JPH09111131A - High-molecular frame retardant and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition. which hardly undergoes coloration is thermal molding and gives a good molded item by using as a high-molecular flame retardant a polycarbonate having a specified content of nitrogen atoms bonded to the molecular ends, specific bisphenol units as the structural units, and a specified intrinsic viscosity. SOLUTION: This flame retardant has a content of nitrogen atoms bonded to the molecular ends of 200ppm or lower, structural units represented by formula I [wherein R1 to R4 are each F, Cl, Br, J, or an alkyl halide group: and X is a group represented by formula II (wherein R5 and R6 are each H, an alkyl, an alkenyl, etc.; (a) is 0-20; and (b) is 1-100)] or represented by formulas I and III [wherein R7 to R10 are each H, F, Cl, Br, J, etc.; and Y is a group represented by formula IV (wherein R11 and R12 are each H, an alkyl, an alkenyl, etc.; (d) is 0-20; and (e) is 1-100], and an intrinsic viscosity of 0.05-2.0dl/g. The ratio of the amt. of units represented by formula I to the sum of the amts. of units represented by formulas I and III is 0.05-1. The amt. of the flame retardant added to a thermoplastic resin (e.g. polycarbonate) is 0.5-20wt.% of the resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymer type flame retardant. More specifically, the present invention relates to a flame retardant composed of a specific polycarbonate having a low content of impurity nitrogen, which is excellent in heat resistance and does not cause coloring during molding.

[0002]

2. Description of the Related Art Conventionally, polycarbonate produced from tetrahalogenated bisphenols has been used as a flame retardant for thermoplastic resins because it has low volatility and excellent heat resistance. As a method for producing an aromatic polycarbonate (THPC) from tetrahalogenated bisphenols, JP-B-47-44537 and JP-B-47-2466 are available.
0, JP-A-55-25446, JP-A-63-29553
5 and the like. These tetrahalogenated bisphenols have a substituent (halogen) that inhibits polymerization on the benzene ring, as compared with bisphenol A, which is a typical raw material for polycarbonate, so generally the amount of polymerization catalyst added should be increased. Is manufactured in an environment where it is easy to polymerize. In particular, when an aliphatic tertiary amine is used as a polymerization catalyst, it is known that a part of the amine reacts with the polymer terminal to form a urethane bond (carbamate). There are many urethane-bonded nitrogen compounds (carbamates). It is known that the nitrogen compound bonded to this terminal has an adverse effect such as deterioration of hue (for example, Japanese Patent Laid-Open No. 3-539).
-199231, JP-A-2-133425).

When the amount of nitrogen at the terminal is examined, it is several ppm to several tens of ppm in the case of bisphenol A type polycarbonate which is a typical polycarbonate, whereas T
It is recognized that HPC is present in the range of hundreds of ppm to thousands of ppm. In the case of a thermoplastic resin composition using THPC as a flame retardant, THPC may be heated by heating during the molding process.
There was a case where it was colored (yellowed) due to the nitrogen compound present therein.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a thermoplastic resin composition containing a polymer type flame retardant composed of a polycarbonate, which has a small content of impurities nitrogen which does not cause coloration during molding and has excellent heat resistance. It is to provide a specific polymer type flame retardant.

[0005]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to improve the coloring during molding and processing of a thermoplastic resin composition containing a polymeric flame retardant composed of polycarbonate, and as a result, as a result, The inventors have found that the use of a polymer type flame retardant composed of a polycarbonate in which the amount of bonded nitrogen is reduced can significantly improve the coloring during the molding process, and arrived at the present invention.

That is, the present invention has a structural unit represented by the following general formula (A) or the following general formula (A) and the following general formula (B), in which nitrogen bonded to the molecular end is 200 ppm or less, The present invention relates to a polymeric flame retardant composed of polycarbonate having a viscosity of 0.05 to 2.0 dl / g.

[0007]

Embedded image

(In the formula, R _{1 to} R ₄ represent a fluorine, chlorine, bromine, iodine or halogenated alkyl group. X is a group shown below.

[0009]

[Chemical 6]

Here, R ₅ and R ₆ each represent hydrogen, an alkyl group having 1 to 5 carbon atoms which may have a substituent, an alkenyl group, an alkoxy group or an aryl group having 6 to 12 carbon atoms, or R ₅ and R ₆ represent a group which forms a carbocycle or a heterocycle by being bonded together, and the substituent which may be present on the carbon of these groups is an alkyl group or an alkenyl group having 1 to 5 carbon atoms. A halogen selected from an alkoxy group having 1 to 5 carbon atoms, fluorine, chlorine, bromine and iodine. a is 0
Is an integer of 20 and b is an integer of 1 to 100. )

[0011]

Embedded image

(In the formula, each of R _{7 to} R ₁₀ is hydrogen, fluorine, chlorine, bromine, iodine, an alkyl group having 1 to 5 carbon atoms which may have a substituent, and an alkyl group having 6 to 12 carbon atoms. Aryl group, C2-C5 alkenyl group, C1-C5
And an aralkyl group having 7 to 17 carbon atoms, and the substituents that may be present on any of the carbons of these groups are alkyl groups having 1 to 5 carbon atoms or alkenyl groups, and 1 to 5 carbon atoms. An alkoxy group, a halogen selected from fluorine, chlorine, bromine and iodine, and a dimethylpolysiloxy group are shown. Y is a group shown below.

[0013]

Embedded image

Here, R ₁₁ and R ₁₂ each represent hydrogen, an alkyl group having 1 to 5 carbon atoms which may have a substituent, an alkenyl group, an alkoxy group or an aryl group having 6 to 12 carbon atoms, or R ₁₁ and R ₁₂ represent a group which is bonded together to form a carbocycle or a heterocycle, and the substituent which may be present on the carbon atom of these groups is an alkyl group or an alkenyl group having 1 to 5 carbon atoms. A halogen selected from an alkoxy group having 1 to 5 carbon atoms, fluorine, chlorine, bromine and iodine. d is 0
The integer of -20, e represents the integer of 1-100. )

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the ratio (C) of the structural unit represented by the general formula (A) to the structural unit represented by the general formula (B) is (C) = (A) / ((A) +
(B)) = 0.05 to 1.

In the present invention, the method for producing the polymeric flame retardant comprising polycarbonate is a known method used in producing polycarbonate from bisphenols, that is, an interfacial polymerization method using bisphenol and phosgene (phosgene). Method) and a method of transesterification of bisphenol and diphenyl carbonate (transesterification method). Polycarbonate produced by the transesterification method can be produced substantially without nitrogen at the molecular end, but it is generally difficult to remove inorganic compounds and antioxidants used as catalysts, It is not preferable as a method for producing the polymeric flame retardant referred to in the present invention. Therefore, the polycarbonate type flame retardant in the present invention refers to one produced by the interfacial polymerization method.

In the interfacial polymerization method, dihydric phenol and phosgene are usually reacted in the presence of an acid binder and a solvent. Examples of the acid binder include pyridine and hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, and examples of the solvent include methylene chloride, chloroform, chlorobenzene, and xylene. Further, a catalyst such as a tertiary amine or a quaternary ammonium salt is added to accelerate the polycondensation reaction.

Further, in order to control the degree of polymerization, it is desirable to add a molecular weight regulator to carry out the reaction. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfite or a branching agent such as phloroglucin or isatin bisphenol may be added.

The reaction is usually 0 to 150 ° C., preferably 5 to
A temperature in the range of 40 ° C is suitable. The reaction time depends on the reaction temperature, but is usually 0.5 minutes to
It is 10 hours, preferably 1 minute to 2 hours. During the reaction, it is desirable to maintain the pH of the reaction system at 10 or more.

Specific examples of the bisphenol for deriving the structural unit represented by the general formula (A) used in the production of the polymeric flame retardant comprising the polycarbonate of the present invention include 2,2-bis (4- Hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-)
3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-difluorophenyl) propane, 2,2-bis (4-hydroxy-3,5-diiodophenyl) propane, 2,2 -Bis (4-hydroxy-3,5-di-trifluoromethylphenyl) propane, 1,1-bis (4-hydroxy-3,5-dibromophenyl) cyclohexane, 1,1-bis (4-hydroxy-3) , 5-dichlorophenyl) cyclohexane,
1,1-bis (4-hydroxy-3,5-dichlorophenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3,5-dibromophenyl) -1-phenylethane and the like can be mentioned. Among them, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane is preferable in terms of reactivity and cost performance.

Specific examples of the bisphenol for deriving the constitutional unit represented by the general formula (B) used in the production of the polymeric flame retardant comprising the polycarbonate of the present invention include biphenol and bis (4-hydroxyphenyl) methane. ,
Bis (4-hydroxyphenyl) ether, bis (4-
Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-Hydroxyphenyl) propane (bisphenol A; BPA), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ
), 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) Propane (dimethylbisphenol A; DMBPA), 2,2-bis (4-hydroxy-)
3,5-Dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol AP; BPAP), bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy) Phenyl) hexafluoropropane, 2,2-bis (4-hydroxy-3-allylphenyl) propane,
α, ω-bis [2- (p-hydroxyphenyl) ethyl]
Examples thereof include polydimethylsiloxane and 2,2-bis (4-hydroxy-3-allylphenyl) propane.
These may be used in combination of two or more.

Among these, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane and 2,2-bis (4-) are particularly preferable.
Hydroxy-3-methylphenyl) propane, 1,1-
It is preferably selected from bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) ether and bis (4-hydroxyphenyl) sulfide.

As the tertiary amine polymerization catalyst used for producing the polymer type flame retardant comprising the polycarbonate of the present invention, there are triethylamine, tri-n-propylamine, tri-n-butylamine, diethylaminopyridine, etc. Triethylamine is preferred from the standpoint of cleaning and removal. Further, a polymerization promoter may be used in combination, and specifically, tetramethylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetraethylammonium bromide, tetraiodide-
Although quaternary ammonium salts such as n-butylammonium can be used, benzyltriethylammonium chloride is preferable from the viewpoint of easy handling and reactivity.

In the case of the interfacial polymerization method, the polymerization catalyst is usually added in an amount of about 0.001 to 1.0 mol% with respect to the raw material bisphenol. When the halogenated bisphenol as in the present invention is used as the raw material. Since the reaction is extremely difficult to proceed, a large amount of catalyst is generally used, and it is usually preferable to add 5.0 to 50.0 mol% to the starting phenol. Further, the reaction promoter is preferably added in an amount of 0.01 to 10.0 mol% with respect to the raw material bisphenol.

Further, a molecular weight modifier is used as desired in the production of the polymer type flame retardant comprising the polycarbonate of the present invention. Examples of the molecular weight modifier used include monohydric phenols, carboxylic acids and acid chlorides. Examples of monofunctional compounds include monofunctional phenols, among which monohydric phenols are preferred because of their reactivity and ease of handling.

Specific examples of the monohydric phenol used as the molecular weight modifier include phenol, para-tertiary butyl phenol, para-ethyl phenol, para-n-octyl phenol and other alkyl-substituted phenols, ethyl para-hydroxybenzoate, para-hydroxybenzoic acid. Alkyl ester-substituted phenols such as butyl acid, eugenol, O-allylphenol, alkenyl-substituted phenols such as parahydroxystyrene and paraisopropenylphenol, monochlorophenol, dichlorophenol, trichlorophenol, monobromophenol, dibromophenol, tribromophenol , Halogenated phenols such as monofluorophenol, difluorophenol, and trifluorophenol. Among these, halogenated phenols are especially
It is one of the preferable ones because it can impart further flame retardancy.

In the present invention, as a method of reducing the amount of nitrogen bonded to the molecular end of the polycarbonate to 200 ppm or less, for example, a method of reducing the amount of tertiary amine and using a large amount of reaction cocatalyst, or bringing the produced polymer into contact with an alkaline aqueous solution. There are ways. If a reaction co-catalyst is used, the reaction of phosgene and bisphenol will be promoted even if the amount of tertiary amine is reduced, and the polymerization rate will be increased, while nitrogen remaining at the molecular end much more than when a large amount of tertiary amine is used. The amount can be reduced. The reaction promoter concentration used in this case is 0.01 to 10.0 with respect to the raw material bisphenol.
It is preferable to add it in the range of mol%.

On the other hand, in the method of contacting with an alkaline aqueous solution, the molecular terminal is prepared by contact stirring of an alkaline aqueous solution in which sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, sodium carbonate and the like are dissolved and a polymer (polycarbonate) solution. The nitrogen compound (carbamate) bound to is decomposed, and the molecular terminal nitrogen is reduced. When this method is used, the concentration of the aqueous alkali solution is preferably about 0.5 to 3.0 w / v%, and if it is less than 0.5 w / v%, it takes time to remove nitrogen, and if it exceeds 3.0 w / v%. The carbonate bond is severely broken, which is not preferable. In addition, the ratio of the contact stirring of the polycarbonate resin solution and the alkaline aqueous solution is 0.2 to 1 volume of the polycarbonate resin solution.
The contact efficiency of 2.0 times gives good decomposition efficiency. The stirring time is
Although it depends on the alkali concentration, the amount of the resin solution, etc., it is preferable that the contact is as short as possible in order to reduce the decomposition of the carbonate bond. When the volume ratio with the alkaline aqueous solution is the above, the amount of terminal nitrogen is usually 200 pp if contacted for 5 to 120 minutes.
m or less. Furthermore, if the method of using the reaction promoter and the method of contacting with the alkaline aqueous solution are used together, the terminal nitrogen can be reduced more efficiently.

The polymer type flame retardant made of polycarbonate in the present invention has a nitrogen bonded to the molecular end of 200 p
pm or less, and 200 pp nitrogen attached to the end of the molecule
When it exceeds m, the heat resistance is lowered, and the coloring (yellowing) of the thermoplastic resin containing the flame retardant during the heat molding is promoted, and a molded product having an excellent color tone cannot be obtained.

In the polymer type flame retardant made of the polycarbonate of the present invention, the nitrogen bonded to the molecular terminal is adjusted to 200 ppm or less by using the above-mentioned technology for reducing terminal nitrogen. Incidentally, free tertiary amines and quaternary ammonium salts are removed as salts in the aqueous phase side at the stage of the neutralization treatment after the completion of the polymerization reaction, and most of them are removed without causing a problem.

The polymer type flame retardant made of polycarbonate in the present invention can be added to a thermoplastic resin to impart flame retardancy. Considering sufficient flame retardancy and moldability when added to the thermoplastic resin, it is added in the range of 0.5 to 20% by weight with respect to the thermoplastic resin.

The thermoplastic resin in which the polymer type flame retardant of the present invention is preferably used is polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polyarylate, polyethylene, polypropylene, polystyrene, polyoxymethylene, polyphenylene ether, ABS, Polyamide and the like are exemplified, but when it is applied to polycarbonate, polybutylene terephthalate, polyethylene terephthalate, and polyarylate, which are particularly required to have high-temperature molding and color, preferable results can be obtained.

In the polymer type flame retardant made of the polycarbonate of the present invention, the ratio (C) of the constitutional unit represented by the general formula (A) to the constitutional unit represented by the general formula (B) is as described above. , (C) = (A) / ((A) + (B)) =
Although it is in the range of 0.05 to 1, it is preferable that (C) is in the range of 0.5 to 1 in order to impart sufficient flame retardancy.

The polymeric flame retardant of the present invention has an intrinsic viscosity [η] in the range of 0.05 to 2.0 dl / g (20 ° C., methylene chloride solution), and the intrinsic viscosity [η]. When it is less than 0.05 dl / g, the volatility at the time of high temperature molding is increased, and when it exceeds 2.0 dl / g, the melt viscosity is high and the blendability with other resins and the moldability are deteriorated. Taking into consideration the nonvolatility and the ease of blending with the thermoplastic resin, those having an intrinsic viscosity [η] of 0.3 dl / g or less are preferable.

Specific examples will be described below with reference to Examples and Comparative Examples.

Example 1 3.7 kg of sodium hydroxide was dissolved in 42 l of water,
2,2-bis (4-hydroxy-3, while maintaining at ℃
5-dibromophenyl) propane (hereinafter "TBBPA")
17.2 kg and hydrosulfite 8 g were dissolved. While adding 28 liters of methylene chloride to this and stirring, pt-butylphenol (hereinafter referred to as "PT
1.5 kg, triethylbenzylammonium chloride (hereinafter referred to as "TEBAC") 10
phosgene 7.0k while maintaining the temperature below 20 ° C
b was blown in 70 minutes. During the blowing of phosgene, a 35 w / v% sodium hydroxide aqueous solution was added at an appropriate time so that the pH in the system did not fall below 11. After blowing phosgene, stir vigorously to emulsify the reaction solution, and after emulsification, 450
g of triethylamine was added, and stirring was continued for about 1 hour for polymerization. After the reaction, the polymerization liquid was separated into an aqueous phase and an organic phase, and 2 w / v
% Of sodium hydroxide aqueous solution and contact stirring was performed for 20 minutes. After that, the polymerization liquid was separated again into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and then washing with water was repeated until the pH of the washing liquid became neutral. Then, the polymer is added to 80
Granulation was carried out by appropriately lowering the temperature to warm water heated to ℃. The obtained granular material was filtered and then dried to obtain a polymeric flame retardant composed of powdered polycarbonate having an intrinsic viscosity of 0.12 dl / g (20 ° C., methylene chloride solution) (hereinafter referred to as “P”). -1 "). The total amount of nitrogen contained in the polymeric flame retardant composed of this polycarbonate was measured and found to be 172 ppm.

Example 2 The procedure of Example 1 was repeated, except that TEBAC was changed to 50 g and triethylamine was changed to 300 g. The polymer type flame retardant composed of the obtained powdery polycarbonate (hereinafter referred to as "P
-2 ") had an intrinsic viscosity of 0.12 dl / g. The total amount of nitrogen contained in the polymeric flame retardant composed of this polycarbonate was measured and found to be 144 ppm.

Example 3 Instead of 17.2 Kg of TBBPA, TBBPA 8.6
Kg, 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as “BPA”) 3.6 Kg was used in the same manner as in Example 1 except that it was used. Polymeric flame retardant composed of the obtained powdery polycarbonate (hereinafter referred to as "P-3").
(Hereinafter referred to as)) had an intrinsic viscosity of 0.11 dl / g. The total amount of nitrogen contained in the polymeric flame retardant made of this polycarbonate was measured and found to be 154 ppm.

Example 4 1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter referred to as "BPZ") 4.2K instead of BPA
The same procedure as in Example 1 was carried out except that g was used. The polymer type flame retardant (hereinafter referred to as "P-4") composed of the obtained powdery polycarbonate has an intrinsic viscosity of 0.12 dl.
/ G. When the total amount of nitrogen contained in the polymer type flame retardant composed of this polycarbonate was measured, it was found to be 130
ppm.

Example 5 Example 4 was repeated except that 3.3 kg of 2,4,6-tribromophenol (hereinafter referred to as "TBP") was used instead of PTBP. Polymeric flame retardant composed of the obtained powdery polycarbonate (hereinafter referred to as "P-5")
Had an intrinsic viscosity of 0.11 dl / g. The total amount of nitrogen contained in the polymeric flame retardant composed of this polycarbonate was measured and found to be 181 ppm.

Example 6 After the completion of the polymerization reaction, the same procedure as in Example 1 was carried out except that the contact time with the aqueous alkali solution was changed to 40 minutes. The intrinsic viscosity of the obtained polymer flame retardant (hereinafter referred to as “P-6”) made of powdered polycarbonate was 0.12 dl / g.
The total nitrogen content in the polymeric flame retardant composed of this polycarbonate was measured and found to be 134 ppm.

Example 7 In place of TEBAC, 10 g of triethylamine was used, and the contact time with the alkaline aqueous solution after completion of the polymerization reaction was 4 times.
Example 1 was repeated except that the time was set to 0 minutes. The intrinsic viscosity of the polymer flame retardant (hereinafter, “P-7”) made of the obtained powdery polycarbonate was 0.13 dl / g.
The total amount of nitrogen contained in the polymeric flame retardant composed of this polycarbonate was measured and found to be 185 ppm.

Comparative Example 1 After the completion of the polymerization reaction, the same procedure as in Example 1 was carried out except that the solution was not contacted with an alkaline aqueous solution but was immediately neutralized. The intrinsic viscosity of the obtained powdery polycarbonate resin (hereinafter “P-8”) was 0.12 dl / g. The total amount of nitrogen contained in this polycarbonate resin was measured and found to be 256 ppm.
Met.

Comparative Example 2 After the completion of the polymerization reaction, the same procedure as in Example 6 was carried out except that neutralization was carried out immediately without contact with an alkaline aqueous solution. The intrinsic viscosity of the obtained powdery polycarbonate resin (hereinafter “P-9”) was 0.12 dl / g. When the total amount of nitrogen contained in this polycarbonate resin was measured, it was 410 p.
pm.

Test Example 1 To a commercially available polycarbonate powder (Upilon S-3000 manufactured by Mitsubishi Gas Chemical Co., Inc.), 10 wt% of the polymer type flame retardant (P-1) made of the polycarbonate of Example 1 was added, and a 20 mm vent was used. It was extruded at 280 ° C. with an attached extruder and melt-pelletized. The obtained pellets are heated at 320 ° C.
Injection molding was performed to obtain an injection molded product of 90 × 50 × 3 mm. The YI value (yellow index) of the obtained injection-molded product was measured with a color difference meter to examine the degree of coloring.

Test Example 2 Test Example 2 was repeated except that the polymer type flame retardant (P-6) made of the polycarbonate of Example 6 was used.

Test Examples 3 and 4 The same procedure as Test Example 1 was repeated except that the polycarbonate resins of Comparative Examples 1 and 2 were used.

The compositional analysis of the polymeric flame retardants composed of the polycarbonates of Examples 1 to 7 and the polycarbonate resins of Comparative Examples 1 to 2 is shown in Table 1, and the YI values of Test Examples 1 and 2 and Test Examples 3 and 4 are shown in Table 1. The results are shown in Table 2.

[0049]

[Table 1] ─────────────────────────────── Example PC terminal group measurement intrinsic viscosity and type Terminal nitrogen content Terminal Cl Quantity Terminal OH Comparative Example (ppm) (ppm) (ppm) (dl / g) Example 1 P-1 172 2.5 ND 0.12 Example 2 P-2 144 1.9 ND 0.12 Example 3 P-3 154 1.8 ND 0.11 Implementation Example 4 P-4 130 2.2 ND 0.12 Example 5 P-5 181 2.6 ND 0.11 Example 6 P-6 134 1.1 14 0.12 Example 7 P-7 185 0.9 22 0.13 Comparative Example 1 P-8 256 4.4 ND 0.12 Comparative Example 2 P-9 410 3.1 ND 0.12 ────────────────────────────────

The description in Table 1 is as follows. Terminal nitrogen amount: Measured with a total nitrogen analyzer manufactured by Mitsubishi Chemical Corporation. The amount of terminal Cl: 0.5 w / v% methylene chloride solution was used as a sample and measured by a nitropyridine colorimetric method. Amount of terminal OH: 1 w / v% methylene chloride solution was used as a sample and measured by a titanium tetrachloride colorimetric method. The detection limit is 10pp
m. Intrinsic viscosity: 1w / v% methylene chloride solution as a sample,
It measured at 20 degreeC and the Uberode-viscosity tube.

[0051]

[Table 2] Test Example Flame Retardant YI Value Test Example 1 P-1 2.1 Test Example 2 P-6 2.0 Test Example 3 P-7 3.3 Test Example 4 P-8 3.7 YI Value: 3 mm The YI value (yellow index) in the thickness direction of one of the thick test pieces was measured using a color difference meter.

[0052]

EFFECT OF THE INVENTION The polymer type flame retardant made of the polycarbonate of the present invention has a smaller nitrogen content than the conventional polycarbonate type flame retardant, has improved heat resistance of the flame retardant itself, and is a thermoplastic resin containing a flame retardant. The composition is suitable for engineering plastics such as polycarbonate and polybutylene terephthalate, which are molded at a high temperature, because the composition gives less coloration during heat molding and gives a molded article having a good appearance.

Claims (6)

[Claims] 1. A structural unit represented by the following general formula (A) or the following general formula (A) and general formula (B) in which nitrogen bonded to a molecular end is 200 ppm or less, and an intrinsic viscosity of 0. A polymer type flame retardant composed of polycarbonate having an amount of 05 to 2.0 dl / g. Embedded image (In the formula, R _{1 to} R ₄ represent a fluorine, chlorine, bromine, iodine, or halogenated alkyl group. X is a group shown below. Here, R ₅ and R ₆ each represent hydrogen, an alkyl group having 1 to 5 carbon atoms which may have a substituent, an alkenyl group, an alkoxy group or an aryl group having 6 to 12 carbon atoms, or R
₅ , R ₆ represents a group which is bonded together to form a carbocycle or a heterocycle, and the substituent which may be present on the carbon of these groups is an alkyl group or an alkenyl group having 1 to 5 carbon atoms, It is a halogen selected from an alkoxy group having 1 to 5 carbon atoms, fluorine, chlorine, bromine and iodine. a is an integer from 0 to 20,
b represents an integer of 1 to 100. ) (In the formula, R _{7 to} R ₁₀ are each hydrogen, fluorine, chlorine,
Bromine, iodine, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, each of which may have a substituent. It is an aralkyl group having 7 to 17 carbon atoms, and the substituent which may be present on any of the carbon atoms of these groups is 1 to 5 carbon atoms.
And an alkenyl group, an alkoxy group having 1 to 5 carbon atoms, a halogen selected from fluorine, chlorine, bromine and iodine, and a dimethylpolysiloxy group. Y is a group shown below. Embedded image Here, R ₁₁ and R ₁₂ each represent hydrogen, an alkyl group having 1 to 5 carbon atoms, which may have a substituent, an alkenyl group, an alkoxy group, or an aryl group having 6 to 12 carbon atoms, or R
₁₁ and R ₁₂ represent a group which is bonded together to form a carbocycle or a heterocycle, and the substituent which may be present on the carbon of these groups is an alkyl group or an alkenyl group having 1 to 5 carbon atoms, It is a halogen selected from an alkoxy group having 1 to 5 carbon atoms, fluorine, chlorine, bromine and iodine. d is an integer from 0 to 20,
e represents an integer of 1 to 100. ) 2. A ratio (C) of the general formula (A) and the general formula (B).
However, (C) = (A) / ((A) + (B)) = 0.05-
The flame retardant according to claim 1, which is in the range of 1. 3. The constitutional unit represented by the general formula (A) is 2,2.
-Bis (4-hydroxy-3,5-dibromophenyl)
The flame retardant according to claim 1, which is a structural unit derived from propane. 4. The constitutional unit represented by the general formula (B) is 2,2.
-Bis (4-hydroxyphenyl) propane, 1,1-
Bis (4-hydroxyphenyl) cyclohexane, 2,
2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-
The flame retardant according to claim 1, which is a structural unit derived from the group consisting of phenylethane, bis (4-hydroxyphenyl) ether, and bis (4-hydroxyphenyl) sulfide. 5. The polymer-type flame retardant according to claim 1 is added in an amount of 0.5 to 5.
A thermoplastic resin composition containing 20% by weight. 6. The thermoplastic resin composition according to claim 5, wherein the thermoplastic resin is polycarbonate, polybutylene terephthalate, polyethylene terephthalate, or polyarylate.