JP6334150B2 - Flame retardant resin composition and molded product thereof - Google Patents

Description

  The present invention relates to a flame retardant resin composition substantially free of halogen. In particular, the present invention relates to a flame-retardant polyamide-based resin composition that is excellent in transparency, mechanical strength, and flame retardancy, and is suitably used for various applications such as automobile parts, mechanical parts, and electrical / electronic parts.

  Polyamide resins are used in various fields such as automobile parts, mechanical parts, and electric / electronic parts because of their excellent mechanical strength and heat resistance. In particular, in recent years, the level of demand for flame retardancy has increased in applications for electrical and electronic components, and higher flame retardancy is required than the self-extinguishing properties inherent in polyamide resins. UL- of the Underwriters Laboratory Many studies have been made to improve the flame retardant level conforming to the 94 standard.

  Many of these studies are methods of adding a halogen-based flame retardant. For example, Patent Document 1 discloses an example of adding a chlorine-substituted polycyclic compound to a polyamide resin. Patent Document 2 discloses an example in which decabromodiphenyl ether is added, Patent Document 3 is added with brominated polystyrene, and Patent Document 4 is added with brominated polyphenylene ether.

  As described above, a halogen-based flame retardant has been conventionally used as a method for imparting flame retardancy to a polyamide resin. It is generally known that halogen flame retardants can be used in combination with antimony oxide to achieve a high degree of flame retardancy, and in recent years, environmental problems such as generation of harmful gases during combustion, Because of the corrosive problem caused by the gas generated during combustion, halogen-based flame retardants have been avoided, especially in electrical and electronic component applications, and non-halogen-based flame retardants in this field are strongly desired.

  As such a non-halogen flame retardant technique, a method using red phosphorus is conventionally known. However, a resin composition using red phosphorus generates a toxic phosphine gas at the time of extrusion kneading and molding, and further has a reddish brown color peculiar to red phosphorus, so its practical use is very limited. In addition, as other non-halogen flame retardant techniques, Patent Document 5, Patent Document 6, and Patent Document 7 report methods using an organophosphorus compound, and it is difficult to achieve high flame retardancy and mechanical strength. A flammable resin composition is provided. However, the composition that coexists with transparency, mechanical strength, and flame retardancy has not been studied, and it has been unsuitable for applications such as molded products, films / sheets, and lenses that require transparency.

On the other hand, as a technique for increasing transparency while maintaining the excellent properties of conventional polyamide resins such as chemical resistance and mechanical strength, Patent Document 8 and Patent Document 9 include amorphous or microcrystalline polyamide resins. The method used is reported.
However, a technique for improving the flame retardancy while maintaining the transparency of the amorphous or microcrystalline polyamide resin has not been studied so far.

JP 48-029846 A JP 47-007134 A JP 51-070444 A JP 54-1116054 A JP 2007-23206 A JP 2012-132027 A JP 2004-115763 A JP-A-8-239469 Special table 2008-525604 gazette

  An object of the present invention is to provide a flame retardant resin composition that is substantially free of halogen and excellent in transparency, mechanical strength, and flame retardancy.

（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はその芳香環に置換基を有してもよいフェニル基、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成分のポリアミド樹脂のガラス転移温度が９０℃〜２５０℃である前項１記載の難燃性樹脂組成物。
３．Ａ成分のポリアミド樹脂が、少なくとも１種の脂環式構造を有する前項１記載の難燃性樹脂組成物。 The present invention adopts the following configuration in order to solve the above problems.
1. (A) 100 parts by weight of a resin component (component A) that is at least one polyamide resin selected from the group consisting of an amorphous polyamide resin and a microcrystalline polyamide resin , and (B) In a smooth flat plate having a thickness of 2 mm, containing 1 to 50 parts by weight of the organophosphorus compound (component B) represented by (1) and having an arithmetic average roughness (Ra) of 0.03 μm or less, the total light transmittance is 80% or more. A flame retardant resin composition characterized by being:

(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 straight-chain aliphatic hydrocarbon group having 1 to 5 carbon atoms, and Ar is a phenyl group, naphthyl group or anthryl group which may have a substituent on the aromatic ring. N represents an integer of 1 to 3, and Ar can be bonded to any carbon atom in AL.)
2 . 2. The flame retardant resin composition according to item 1, wherein the polyamide resin of component A has a glass transition temperature of 90 ° C. to 250 ° C.
3 . 2. The flame retardant resin composition according to item 1, wherein the polyamide resin of component A has at least one alicyclic structure.

（式中、Ｒ^２、Ｒ^５は同一または異なっていてもよく、置換基を有してもよいフェニル基、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、置換基を有してもよいフェニル基、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。）
５．Ｂ成分の有機リン化合物が、下記式（４）で表される有機リン化合物である前項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。）
６．Ｂ成分の有機リン化合物は、下記式（５）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。

4 . 2. The flame retardant resin composition according to item 1, wherein the organophosphorus compound of component B is an organophosphorus compound represented by the following formula (3).

^(Wherein, R 2, ^{R 5} may be the same or different, a phenyl group which may have a substituent group, ^{.R 1,} R ³ is a naphthyl group or anthryl ^group, R 4, ^{R 6} are the same Or a substituent selected from a hydrogen atom, a branched or straight chain alkyl group having 1 to 4 carbon atoms, an optionally substituted phenyl group, a naphthyl group, or an anthryl group. .)
5 . 2. The flame retardant resin composition according to item 1, wherein the organophosphorus compound of component B is an organophosphorus compound represented by the following formula (4).

(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.)
6 . The flame retardant resin composition according to item 1 above, wherein the organic phosphorus compound of component B is a compound represented by the following formula (5).

7 . 2. The flame retardant resin composition according to item 1, wherein the organic phosphorus compound of component B has an acid value of 0.7 mgKOH / g or less.
8 . The flame retardant resin composition according to item 1, wherein the organophosphorus compound of component B has an HPLC purity of at least 90%.
9 . 2. The flame retardant resin composition according to item 1 above, which achieves at least V-2 at the flame retardant level of UL-94 standard.
10 . 2. The flame retardant resin composition according to item 1 above, wherein the B component is contained at a ratio of 2 to 40 parts by weight with respect to 100 parts by weight of the A component.
11 . 2. The flame retardant resin composition according to item 1, wherein the haze is 10% or less in a smooth flat plate having a thickness of 2 mm having an arithmetic average roughness (Ra) of 0.03 μm or less.
12 . 12. A molded article formed from the flame retardant resin composition according to any one of 1 to 11 above.
13 . Sheets or films formed from the flame-retardant resin composition according to any one of the preceding 1 to 11.

  According to the present invention, it is possible to provide a flame retardant resin composition that is substantially free of halogen and excellent in transparency, mechanical strength, flame retardancy, and chemical resistance.

Hereinafter, the present invention will be described in detail.
<A component>
The resin component (component A) of the present invention is composed of a polyamide resin by 50% by weight or more. The resin component (component A) of the present invention is preferably composed of 70% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, and particularly preferably substantially only a polyamide resin. Within the scope of the present invention, the excellent mechanical properties and chemical resistance, which are characteristics of the polyamide resin, are maintained. Examples of other resin components include polystyrene, cyclic polyolefin, polycarbonate, polyester, polyarylate, polyphenylene ether, polyphenylene sulfide, polysulfone, polyethersulfone, ABS resin, SAN resin, and elastomer.

  The polyamide resin used as the component A of the present invention is not particularly limited as long as it has transparency. As the polyamide resin having transparency, at least one polyamide resin selected from the group consisting of an amorphous polyamide resin and a microcrystalline polyamide resin can be suitably used.

Moreover, it is preferable that a polyamide resin has a glass transition temperature of 90 to 250 degreeC, More preferably, it is 100 to 230 degreeC, More preferably, it is 100 to 200 degreeC. When glass transition temperature is lower than 90 degreeC, the heat resistance of the molded article of the transparent polyamide resin composition obtained falls, and industrial usefulness may fall. Further, when the glass transition temperature is lower than 90 ° C., it is necessary to melt and knead at a low temperature, and the B component imparting flame retardancy remains in the A component in an unmelted state, causing poor dispersion. May decrease. On the other hand, when the glass transition temperature is higher than 250 ° C., melt kneading at a high temperature is required, the transparent polyamide resin is decomposed, and the molded product may be colored. In addition, there is concern about volatilization of the B component accompanying ventilation during extrusion, it becomes difficult to blend the B component with the target composition, and variations in flame retardancy and mechanical properties may occur.
As a raw material of the polyamide resin constituting the component A, a raw material monomer having an asymmetric chemical structure or a raw material monomer having an alicyclic structure can be used.

By introducing an asymmetric chemical structure, an amorphous or microcrystalline polyamide resin having transparency can be obtained. An amorphous or microcrystalline polyamide resin is preferable because it not only has transparency, but can dissolve a large amount of additives in the amorphous region, and problems such as bleeding out hardly occur.
Although it does not specifically limit as a raw material monomer which has an asymmetrical chemical structure, For example, it is comprised from 2-methyl- 1,5-pentanediamine, 2,4,4-trimethylhexamethylenediamine, and 1,2-propylenediamine. Among the groups to be selected, at least one branched aliphatic diamine can be selected.

  Further, by introducing an alicyclic structure into the polyamide resin constituting the component A, it is possible to obtain an amorphous or microcrystalline polyamide resin having transparency. When an alicyclic structure is introduced, the difference in solubility parameter between the polyamide resin component of the A component and the organophosphorus compound of the B component is reduced by increasing the hydrophobicity of the polyamide resin, thereby improving compatibility. It is possible to do. When the compatibility is improved, it is considered that the organophosphorus compound of the B component is uniformly dispersed in the polyamide resin of the A component and the flame retardancy is improved.

The raw material monomer having an alicyclic structure is not particularly limited, and examples thereof include 1,4- or 1,3-bis (aminomethyl) hexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino- At least one alicyclic diamine can be selected from the group consisting of 3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylpropane and isophoronediamine.
Although it does not specifically limit as raw material monomers other than the above, For example, it is comprised from an aliphatic, alicyclic, or aromatic diamine, dicarboxylic acid, lactam, and / or aminocarboxylic acid having 6 to 36 carbon atoms. At least one monomer can be selected from the group.

  The type of the polyamide resin having transparency is not particularly limited. For example, polyamide PA12 / MACMI (PA12 / 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, isophthalic acid), PA12 / MACMT (PA12 / 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, terephthalic acid), PA MACM 12 (4,4'-diamino-3,3'-dimethyldicyclohexylmethane, decanedicarboxylic acid or laurolactam), PA MC 12 (PA12, 1,3-bis (aminomethyl) cyclohexane), PA6I / 6T, PA6I / 6T / MACMI, PA MACM PACM 12 (4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4, 4'-diaminodicyclohexyl Methane, decanedicarboxylic acid or laurolactam), and the like. In addition, the description of the said polyamide resin followed JISK6920-1.

  A commercially available resin component including an amorphous or microcrystalline polyamide resin may be used, and is not particularly limited. For example, the trade name “Grillamide TR55” including PA12 / MACMI (Ms Chemie Japan, Inc.) ), Trade name “PA Grill M TR90” (Ms Chemie Japan) including PA MACM 12, trade name “Trogamide CX” (Daicel Evonik) including PA MC 12, and trade name “Crystamido MS” (including PA12 / MACMT) ( Arkema), trade name “Rilsan M-G350” (Arkema) including PA MACM 14 and the like.

<B component>
The B component is an organophosphorus compound represented by the following formula (1). The A component is a main component of the molding resin composition, whereas the B component is a component for imparting flame retardancy.

（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。）

(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 straight-chain aliphatic hydrocarbon group having 1 to 5 carbon atoms. Examples of the aliphatic hydrocarbon group include an alkanediyl group, an alkanetriyl group, and an alkanetetrayl group.

  Specific examples include alkylene groups having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, an isopropyldiyl group, a butylene group, and a pentylene group. Moreover, C1-C5 alkanetriyl groups, such as a methane triyl group, an ethane triyl group, a propane triyl group, a butane triyl group, a pentane triyl group, are mentioned. Moreover, C1-C5 alkane tetrayl groups, such as a methane tetrayl group, an ethane tetrayl group, a propane tetrayl group, a butane tetrayl group, a pentane tetrayl group, are mentioned.

Ar is a phenyl group, a naphthyl group or an anthryl group which may have a substituent. Examples of the substituent include alkyl groups having 1 to 5 carbon atoms such as a methyl group, an ethyl group, and a propyl group, and halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom.
Ar can be bonded to any carbon atom in AL. n is an integer of 1 to 3.

As the organic phosphorus compound (component B), a compound represented by the following formula (3) is preferable.

In the formula, R ² and R ⁵ may be the same or different and are a phenyl group, a naphthyl group or an anthryl group which may have a substituent. Examples of the substituent include alkyl groups having 1 to 5 carbon atoms such as a methyl group, an ethyl group, and a propyl group, and halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom.

R ¹ , R ³ , R ⁴ , and R ⁶ may be the same or different, a hydrogen atom, a branched or straight chain alkyl group having 1 to 4 carbon atoms, a phenyl group that may have a substituent, It is a substituent selected from a naphthyl group or an anthryl group. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and t-butyl. Examples of the substituent for the phenyl group, naphthyl group or anthryl group include alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group and propyl group, halogen atoms such as fluorine atom, chlorine atom and bromine atom.

As the organic phosphorus compound (component B), a compound represented by the following formula (4) is more preferable.

In the formula, 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 preferable.
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.

As the organophosphorus compound (component B), a compound represented by the following formula (5) is particularly preferred.

  The organophosphorus compound represented by the above formula (1) has low solubility in various solvents, and even when blended in a polyamide resin, the chemical resistance inherent in the polyamide resin can be maintained.

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 and reacting aralkyl alcohol with a compound obtained by reacting pentaerythritol with phosphorus trichloride, followed by Arbuzov transfer 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.
Alternatively, it can be obtained by reacting pentaerythritol with phosphorus trichloride and heat-treating the resulting product and the reaction product of benzyl alcohol in the presence of a catalyst.

  As the aforementioned component B, those having an acid value of preferably 0.7 mgKOH / g or less, more preferably 0.5 mgKOH / g or less are used. By using the B component having an acid value in this range, a flame retardant resin composition excellent in flame retardancy, hue and 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 having an HPLC purity of preferably at least 90%, more preferably at least 95%, and further preferably at least 99% is used. Such a high-purity product is preferred because it is excellent in flame retardancy, hue, and thermal stability of the flame-retardant resin composition. Here, the HPLC purity of the B component can be measured effectively by using the following method.

  The column was TSKgel ODS-120T 2.0 mm × 150 mm (5 μm) manufactured by Tosoh Corporation, and a mixed solution of distilled water and acetonitrile was used as the eluent, and the column temperature was 40 ° C. and the detector UV-264 nm was 0 → HPLC analysis was performed with a gradient program of 12 min: acetonitrile 50%, 12 → 17 min: acetonitrile 50 → 80%, 17 → 27 min: acetonitrile 80%, 27 → 34 min: acetonitrile 80 → 100%, 34 → 60 min: 100%. . The measurement was performed by dissolving 50 ± 0.5 mg of component B in 25 ml of acetonitrile, and then filtering with a PTFE filter having a pore size of 0.2 μm. Purity was calculated as area%.

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.
Furthermore, the average particle size of the component B is preferably 5 to 100 μm, more preferably 7 to 50 μm.

  The B component is blended in an amount of 1 to 50 parts by weight, preferably 2 to 40 parts by weight, and more preferably 3 to 30 parts by weight with respect to 100 parts by weight of the resin component (A component). The suitable range of the blending ratio of the B component is determined by the desired flame retardancy level, the type of the resin component (A component), and the like. Furthermore, the compounding quantity of B component can be changed also by use of another flame retardant and a flame retardant adjuvant, and in many cases, the compounding ratio of B component can be reduced by using these.

<Other ingredients>
Examples of other flame retardants (C component) include (C-1) to (C-11) below, but are not limited thereto.

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

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

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

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

(C-6); phosphinate compound represented by the following formula (C-6)

(C-7); diphosphinate compound represented by the following formula (C-7)

(C-8); ammonium polyphosphate (C-9); melamine (C-10); melamine polyphosphate (C-11); melamine cyanurate

In the formulas (C-2) to (C-4), Q ^{1 to} Q ⁴ may be the same or different and each is an aryl group having 6 to 15 carbon atoms, preferably an aryl group having 6 to 10 carbon atoms. is there. Specific examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group. These aryl groups may have 1 to 5, preferably 1 to 3 substituents, including (i) methyl group, ethyl group, propyl group, isopropyl group, n-butyl. Group, sec-butyl group, tert-butyl group, neopentyl group and nonyl group, such as an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 9 carbon atoms, (ii) a methoxy group, an ethoxy group and a 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- (here And W ¹ represents —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. Is shown).

In the formulas (C-3) and (C-4), Ar ⁴ and Ar ⁵ may be the same or different when both are present (in the case of C-4), 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) an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group and 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, (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 (C-3) and (C-4), m represents an integer of 1 to 5, preferably an integer of 1 to 3, particularly preferably 1.
In the formula (C-4), Z is a single bond or group that bonds Ar ⁴ and Ar ⁵ , and —Ar ⁴ —Z—Ar ⁵ — is a residue usually derived from bisphenol. Thus, Z represents a single bond, —O—, —CO—, —S—, —SO ₂ — or an alkylene group having 1 to 3 carbon atoms, preferably a single bond, —O— or isopropylidene.

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

In the formulas (C-6) and (C-7), R ₁ and R ₂ are each a linear or branched alkyl group having 1 to 6 carbon atoms and / or an aryl group having 1 to 10 carbon atoms. R ₃ represents a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 7 to 10 carbon atoms, or an aryl alkylene group having 7 to 10 carbon atoms. Represents. M is selected from Ca, Mg, Al, Zn, m represents the valence of M, 2n = mx, n is 1 or 3, and x is 1 or 2.

The phosphorus or phosphorus compound of (C-1) to (C-11) can be used in combination with the component B as long as the present invention is not impaired.
When the phosphorus or phosphorus compound of (C-1) to (C-11) is blended in the resin composition, the ratio is preferably 1 to 50 parts by weight per 100 parts by weight of the organic phosphorus compound (component B). A range of 2 to 40 parts by weight, particularly preferably 3 to 30 parts by weight is more preferable. Of the phosphorus or phosphorus compounds of (C-1) to (C-11), the phosphorus compounds of (C-2) to (C-5) are preferred.

Other flame retardant aids can be added to the resin composition of the present invention. For example, dicumyl (D component) represented by the following chemical formula (D-1) can be blended.

The aromatic ring of this biscumyl compound may have 1 to 5, preferably 1 to 3 substituents, and examples of the substituent include (i) a methyl group, an ethyl group, a propyl group, and an isopropyl group. N-butyl group, sec-butyl group, tert-butyl group, neopentyl group and nonyl group, preferably an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 9 carbon atoms, (ii) methoxy group, ethoxy Group, a propoxy group, a butoxy group and a pentoxy group having 1 to 12 carbon atoms, preferably an alkyloxy group having 1 to 9 carbon atoms, (iii) a methylthio group, an ethylthio group, a propylthio group, a butylthio group and a pentylthio group. A C1-C12 alkylthio group such as a group, preferably a C1-C9 alkylthio group, and (iv) Ar ⁶ -W ^1- Group wherein W ¹ represents —O—, —S— or an alkylene group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and Ar ⁶ represents 6 to 15 carbon atoms, preferably 6 carbon atoms. To 10 aryl groups).

  This dicumyl (component D) is blended in an amount of 0.01 to 3 parts by weight, preferably 0.02 to 2 parts by weight, particularly preferably 0.03 to 1 part by weight, based on 100 parts by weight of the resin component (component A). The It is presumed that the flame retardant effect by adding this dicumyl in the above proportion is due to radical generation, and as a result, the level of flame retardancy is improved.

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

  The flame retardant resin composition of the present invention is prepared by premixing components A and B and, if necessary, other components using a mixer such as a V-type blender, super mixer, super floater, Henschel mixer, etc. However, in many cases, the mixture is usually a mixture obtained by uniformly melt-mixing the preliminary mixture. Depending on the resin type of component A, such a mixture can be obtained, for example, by melt-kneading at a temperature of preferably about 200 to 350 ° C., more preferably about 220 to 300 ° C., and pelletizing. As the kneading means, various melt mixers such as a kneader, a single screw or a twin screw extruder can be used, but the resin composition is melted using a twin screw extruder and the liquid component is removed by a side feeder. It is often injected, extruded, and pelletized by a pelletizer.

  The flame-retardant resin composition of the present invention is useful as a material for molding various molded articles such as office automation equipment parts, home appliance parts, and automobile parts. Such a molded article can be produced by injection molding a pellet-type flame retardant resin composition at a cylinder temperature of, for example, about 200 to 350 ° C. using a conventional method, for example, an injection molding machine. Moreover, as a manufacturing method of a sheet | seat or a film, well-known methods, such as a melt extrusion method, a hot press method, a calendar method, can be mentioned, for example. In particular, the melt extrusion method is preferable from the viewpoint of productivity. In the melt extrusion method, a method of extruding a resin using a T die and feeding it to a cooling roll is preferably used. The melting temperature at this time is determined from the molecular weight, Tg, melt flow characteristics, etc. of the polycarbonate resin, but is preferably in the range of 210 ° C. to 260 ° C., more preferably in the range of 210 ° C. to 250 ° C. As thickness of a sheet | seat or a film, the range of 0.03-10 mm is preferable, More preferably, it is the range of 0.04-5 mm, More preferably, it is the range of 0.05-3 mm.

<Total light transmittance>
The resin composition of the present invention is a smooth plate having a thickness of 2 mm having an arithmetic average roughness (Ra) of 0.03 μm or less, and the total light transmittance is 80% or more, preferably 85% or more, more preferably Is 88% or more. It is preferable that the total light transmittance is 80% or more because of excellent visibility. The total light transmittance is measured according to JIS K7105.

<Haze>
The resin composition of the present invention is a smooth flat plate having a thickness of 2 mm having an arithmetic average roughness (Ra) of 0.03 μm or less. The haze is preferably 10% or less, more preferably 5% or less, and still more preferably Is 2% or less, particularly preferably 1.5% or less. When the haze is 10% or less, transparency is excellent and preferable. Haze is measured according to JIS K7105.

<Flame retardance>
The flame-retardant resin composition of the present invention is a composition that does not substantially contain halogen, and is at least V- at the flame-retardant level of the UL-94 standard in a molded article having a thickness of 1/16 inch (1.6 mm). Two levels of flame retardancy, more preferably V-0 levels, are achieved.

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

<Flame Retardant>
(1) Acid value It measured based on JIS-K-3504.
(2) HPLC purity After 50 ± 0.5 mg of flame retardant was dissolved in 25 ml of acetonitrile, it was filtered with a PTFE filter having a pore size of 0.2 μm and measured by the following analytical method. Purity was calculated as area%.
The column was TSKgel ODS-120T 2.0 mm × 150 mm (5 μm) manufactured by Tosoh Corporation, and a mixed solution of distilled water and acetonitrile was used as the eluent, and the column temperature was 40 ° C. and the detector UV-264 nm was 0 → HPLC analysis was performed with a gradient program of 12 min: acetonitrile 50%, 12 → 17 min: acetonitrile 50 → 80%, 17 → 27 min: acetonitrile 80%, 27 → 34 min: acetonitrile 80 → 100%, 34 → 60 min: 100%. .

<Resin composition>
(1) Flame retardancy (UL-94 evaluation)
Flame retardancy was evaluated using a test piece having a thickness of 1/16 inch in accordance with a vertical flame test defined in UL-94 of the US UL standard as a flame retardance evaluation scale.
(2) Total light transmittance of a three-stage plate (having a thickness of 1.0 mm, 2.0 mm, and 3.0 mm portions) plate (arithmetic average surface roughness Ra; 0.03 μm) formed by the method described in the examples. The total light transmittance of 2.0 mm thickness was measured with an integrating sphere type total light transmittance measuring machine NDH-2000 (C light source) manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K7105.
(3) Haze Nippon Denshoku Co., Ltd., in accordance with JIS K7105, a haze having a thickness of 2.0 mm of a three-stage plate (arithmetic average surface roughness Ra; 0.03 μm) molded by the method described in the examples. It measured by NDH-300A made from.
Haze (H) was calculated | required by the following formula.
H = Td / Tt × 100 (%)
(Where Td: diffuse transmittance (%), Tt: total light transmittance (%))
Haze is the turbidity of the molded product, and the lower the value, the less turbidity.
(4) Glass transition temperature A 2910 type DSC manufactured by TA Instruments Japan Co., Ltd. was used, and the glass transition temperature was measured at a heating rate of 20 ° C./min in a nitrogen atmosphere.
(5) Melting point Measurement was performed using a 2910 type DSC manufactured by TA Instruments Japan Co., Ltd. under a nitrogen atmosphere at a temperature rising rate of 20 ° C./min.
(6) Tensile test Using dumbbell-shaped test pieces molded under the conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. using Nippon Steel's injection molding machine J-75EIII, the IS0 527-1 and 527-2 Accordingly, the tensile strength at 23 ° C. was measured, and the nominal fracture strain, yield stress and tensile fracture stress were determined.
(7) Bending test Using a bending test piece molded under the conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. using an injection molding machine J-75EIII manufactured by Nippon Steel Works, bending strength and bending elastic modulus are measured according to ISO 178. Was measured.
(8) Charpy impact strength (notched)
Measure Charpy impact strength (with notch) at 23 ° C according to ISO 179 using a test piece molded under the conditions of a cylinder temperature of 280 ° C and a mold temperature of 80 ° C using an injection molding machine J-75EIII manufactured by Nippon Steel. did.

[Preparation Example 1]
Preparation of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dibenzyl-3,9-dioxide (FR-1) 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 the ³¹ P-NMR purity was 99%. The HPLC purity measured by the method described in the text was 99%. The acid value was 0.05 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 , 120 MHz): δ 23.1 (S), melting point: 257 ° C., average particle size: 30 μm

(A) Polyamide resin (component A)
(1) A commercially available amorphous polyamide (Milamide TR-90 manufactured by Emschemy Japan Co., Ltd.) was used (hereinafter referred to as PA-1). The glass transition temperature of the resin alone was 151 ° C.
(2) A commercially available microcrystalline polyamide (Trogamide myCX manufactured by Daicel-Evonik Co., Ltd.) was used (hereinafter referred to as PA-2). The resin itself had a glass transition temperature of 131 ° C. and a melting point of 250 ° C.

(B) Organophosphorus compound (component B)
(1) 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-dibenzyl-3,9-dioxide synthesized in Preparation Example 1 {of the above formula (5) Phosphorus compound (hereinafter referred to as FR-1)}

(C) Other flame retardants (1) Diethylphosphinic acid aluminum salt A commercially available phosphinate compound (Exolit OP1240 manufactured by Clariant Co., Ltd.) was used (hereinafter referred to as FR-2).
(2) Melamine polyphosphate A commercially available melamine polyphosphate (MELAPUR200 manufactured by Ciba Specialty Chemicals Co., Ltd.) was used (hereinafter referred to as FR-3).
(3) Condensed phosphate ester A commercially available condensed phosphate ester (FP-600 manufactured by ADEKA Corporation) was used (hereinafter referred to as FR-4).

[Examples 1 to 4, Comparative Examples 1 to 5]
Each component listed in Tables 1 and 2 is blended in a tumbler in the amount (expressed in parts by weight) listed in the table, and pelletized at a cylinder temperature of 250 ° C. with a 15 mmφ twin screw extruder (Technobel, KZW15). The obtained pellets were dried with a hot air dryer at 80 ° C. for 8 hours. The pellets were molded using an injection molding machine J-75EIII manufactured by Nippon Steel Works under conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. to obtain various test pieces.
It turns out that the flame retardance is improving the resin composition created in the Example, maintaining transparency, compared with the resin composition created in the comparative example.

  The present invention provides a transparent polyamide-based resin composition having high flame retardancy without substantially containing a halogen, and the resin composition is used for an electric / electronic component and an automobile that require transparency. It is useful as a material for molding various molded products such as parts and lenses, and films and sheets, and is extremely useful industrially.

Claims (13)

(A) 100 parts by weight of a resin component (component A) that is at least one polyamide resin selected from the group consisting of an amorphous polyamide resin and a microcrystalline polyamide resin , and (B) In a smooth flat plate having a thickness of 2 mm, containing 1 to 50 parts by weight of the organophosphorus compound (component B) represented by (1) and having an arithmetic average roughness (Ra) of 0.03 μm or less, the total light transmittance is 80% or more. A flame retardant resin composition characterized by being:

(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 straight-chain aliphatic hydrocarbon group having 1 to 5 carbon atoms, and Ar is a phenyl group, naphthyl group or anthryl group which may have a substituent on the aromatic ring. N represents an integer of 1 to 3, and Ar can be bonded to any carbon atom in AL.)   The flame-retardant resin composition according to claim 1, wherein the polyamide resin of the component A has a glass transition temperature of 90C to 250C.   The flame-retardant resin composition according to claim 1, wherein the polyamide resin of component A has at least one alicyclic structure. The flame retardant resin composition according to claim 1, wherein the organophosphorus compound of component B is an organophosphorus compound represented by the following formula (3).

^(Wherein, R 2, ^{R 5} may be the same or different, a phenyl group which may have a substituent group, ^{.R 1,} R ³ is a naphthyl group or anthryl ^group, R 4, ^{R 6} are the same Or a substituent selected from a hydrogen atom, a branched or straight chain alkyl group having 1 to 4 carbon atoms, an optionally substituted phenyl group, a naphthyl group, or an anthryl group. .) The flame retardant resin composition according to claim 1, wherein the organophosphorus compound of component B is an organophosphorus compound represented by the following formula (4).

(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 of component B is a compound represented by the following formula (5).

  The flame retardant resin composition according to claim 1, wherein the organic phosphorus compound of component B has an acid value of 0.7 mgKOH / g or less.   The flame retardant resin composition according to claim 1, wherein the organophosphorus compound of 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.   The flame-retardant resin composition according to claim 1, wherein the B component is contained at a ratio of 2 to 40 parts by weight with respect to 100 parts by weight of the A component.   2. The flame retardant resin composition according to claim 1, wherein a haze is 10% or less in a smooth flat plate having a thickness of 2 mm having an arithmetic average roughness (Ra) of 0.03 μm or less. Claim 1-11 molded article formed from the flame-retardant resin composition according to any one of. Sheets or films formed from the flame-retardant resin composition according to any one of claims 1 to 11.