JP2001019837A - Flame-retarded polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide flamed-retarded polycarbonate resin compositions which excel in mechanical properties, weatherability and flame retardance and, at the same time, excel in mold depositing properties. SOLUTION: Flame-retarded polycarbonate resin compositions comprise (a) 100 pts.wt. aromatic polycarbonate, (b) 0.5-40 pts.wt. nitrogen-containing phosphate ester represented by the formula (wherein R1 is a 1-6C alkylene group, a halogen substituted alkylene group, an arylene group or a halogen substituted arylene group; R2 and R3 are each hydrogen, a 1-6C alkyl group or an aryl group and R2 and R3 may be linked with an alkylene group; and Ph is an aryl group or a halogen substituted aryl group and the aryl group excludes the one having an alkyl group in the aromatic ring), (c) 0.01-5 pts.wt. polyfluoroethylene, (d) 0.5-30 pts.wt. impact resistance improver, and (e) 0.01-2 pts.wt. ultraviolet absorber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant polycarbonate resin composition, and more particularly, to a flame-retardant polycarbonate resin composition having excellent weather resistance.

[0002]

2. Description of the Related Art Polycarbonate resin compositions have been used in various fields as excellent engineering plastics, and have also been used in applications requiring flame retardancy. As the flame-retardant polycarbonate resin, a number of resin compositions containing a phosphorus-based flame retardant represented by a phosphoric ester as a non-halogen material are disclosed, and in particular, a structure derived from resorcinol due to the problem of mold deposit during molding. Examples of using a condensed phosphate having the formula

Further, JP-A-6-228426 and JP-A-7-53876 disclose resin compositions in which a condensed phosphate having a structure derived from bisphenol is blended with a thermoplastic resin such as a polycarbonate resin. It discloses that the bleeding property or the hydrolysis resistance is improved. However, a polycarbonate resin composition containing such a condensed phosphate ester was not always a resin composition that was satisfactory in terms of weather resistance. JP-A-10-175895 discloses a nitrogen-containing phosphate compound and a flame-retardant composition comprising the compound. However, even in this patent, the weather resistance is not sufficient.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a flame-retardant polycarbonate resin composition which is excellent in mechanical properties, weather resistance and flame retardancy, and is excellent in low mold depositability.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problem, and its gist is as follows:
To 100 parts by weight of the aromatic polycarbonate resin, (b) a nitrogen-containing phosphate represented by the following general formula (1):
40 parts by weight, (c) polyfluoroethylene 0.01 to 5
Parts by weight, (d) 0.5 to 30 parts by weight of an impact resistance improver, and (e) 0.01 to 2 parts by weight of an ultraviolet absorber.

Embedded image (Wherein, R ¹ comprises an alkylene group having 1 to 6 carbon atoms, a halogen-substituted alkylene group, an arylene group, or a halogen-substituted arylene group; R ² and R ³ represent hydrogen, an alkyl group having 1 to 6 carbon atoms, aryl R ² and R ³ may be linked by an alkylene group, and Ph is an aryl group or a halogen-substituted aryl group, and the aryl group does not include those having an alkyl group on an aromatic ring. )

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The aromatic polycarbonate resin (a) in the present invention includes an aromatic hydroxy compound or an optionally branched thermoplastic aromatic polycarbonate resin produced by reacting an aromatic hydroxy compound or a small amount of the polyhydroxy compound with phosgene or a carbonic acid diester. It is a union or a copolymer. The production method is not limited,
It can be produced by a phosgene method (interfacial polymerization method) or a melting method (ester exchange method). Further, an aromatic polycarbonate resin produced by a melting method and having an adjusted amount of terminal OH groups can be used.

The aromatic dihydroxy compound includes
2,2-bis (4-hydroxyphenyl) propane (=
Bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -P-diisopropylbenzene, hydroquinone, resorcinol,
4,4-dihydroxydiphenyl and the like are preferable, and bisphenol A is preferable.

To obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-dimethyl-2,4,4
6-tri (4-hydroxyphenyl) heptene-2,
4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-
Tri (4-hydroxyphenyl) heptene-3,1,
3,5-tri (4-hydroxyphenyl) benzene,
Polyhydroxy compounds represented by 1,1,1-tri (4-hydroxyphenyl) ethane or 3,3-
Bis (4-hydroxyaryl) oxindole (=
Isatin bisphenol), 5-chlorisatin bisphenol, 5,7-dichlorisatin bisphenol,
5-bromoisatin bisphenol or the like may be used as a part of the aromatic dihydroxy compound, and the amount used is 0.01 to 10 mol%, preferably 0.1 to 10 mol%.
2 mol%.

In the present invention, (a) the aromatic polycarbonate resin is preferably a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane or 2,2-bis (4-hydroxyphenyl) propane And other aromatic dihydroxy compounds.
(A) The molecular weight of the aromatic polycarbonate resin is a viscosity average molecular weight calculated from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, and is preferably 16,000 to 30,000, more preferably 1
8,000-26,000.

In the above-mentioned production method, in order to adjust the molecular weight, a monovalent aromatic hydroxy compound may be used as a part of the aromatic dihydroxy compound, and m- and p-methylphenol, m- and p-propyl may be used. Phenol, p
-Tert-butylphenol and p-long-chain alkyl-substituted phenols. In the present invention, (a)
As the aromatic polycarbonate resin, a mixture of two or more resins may be used. In the present invention, (b)
The nitrogen-containing phosphoric ester is represented by the following general formula (1).

[0011]

Embedded image

Wherein R ¹ is an alkylene group having 1 to 6 carbon atoms, a halogen-substituted alkylene group, an arylene group or a halogen-substituted arylene group; R ² and R ³ are hydrogen, alkyl having 1 to 6 carbon atoms; R ² and R ³
May be linked by an alkylene group. Ph is an aryl group or a halogen-substituted aryl group, and the aryl group does not include those having an alkyl group on an aromatic ring. )

Ph in the general formula (1) is an aryl group or a halogen-substituted aryl group, but the aryl group does not include those having an alkyl group on an aromatic ring. In the present invention, a phenyl group is particularly desirable. For example, in the case of a group having an alkyl group such as a methyl group in an aromatic ring such as a benzene ring such as a toluyl group, the melting point of the flame retardant increases, but the weather resistance deteriorates. Further, the aryl group may have a halogen atom as a substituent. In the above general formula (1), R ¹ is preferably an alkylene group having 1 to 6 carbon atoms or an arylene group. Also in this case, the arylene group preferably has no substituent such as an alkyl group on an aromatic ring such as a benzene ring. As R ² and R ³ ,
They may be the same or different. In the case of an aryl group, it is preferable that an aromatic ring such as a benzene ring has no substituent such as an alkyl group. Further, R ² and R ³ may be linked by an alkylene group. When linked by an alkylene group, 2
It is preferable to form a nitrogen-containing 5-membered ring such as a piperazine ring or a nitrogen-containing 6-membered ring together with two nitrogen atoms and a group represented by R ¹ . In the present invention, the amount of the nitrogen-containing phosphoric acid ester (b) to be added is 100 parts of the aromatic polycarbonate resin.
0.5 to 40 parts by weight, preferably 1 to
30 parts by weight. (B) When the addition amount of the nitrogen-containing phosphoric acid ester is less than 0.5 part by weight, the flame retardancy is not sufficiently improved, and when it exceeds 40 parts by weight, the heat resistance is greatly reduced.

The polyfluoroethylene (c) in the present invention includes, for example, polytetrafluoroethylene having a fibril-forming ability, which is easily dispersed in a polymer and binds the polymers to form a fibrous material. It shows the tendency to make. Polytetrafluoroethylene having fibril-forming ability is classified into Type 3 according to ASTM standards. Examples of the polytetrafluoroethylene having a fibril-forming ability include Teflon 6J (trade name) or Teflon 3 from Mitsui-DuPont Fluorochemical Co., Ltd.
It is commercially available as 0J (trade name) or as Polyflon (trade name) from Daikin Industries, Ltd.

(C) The blending amount of polyfluoroethylene is
0.1 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin.
It is 01 to 5 parts by weight. Polyfluoroethylene is 0.0
If the amount is less than 1 part by weight, the flame retardancy is insufficient, and if it exceeds 5 parts by weight, the appearance of the molded article tends to deteriorate. The compounding amount of the polyfluoroethylene is preferably 0.02 to 4 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the aromatic polycarbonate resin.

As the (d) impact modifier used in the present invention, acrylic rubber, styrene / hydrogenated butadiene / styrene block copolymer, styrene / hydrogenated isoprene / styrene block copolymer, AES resin, AAS resin, polybutadiene, butadiene / styrene copolymer,
Polyisoprene and the like, preferably acrylic rubber, styrene / hydrogenated butadiene / styrene block copolymer, styrene / hydrogenated isoprene / styrene block copolymer, AES resin, AAS resin and the like are more preferable. Include acrylic rubber.

Examples of the acrylic rubber include, for example, a multilayer structure polymer containing an alkyl (meth) acrylate polymer. The alkyl group in the alkyl acrylate polymer has about 1 to 8 carbon atoms. Examples of the alkyl acrylate polymer include ethyl acrylate, butyl acrylate, ethylhexyl acrylate, and the like. A crosslinking agent such as an ethylenically unsaturated monomer may be used in the alkyl acrylate polymer. Examples of the crosslinking agent include alkylene diol, di (meth) acrylate, polyester di (meth) acrylate, Examples thereof include divinylbenzene, trivinylbenzene, triallyl cyanurate, and allyl (meth) acrylate.

The multi-layered polymer containing the alkyl (meth) acrylate polymer is, for example, a polymer produced by continuous multi-stage seed polymerization in which the polymer is coated one after another. As a polymer structure, the outermost layer (shell) made of an alkyl (meth) acrylate polymer compound that improves the adhesion between the inner core layer (core), which is a crosslinking component having a low glass transition temperature, and the matrix of the composition. Is a multilayer structure polymer having The inner core layer is preferably made of a saturated or unsaturated rubber component, and more preferably a crosslinked rubbery polymer. Furthermore, the innermost core layer is formed of a polymer composed of an aromatic vinyl monomer, the intermediate layer is formed of a rubbery polymer having a low glass transition temperature, and the outermost layer is formed of an alkyl (meth) acrylate polymer. A polymer having a multilayer structure as formed may also be mentioned, but this is preferable because it is effective in improving poor appearance such as pearl luster. Examples of the saturated or unsaturated rubber component include alkyl acrylate, butadiene, and a butadiene / styrene copolymer. Examples of the alkyl (meth) acrylate include an alkyl (meth) acrylate having an alkyl group having about 1 to 8 carbon atoms.

(D) The compounding amount of the impact modifier is (a)
0.1 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin.
5 to 30 parts by weight. (D) 0.5 of impact modifier
When the amount is less than 30 parts by weight, the impact resistance is insufficient. In the present invention, the amount of the (d) impact modifier is preferably 1 to 25 parts by weight, more preferably 2 to 2 parts by weight.
0 parts by weight.

As the ultraviolet absorber (e) in the present invention, benzophenone type, benzotriazole type, phenyl salicylate type, hindered amine type and the like can be mentioned.
Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, Hydroxy-4-octadecyloxy-benzophenone, 2,2′-dihydroxy-4-methoxy-benzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-benzophenone, 2,
2 ', 4,4'-tetrahydroxy-benzophenone and the like.

As the benzotriazole-based ultraviolet absorber, 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ',
5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole and the like.

Examples of the phenyl salicylate-based ultraviolet absorber include phenylsalicylate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate and the like. Examples of the hindered amine-based ultraviolet absorber include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

(E) In addition to the above, compounds having a function of converting the energy possessed by ultraviolet rays into vibrational energy within the molecule and releasing the vibrational energy as heat energy are also included as the ultraviolet absorbent. further,
Those that exhibit an effect when used in combination with an antioxidant or a coloring agent, or a light stabilizer called a quencher that acts as a light energy conversion agent can also be used in combination.

The amount of the ultraviolet absorbent (e) is 0.0 to 100 parts by weight of the aromatic polycarbonate resin (a).
1 to 2 parts by weight. (E) If the amount of the ultraviolet absorber is less than 0.01 part by weight, the weather resistance is insufficient, and if it exceeds 2 parts by weight, the yellowness becomes strong, so that the toning property is inferior and bleed-out is caused. Cheap. (E) The compounding amount of the ultraviolet absorber is preferably 0.05 to 1.8 parts by weight, more preferably 0.1 to 1.5 parts by weight, per 100 parts by weight of the aromatic polycarbonate resin (a). Department.

In the flame-retardant polycarbonate resin composition of the present invention, it is preferable to add (f) a surface-treated titanium oxide as an optional component. The titanium oxide is
Improve the whiteness, light-shielding properties, light reflectance, etc. of the molded product.
Titanium oxide is manufactured by the sulfuric acid method or the chlorine method, but titanium oxide manufactured by the sulfuric acid method is inferior to titanium oxide manufactured by the chlorine method in terms of whiteness. It is suitable. The crystal forms of titanium oxide include a rutile type and an anatase type, and the rutile type is excellent in terms of whiteness, light reflectance and light resistance, and the rutile type is preferable.

In general, when the surface of titanium oxide is not treated, it is likely to cause a decrease in the molecular weight and discoloration of the polycarbonate resin when the resin composition is melt-kneaded at a high temperature. The surface treatment of titanium oxide is performed with one or more inorganic surface treatment agents selected from alumina hydrate and silicic acid hydrate. Further, titanium oxide treated with an organic surface treatment agent, particularly a silicone compound, is preferable. As the silicone compound, polyorganosiloxane (JP-B-63-2)
No. 6140), polyhydrocarbon siloxane (see JP-B-63-31513), silane coupling agent (see JP-B-3-2189), and the like.

The average particle size of the titanium oxide is preferably 0.05 to 0.5 μm. Average particle size 0.05μ
If it is less than 0.5 m, the light-shielding properties and light reflectance of the obtained molded article are likely to be insufficient, and if it exceeds 0.5 μm, the light-shielding properties and light reflectance of the molded article are likely to be insufficient, and It is easy to cause a drop and a drop in impact strength. The average particle size is more preferably from 0.08 to 0.45 μm, and most preferably from 0.1 to 0.4 μm.

The amount of the (f) surface-treated titanium oxide is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the polycarbonate resin (a). (F) By blending the surface-treated titanium oxide, the light-shielding property of the molded article is improved, but if it exceeds 30 parts by weight, the impact strength tends to be reduced. Therefore, the amount of (f) the surface-treated titanium oxide is more preferably in the range of 1 to 25 parts by weight.

The method for producing the flame-retardant polycarbonate resin composition of the present invention is not particularly limited.
A method in which (a) an aromatic polycarbonate resin, (b) a nitrogen-containing phosphate ester, (c) polyfluoroethylene, (d) an impact resistance improver, and (e) an ultraviolet absorber are melt-kneaded together, (a) A method in which an aromatic polycarbonate resin, (b) a nitrogen-containing phosphate ester and (c) polyfluoroethylene are kneaded in advance, and then (d) an impact resistance improver and (e) an ultraviolet absorber are blended and melt-kneaded. No.

The flame-retardant polycarbonate resin composition of the present invention may further comprise, if necessary, a stabilizer such as an antioxidant in addition to the components (a) to (e) or (a) to (f). Agents, pigments, dyes, lubricants, other flame retardants, release agents, additives such as slidability improvers, fibrous reinforcing materials such as glass fibers and carbon fibers,
A plate-like reinforcing material such as mica, talc, glass flake, or a whisker such as potassium titanate or aluminum borate can be added and blended.

In the flame-retardant polycarbonate resin composition of the present invention, other heat-resistant materials such as styrene resins, polyester resins such as polybutylene terephthalate and polyethylene terephthalate, polyamide resins, polyolefin resins, etc., are not impaired. A plastic resin can be blended. The compounding amount of such other thermoplastic resin is preferably 40% by weight or less, more preferably 30% by weight or less of the whole resin composition.

The flame-retardant polycarbonate resin composition of the present invention is a flame-retardant polycarbonate resin composition containing a non-halogenated nitrogen-containing phosphoric acid ester compound. Are non-chlorine and non-bromine, and are preferred materials for eliminating the problem of corrosion of molding machines and molds.

[0033]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. The following raw materials were used in Examples and Comparative Examples. (1) Polycarbonate resin: Iupilon (registered trademark)
S-3000, product of Mitsubishi Engineering-Plastics Corporation, viscosity average molecular weight 21,000, poly-4,
4-isopropylidene diphenyl carbonate (hereinafter also referred to as “PC”)

(2) Nitrogen-containing phosphate ester 1: produced by the following synthesis example 1 (structure represented by formula (2))

[0035]

Embedded image

(3) Nitrogen-containing phosphoric acid ester 2: produced by the following synthesis example 2 (structure represented by formula (3))

[0037]

Embedded image

(4) Phosphate ester 1: Triphenylphosphine (TPP), a product of Daihachi Chemical Industry Co., Ltd. (5) Phosphate ester 2: Condensed phosphoric ester represented by the formula (4) (n = 1.3), trade name: CR-733, manufactured by Daihachi Chemical Industry Co., Ltd.

[0039]

Embedded image

(6) Phosphate ester 3: Condensed phosphate ester (n = 1.01) represented by the formula (5), trade name: FP-
500, Asahi Denka Kogyo Co., Ltd. product.

[0041]

Embedded image

(7) Phosphate ester 4: Condensed phosphate ester (n = 1.1) represented by the formula (6), trade name: CR-7
47, Daihachi Chemical Industry Co., Ltd. products.

[0043]

Embedded image

(8) Polytetrafluoroethylene (hereinafter referred to as "PTFE"): Trade name: Polyflon F-
201L, Daikin Corporation product.

(9) Impact modifier 1: Multilayer polymer having an alkyl acrylate core / methyl acrylate shell, trade name: EXL2315, a product of Kureha Chemical Industry Co., Ltd. (10) Impact modifier 2: Multilayer polymer having butadiene core / methyl acrylate shell, trade name: EXL2
603, products of Kureha Chemical Industry Co., Ltd. (11) UV absorber: 2- (2′-hydroxy-5 ′)
-T-octylphenyl) benzotriazole. (12) Titanium oxide: surface-treated titanium oxide, trade name: P
C-3, a product of Ishihara Sangyo Co., Ltd. This titanium oxide is produced by a chlorine method, has an average particle diameter of 0.28 μm, is surface-treated with an inorganic surface treating agent, alumina hydrate and silicic acid hydrate, and then is treated with an organic surface treating agent, organohydrogensiloxane. It is a rutile-type titanium oxide whose surface has been treated.

The physical properties of the test pieces were evaluated as described below. (A) Flammability: A vertical combustion test was performed using a 0.8 mm thick UL standard test piece, and evaluated in accordance with UL standard (UL-94). (B) Hue (YI) and reflectance: 90 mm × 50 mm ×
A 3 mm plate is molded and the hue is measured using a multi-source spectrophotometer M
It is measured with SC-5N (trade name, manufactured by Suga Test Instruments Co., Ltd.), and the reflectance is measured by a spectrophotometer U-3400 (trade name, manufactured by Co., Ltd.)
The light reflectance at a wavelength of 550 nm was measured by Hitachi, Ltd.). (C) Mold depositability: 500 shots were continuously molded under the molding conditions of the combustion test piece described in each experimental example, and after the completion, the presence or absence of a deposit on the mold was evaluated.
：: There is little deposit on the mold. ×: There are many deposits on the mold.

Synthesis Example 1 (Synthesis of Nitrogen-containing Phosphate 1) In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, 53.75 g of diphenyl phosphorochloridate,
8.61 g of piperidine and 200 ml of dichloroethane were charged, and while cooling so as to keep the internal temperature at 50 ° C. or lower, 22.26 g of triethylamine was added dropwise over 10 minutes, and further kept at a temperature of 85 ° C. for 1 hour. After the reaction product was concentrated under reduced pressure, 200 ml of water was poured thereinto, stirred for 30 minutes, and then the precipitate was collected by filtration. The precipitate was further washed with 200 ml of water, and the taken out white powdery solid was dried under reduced pressure. The melting point of this product is 184 ° C., and from NMR and IR results, it is N, N′-bis (diphenoxyphosphyl) piperazine [50.16 g (91.1% yield)] (the above formula (2)). Structure) was confirmed.

Synthesis Example 2 (Synthesis of nitrogen-containing phosphoric ester 2) Diphenyl phosphorochloridate was changed to di-P-cresyl phosphorochloridate, and the same reaction and purification as in Synthesis Example 1 were performed to obtain a white powdery solid. I got Melting point of this product is 125
~ 126 ° C, and from the results of NMR and IR, N, N '
-Bis [bis (4-methylphenoxy) phosphyl] piperazine (structure of the above formula (3)) was confirmed.

Example 1 11.8 parts by weight of a nitrogen-containing phosphoric ester 1, 5.9 parts by weight of an impact modifier 1, 0.35 parts by weight of PTFE and 100 parts by weight of an aromatic polycarbonate resin 0.35 parts by weight of an ultraviolet absorber was blended, mixed for 20 minutes by a tumbler, pelletized at a cylinder temperature of 270 ° C. by a 30 mm twin screw extruder, and then pelletized at a cylinder temperature of 280 ° C. by an injection molding machine. A combustion test piece having a thickness of 8 mm was molded and evaluated according to the UL test method. Further, continuous molding was performed at a cylinder temperature of 280 ° C. for 500 shots, and the adhered mold was visually determined after the molding. Further, a plate was molded at 280 ° C., and weather resistance was evaluated on the plate by sunshine fade (200 hours), and the hue before and after the evaluation was evaluated. The test pieces used for the evaluation of Izod impact strength and load deflection temperature
It was molded at 0 ° C. and used. The evaluation results are shown in Table 1 below.

Comparative Example 1 Pellets were formed in the same manner as in Example 1 except that the impact modifier 1 was not used, and molding and evaluation were performed in the same manner. Table 1 shows the results. [Comparative Example 2] In Example 1, the nitrogen-containing phosphoric acid ester 1
Was changed to nitrogen-containing phosphoric acid ester 2 and pelletized in the same manner as in Example 1, and molded and evaluated in the same manner.
The results are shown in Table 1 below. [Comparative Example 3] In Example 1, the nitrogen-containing phosphoric acid ester 1
Was changed to phosphoric acid ester 2 and pelletized in the same manner as in Example 1, and molded and evaluated in the same manner. The results are shown in Table 1 below. [Comparative Example 4] In Example 1, the nitrogen-containing phosphoric acid ester 1
Was pelletized in the same manner as in Example 1 except that the phosphoric acid ester was changed to phosphoric acid ester 3, and molding and evaluation were performed in the same manner. The results are shown in Table 1 below.

Comparative Example 5 A pellet was formed in the same manner as in Example 1 except that the nitrogen-containing phosphoric acid ester 1 was changed to the phosphoric acid ester-4, and molding and evaluation were performed in the same manner. The results are shown in Table 1 below. [Example 2] To the composition of Example 1, 16.2 parts by weight of titanium oxide was further added, pelletized in the same manner as in Example 1, and molded and evaluated in the same manner. In the evaluation, the reflectance of the plate before and after the weather resistance evaluation was also measured.
The results are shown in Table 2 below. Example 3 A pellet was formed in the same manner as in Example 2 except that the impact modifier 1 was changed to the impact modifier 2, and molding and evaluation were performed in the same manner. The results are shown in Table 2 below.

Comparative Example 6 A pellet was formed in the same manner as in Example 2 except that the nitrogen-containing phosphoric acid ester 1 was changed to the phosphoric acid ester 1, and molding and evaluation were performed in the same manner. The results are shown in Table 2 below. [Comparative Example 7] In Example 2, the nitrogen-containing phosphoric acid ester 1
Was changed to phosphate ester 2 and pelletized in the same manner as in Example 2, and molded and evaluated in the same manner. The results are shown in Table 2 below.

Comparative Example 8 A pellet was formed in the same manner as in Example 2, except that the nitrogen-containing phosphoric acid ester 1 was changed to the phosphoric acid ester 3, and molding and evaluation were performed in the same manner. The results are shown in Table 2 below. [Comparative Example 9] In Example 2, the nitrogen-containing phosphoric acid ester 1
Was pelletized in the same manner as in Example 2 except that the phosphoric acid ester was changed to phosphoric acid ester 4, and molded and evaluated in the same manner. The results are shown in Table 2 below.

[0054]

[Table 1]

[0055]

[Table 2]

A comparison between Comparative Example 1 and Example 1 shows that in Example 1, the Izod impact strength was increased by incorporating the impact resistance improver, and the flammability (0.8 mm) was V-0. . Comparison between Comparative Example 2 and Example 1 shows that the nitrogen-containing phosphate having a substituent on the phenyl group of Ph is used, and the weather resistance of the nitrogen-containing phosphate is not good. It seems that it has risen.
In Comparative Example 3, phosphate ester 2 having a resorcinol structure and containing no nitrogen in the structure was used, and it is considered that YI after the evaluation of weather resistance was increased. In Comparative Example 4,
It has a resorcinol structure and does not contain nitrogen in its structure.
Since the phosphoric ester 3 having a substituent on the phenyl group is used, it is considered that the YI after the evaluation of the weather resistance is increased. In Comparative Example 5, since the phosphoric ester 4 having a bisphenol residue structure and a cresyl group was used, the YI after the evaluation of weather resistance increased.

Example 2 was a composition in which titanium oxide was added to Example 1, and the YI after the evaluation of the weather resistance was further suppressed. Further, in Example 3, the evaluation was performed by changing the impact modifier 1 to the impact modifier 2, but similarly, the YI after the weather resistance evaluation was suppressed to a low level. On the other hand, in Comparative Example 6, a structure containing no nitrogen and having a monophosphate structure was used, and the YI after the evaluation of the weather resistance was suppressed to a low level. There are many deposits, which is a practical problem. Further, Comparative Examples 7, 8 and 9 are compositions obtained by adding titanium oxide to the formulations of Comparative Examples 3, 4 and 5.
For the same reason as described above, YI after the evaluation of weather resistance increased.

[0058]

Industrial Applicability The flame-retardant polycarbonate resin composition of the present invention has excellent impact strength, flame retardancy, heat resistance and weather resistance, and furthermore, corrodes molds and screws during molding. It has excellent moldability without moldability problems and mold deposits, so it can be used not only in the fields of electric / electronics, automobiles and general industry but also in fields where weather resistance is required. No secondary processing such as painting is required, and the product can be made unpainted, which is of great industrial value.

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Claims (5)

[Claims] (A) Aromatic polycarbonate resin 10
0 parts by weight, (b) 0.5 to 40 parts by weight of a nitrogen-containing phosphoric ester represented by the following general formula (1), (c) 0.01 to 5 parts by weight of polyfluoroethylene, (d) improvement of impact resistance 0.5 to 30 parts by weight of an agent, and (e) an ultraviolet absorber 0.01
A flame-retardant polycarbonate resin composition comprising up to 2 parts by weight. Embedded image (Wherein, R ¹ comprises an alkylene group having 1 to 6 carbon atoms, a halogen-substituted alkylene group, an arylene group, or a halogen-substituted arylene group; R ² and R ³ represent hydrogen, an alkyl group having 1 to 6 carbon atoms, aryl R ² and R ³ may be linked by an alkylene group, and Ph is an aryl group or a halogen-substituted aryl group, and the aryl group does not include those having an alkyl group on an aromatic ring. ) 2. The flame-retardant polycarbonate resin composition according to claim 1, wherein (d) the impact modifier is an acrylic rubber. 3. The flame-retardant polycarbonate resin composition according to claim 2, wherein the acrylic rubber is a multilayer structure polymer containing an alkyl (meth) acrylate polymer. 4. The flame-retardant polycarbonate resin composition according to claim 1, wherein (a) the aromatic polycarbonate resin has a viscosity average molecular weight of 16,000 to 30,000. . 5. (a) Aromatic polycarbonate resin 10
The flame-retardant polycarbonate resin according to any one of claims 1 to 4, wherein 0.1 to 20 parts by weight of (f) surface-treated titanium oxide is further blended with respect to 0 parts by weight. Composition.