same or different, and are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a phenyl group, a naphthyl group or an anthryl group, and have a substituent in the aromatic ring. AL ¹ and AL ² may be the same or different and are branched or straight-chain aliphatic hydrocarbon groups having 1 to 4 carbon atoms, Ar ³ and Ar ⁴ may be the same or It may be different, and may be a phenyl group, a naphthyl group or an anthryl group, and may have a substituent on the aromatic ring, p and q each represent an integer of 0 to ^3, and Ar ³ and Ar ⁴ each represent AL ¹ Contact It can be attached to any carbon atom of the fine AL ^2.) The flame retardant resin composition according to claim 1, wherein the organophosphorus compound (component B) is represented by the following formula (5).

(Wherein R ²¹ and R ²² are the same or different and are a phenyl group, a naphthyl group or an anthryl group, and the aromatic ring may have a substituent.) The flame retardant resin composition according to claim 1, wherein the organic phosphorus compound (component B) is a compound represented by the following formula (1-a).

The flame retardant resin composition according to claim 1, wherein the organic phosphorus compound (component B) is represented by the following formula (6).

(In the formula, R ³¹ and R ³⁴ may be the same or different, and are a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. R ³³ and R ³⁶ may be the same or different. And an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R ³² and R ³⁵ may be the same or different and each is a phenyl group, a naphthyl group or an anthryl group, and has a substituent in the aromatic ring. May be.) The flame retardant resin composition according to claim 1, wherein the organic phosphorus compound (component B) is a compound represented by the following formula (1-b).

The flame retardant resin composition according to claim 1, wherein the organophosphorus compound (component B) is represented by the following formula (7).

(In formula, Ar < ¹ > and Ar < ² > may be the same or different, and are a phenyl group, a naphthyl group, or an anthryl group, and may have a substituent in the aromatic ring. R < ¹¹ >, R < ¹² >, R ¹³ and R ¹⁴ may be the same or different, and are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a phenyl group, a naphthyl group or an anthryl group, and have a substituent in the aromatic ring. AL ¹ and AL ² may be the same or different and are branched or straight-chain aliphatic hydrocarbon groups having 1 to 4 carbon atoms, Ar ³ and Ar ⁴ may be the same or It may be different, and may be a phenyl group, a naphthyl group or an anthryl group, and may have a substituent on the aromatic ring, p and q each represent an integer of 0 to ^3, and Ar ³ and Ar ⁴ each represent AL ¹ Contact It can be attached to any carbon atom of the fine AL ^2.) The flame retardant resin composition according to claim 1, wherein the organic phosphorus compound (component B) is a compound represented by the following formula (1-c).

The flame retardant resin composition according to claim 1, wherein the organophosphorus compound (component B) is represented by the following formula (8).

(In the formula, R ⁴¹ and R ⁴⁴ may be the same or different and are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group or an anthryl group, and substituted on the aromatic ring thereof. R ⁴² , R ⁴³ , R ⁴⁵ and R ⁴⁶ may be the same or different and are a phenyl group, a naphthyl group or an anthryl group, and have a substituent on the aromatic ring. May be.) The flame retardant resin composition according to claim 1, wherein the organophosphorus compound (component B) is a compound represented by the following formula (1-d).

  The flame retardant resin composition according to claim 1, wherein the organic phosphorus compound (component B) has an acid value of 0.7 mg KOH / g or less.   The flame retardant resin composition according to claim 1, wherein the organophosphorus compound (component B) has an HPLC purity of at least 90%.   The flame-retardant resin composition according to claim 1, wherein at least V-2 is achieved at a flame-retardant level of UL-94 standard.   A molded article formed from the flame retardant resin composition according to claim 1.