JP5258131B2 - Polycarbonate-based colored flame-retardant resin composition and process for producing the same - Google Patents

Description

  The present invention relates to a polycarbonate-based colored flame-retardant resin composition having excellent flame retardancy in a thin molded article, dispersibility of a colorant, low mold contamination, melt fluidity, and impact resistance, and a method for producing the same. .

  A composition obtained by blending an acrylonitrile / butadiene / styrene resin (ABS) and an organophosphorus compound flame retardant into a polycarbonate resin (PC) (hereinafter referred to as “PC / ABS / phosphorus flame retardant composition”) is non-bromine. -Non-chlorine flame retardant resin material with excellent properties such as melt fluidity, rigidity, impact resistance, heat resistance, and light discoloration resistance, so it can be used for computer monitors, notebook computers, printers. Widely used as housing materials for word processors, copiers, etc.

  In recent years, to reduce the weight and thickness of equipment, the same material meets the good flowability of molten resin that enables thin molding, and flame retardancy levels of V-0 and 5V in UL94 for thin molded products. High flame retardancy is required at the same time. In the PC / ABS / phosphorous flame retardant composition, the melt fluidity can be improved by increasing the blending amount of the ABS resin in the composition, but the flame retardancy is lowered. Furthermore, as the molding thickness of the same material becomes thinner, flame drip tends to occur more easily in the UL94 vertical combustion test, and it becomes more difficult to maintain high flame retardance as the molded body becomes thinner. That is, it has not been easy to improve the melt fluidity and the flame retardancy at the same time.

  Recently, in order to reduce mold contamination during molding, oligomeric phosphorus flame retardants with low volatile components have attracted attention as flame retardants for PC / ABS / phosphorus flame retardant compositions. Bisphenol A-di-phosphate (BDP) type oligomer phosphorus compound flame retardant having excellent decomposability can be improved in the heat-and-moisture resistance of PC / ABS / phosphorus flame retardant composition at the same time, so that it is often used industrially. It is becoming. However, the use of oligomeric phosphorus flame retardants can improve low mold fouling, but it is thinner than the monophosphorus compound flame retardants typified by triphenyl phosphate (TPP). There was a problem that the flame retardant performance of the body deteriorated.

Furthermore, the PC / ABS / phosphorous flame retardant composition is generally used as a molding material after being melt-kneaded using a colorant (mainly a dye / pigment) and colored to a desired color.
In coloring PC / ABS / phosphorus flame retardant compositions, PC / ABS / phosphorus flame retardant compositions containing no colorant (hereinafter referred to as “uncolored PC / ABS”) are used in advance to meet various color needs. / Phosphorus flame retardant composition "), and then blending the colorant into the" uncolored PC / ABS / phosphorous flame retardant composition "pellets and performing melt-kneading. Thus, a method of coloring is widely used.

In this method, for the purpose of improving the dispersibility of the colorant and further eliminating the variation in color tone, a dispersant for the colorant and a spreader for favorably spreading the colorant on the surface of the resin pellet are used. There is a case. However, the use of these dispersants and spreading agents often causes a problem that the flame retardancy of the composition after coloring is lowered. However, when a dispersant or a spreading agent is not used, poor colorant dispersion and color tone fluctuations may occur. Coloring of a PC / ABS / phosphorous flame retardant composition is highly flame retardant and preferable coloration. It has not always been easy to achieve both agent dispersion and low color tone fluctuation.
That is, colored PC as a molding material having high flame retardancy in a thin molded article, good dispersibility of colorant, low mold contamination, and excellent melt fluidity and impact resistance. / ABS / Phosphorus flame retardant composition and the present situation is that no effective solution has been found in spite of strong demand for industrially easy production of the material. .

In PC / ABS / phosphorous flame retardant compositions, various “lubricants” are usually included. As used herein, the term “lubricant” means that the resin processing slipperiness, the dispersibility of dyes and pigments as a resin colorant, and the mold releasability from the mold are improved. These compounds are effective and include compounds generally referred to as “lubricants”, “processing aids”, “dispersing agents”, “release agents”, “spreading agents”, etc., including aliphatic hydrocarbons, polyolefins A compound selected from a compound group such as a wax, a higher carboxylic acid, a higher carboxylic acid metal salt, a fatty acid amide, a fatty acid ester, and a higher alcohol.
Further, as a general concept, silicone oil is included in the category of “lubricant”, but in the present specification, silicone oil is excluded from “lubricant”.
The lubricant may be already contained in the resin raw material of the composition, or may be blended in processing such as resin compounding and coloring.
For example, the raw material PC resin of the PC / ABS / phosphorous flame retardant composition may contain a lubricant component as a mold release agent or a processing aid. Similarly, the raw material ABS resin may contain a fatty acid derived from an emulsifier or Fatty acid metal salts, processing aids, release agents, and the like may be included.

  PC / ABS / Phosphorus flame retardant compositions are generally formed into various molded products by injection molding as with other thermoplastic resins. In order to improve, a release agent may be mix | blended with a PC / ABS / phosphorus flame retardant composition. For example, in JP-A-8-48844, 100 parts by weight of a resin composition comprising (A) polycarbonate, (B) styrene resin, (C) resorcin polyphosphate compound, and (D) polytetrafluoroethylene. (E) 0.1 to 2 parts by weight of a saturated fatty acid ester wax having an average molecular weight of 1,000 to 50,000 and (F) 0.01 to 2 parts by weight of a polyethylene wax having an average molecular weight of 1,000 to 3,000. JP-A-2000-63649 discloses a flame retardant resin composition comprising (A) a polycarbonate, (B) a styrene resin, and (C) an esterified product of pentaerythritol and a saturated aliphatic carboxylic acid. A flame retardant resin composition in which a halogen-free phosphate ester is further added to the composition is disclosed.

Further, in the process of coloring the PC / ABS / phosphorous flame retardant composition with a colorant (mainly dye / pigment), a colorant dispersant is used for the purpose of improving the dispersibility of the colorant in the resin, or the resin. In some cases, a spreading agent is used in order to make the colorant spread well on the pellet surface and improve the uniformity of the color tone.
Thus, in the PC / ABS / phosphorus flame retardant composition used as a molding material, in particular, the colored PC / ABS / phosphorus flame retardant composition, the aforementioned “lubricant” component is generally contained. . The above-mentioned lubricant component contained in the PC / ABS / phosphorous flame retardant composition is generally contained in the resin composition in the order of several thousand to several tens of thousands ppm by weight as the total amount. However, since these lubricant components are trace components, the influence of these lubricant components on the flame retardancy of the PC / ABS / phosphorous flame retardant composition has not been strictly studied so far.

Problems to be solved by the invention

  It is an object of the present invention to color as a molding material having high flame retardancy in a thin molded article, good dispersibility of colorant, low mold contamination, and excellent melt fluidity and impact resistance. PC / ABS / phosphorus flame retardant composition and a method for industrially producing the same material.

Means for solving the problem

As a result of earnestly examining the improvement in flame retardancy of a PC / ABS / phosphorous flame retardant composition in a thin molded article, the present inventors have surprisingly found that the lubricant component contained in a trace amount in the resin composition is a resin. It has been found that it has a great influence on the flame retardancy of the composition.
At the same time, when coloring the uncolored PC / ABS / phosphorous flame retardant composition pellets into a desired color, silicone oil is used as a coloring agent for the uncolored PC / ABS / phosphorous flame retardant composition pellets. By using the extruder as a dispersant and / or spreading agent, performing melt-kneading using an extruder, and controlling the total amount of the lubricant component contained in the colored PC / ABS / phosphorous flame retardant composition, The thin molded article has excellent flame retardancy and good dispersibility of the colorant, and is further colored with excellent melt fluidity, impact resistance, and low mold contamination. The present inventors have found that a PC / ABS / phosphorous flame retardant composition can be obtained and have completed the present invention.

That is, the present invention
[1] At least 1 with respect to 50 to 95 parts by weight of the aromatic polycarbonate resin (A), 50 to 5 parts by weight of the rubber-modified styrenic resin (B), and 100 parts by weight in total of the components (A) and (B). Organic organophosphorus compound oligomer (C) 5-30 parts by weight, fluoropolymer (D) 0.05-1 part by weight, component (A), (B), (C) and component (D) total 100 parts by weight Is a polycarbonate-based colored flame retardant resin composition containing 0.001 to 10 parts by weight of silicone oil (E) and 0.0001 to 10 parts by weight of a colorant (F), an aliphatic hydrocarbon, polyolefin wax, higher carboxylic acids, higher carboxylic acid metal salts, higher fatty acid amides, total amount 171～ 3,000 weight pp higher fatty acid esters lubricants and a compound selected from higher alcohols, (G) , And the polycarbonate-based, characterized in that it does not contain an inorganic filler colored flame retardant resin composition,
[2] The polycarbonate-based colored flame retardant resin composition according to [1], wherein at least one organophosphorus compound oligomer (C) is selected from the group of compounds represented by the following formula (1): ,

[3] At least 1 with respect to 50 to 95 parts by weight of the aromatic polycarbonate resin (A), 50 to 5 parts by weight of the rubber-modified styrenic resin (B), and 100 parts by weight in total of the components (A) and (B). With respect to 100 parts by weight of uncolored polycarbonate flame-retardant resin composition pellets comprising 5 to 30 parts by weight of the organic phosphorus compound oligomer (C) and 0.05 to 1 part by weight of the fluoropolymer (D), silicone oil ( E) A method of obtaining a polycarbonate-based colored flame-retardant resin composition by mixing 0.001 to 3 parts by weight and 0.0001 to 10 parts by weight of a colorant (F) and melt-kneading using an extruder. And selected from aliphatic hydrocarbons, polyolefin waxes, higher carboxylic acids, higher carboxylic acid metal salts, higher fatty acid amides, higher fatty acid esters, and higher alcohols. The total amount of lubricant (G) a compound is 171 to 3,000 weight ppm, a method of manufacturing a polycarbonate-based coloring flame retardant resin composition characterized by containing no inorganic filler,
[4] The polycarbonate-based colored flame retardant resin composition according to [3], wherein at least one organophosphorus compound oligomer (C) is selected from the group of compounds represented by the following formula (1): Manufacturing method,

[ 5 ] The method for producing a polycarbonate-based colored flame-retardant resin composition according to [ 3 ] or [ 4 ], wherein the extruder is a twin-screw extruder,
[ 6 ] A molded product obtained by molding the polycarbonate-based colored flame retardant resin composition according to any one of [1] or [ 2 ],
[7] moldings, the thick 2mm or less is portion is characterized in that at least 30 wt% of the total shaped article [6], wherein the molded article,
It is.

The present invention will be specifically described below.
The aromatic polycarbonate resin (A) preferably used as the component (A) of the composition of the present invention is a resin having a main chain composed of a repeating unit represented by the following formula (2).
(In the formula, Ar is a divalent aromatic residue, and examples thereof include phenylene, naphthylene, biphenylene, pyridylene, and those represented by the following formula (3).)

(In the formula, Ar ¹ and Ar ² are each an arylene group. For example, they represent groups such as phenylene, naphthylene, biphenylene, pyridylene, and Y represents an alkylene group or a substituted alkylene group represented by the following formula (4)). .)

Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms. , An aralkyl group having 7 to 31 carbon atoms, optionally substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms, k is an integer of 3 to 11, and R ⁵ and R ⁶ are Each X is independently selected and is independently a hydrogen atom, or a lower alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 30 carbon atoms, optionally a halogen atom, an alkoxy group having 1 to 10 carbon atoms And may be substituted with a group, X represents a carbon atom.)

Moreover, you may contain the bivalent aromatic residue shown by following formula (5) as a copolymer component.
(In the formula, Ar ¹ and Ar ² are the same as those in formula (3). Z is a simple bond, or —O—, —CO—, —S—, —SO 2 —, —CO 2 —, —CON (R ¹ ). -(R ¹ is the same as in formula (4)).

Examples of these divalent aromatic residues include the aromatic residues shown below.

(In the formula, R ⁷ and R ⁸ are each independently hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 carbon atoms. M and n are integers of 1 to 4, and when m is 2 to 4, each R ⁷ may be the same or different, and n is 2 to 4. In this case, each R ⁸ may be the same or different.)

Especially, what is represented by following formula (6) is a preferable example.
In particular, a polycarbonate containing 85 mol% or more (based on all monomer units in the polycarbonate) of a repeating unit in which Ar is represented by the above formula (6) is particularly preferable.
The polycarbonate that can be used in the present invention may have a branched structure having a trivalent or higher aromatic residue as a branch point.
The molecular structure of the polymer terminal is not particularly limited, but one or more terminal groups selected from a phenol group, an aryl carbonate group, and an alkyl carbonate group can be bonded.

The aryl carbonate end group is represented by the following formula (7).
(In the formula, Ar ³ is a monovalent aromatic residue, and the aromatic ring may be substituted.)

Specific examples of the aryl carbonate terminal group include those represented by the following formula.

The alkyl carbonate end group is represented by the following formula (8).
(In the formula, R ⁹ represents a linear or branched alkyl group having 1 to 20 carbon atoms.)

Specific examples of the alkyl carbonate terminal group include those represented by the following formula.
Of these, a phenol group, a phenyl carbonate group, a pt-butylphenyl carbonate group, p-cumylphenyl carbonate, and the like are preferably used.

In the present application, the ratio of the phenol group terminal to the other terminal is not particularly limited, but from the viewpoint of obtaining excellent mechanical strength and heat stability, the ratio of the phenol group terminal is 20% or more of the total number of terminal groups. It is preferable that it is in the range of 20 to 80%. When the ratio of phenol group ends exceeds 80% of the total number of end groups, the thermal stability during melting tends to be slightly reduced.
The method for measuring the terminal amount of the phenol group is generally a method using NMR (NMR method), a method using titanium (titanium method), or a method using UV or IR (UV method or IR). Can be obtained by these methods.

The weight average molecular weight (Mw) of the polycarbonate resin (A) used in the present invention is generally preferably in the range of 5,000 to 50,000, more preferably 10,000 to 40,000, and still more preferably. Is 15,000 to 30,000, particularly preferably 18,000 to 25,000. If it is less than 5,000, impact resistance tends to be insufficient, and if it exceeds 50,000, melt fluidity tends to be insufficient.
In the present invention, the weight average molecular weight (Mw) of the polycarbonate is measured using gel permeation chromatography (GPC), and the measurement conditions are as follows. That is, it is obtained by using a converted molecular weight calibration curve according to the following formula from the composition curve of standard monodisperse polystyrene using tetrahydrofuran as a solvent and polystyrene gel.
M _PC = 0.3591M _PS ^1.0388
(In the formula, _MPC is the weight average molecular weight of polycarbonate, and _MPS is the weight average molecular weight of polystyrene.)

  What was manufactured by the well-known method can be used for the aromatic polycarbonate resin (A) in the composition of this invention. Specifically, for example, a known method of reacting an aromatic dihydroxy compound and a carbonate precursor, for example, reacting an aromatic dihydroxy compound and a carbonate precursor (for example, phosgene) in the presence of an aqueous sodium hydroxide solution and a methylene chloride solvent. The crystallized carbonate prepolymer obtained by the interfacial polymerization method (for example, phosgene method), the transesterification method (melting method) in which an aromatic dihydroxy compound and a carbonic acid diester (for example diphenyl carbonate) are reacted, the phosgene method or the melting method is solidified. Phase polymerization method (Japanese Patent Laid-Open No. 1-158033 (corresponding to US Pat. No. 4,948,871)), Japanese Patent Laid-Open No. 1-271426, Japanese Patent Laid-Open No. 3-68627 (US Pat. No. 5,204, And the like manufactured by a method such as No. 377)].

As a preferable polycarbonate resin, a polycarbonate resin containing substantially no chlorine atom produced by a transesterification method from a dihydric phenol (aromatic dihydroxy compound) and a carbonic acid diester can be mentioned.
In the present invention, two or more different polycarbonates having different structures and molecular weights can be combined and used as the component (A).
The amount of the component (A) in the composition of the present invention is 50 to 95 parts by weight, preferably 60 to 90 parts by weight, and more preferably 70 to 90 parts by weight with respect to 100 parts by weight as the total of the component (A) and the component (B). 85 parts by weight. If the component (A) is less than 50 parts by weight, the heat resistance and flame retardancy of the thin molded article will be insufficient, while if it exceeds 95 parts by weight, the melt fluidity will be insufficient.

The component (B) used in the present invention is a rubber-modified styrene resin. Here, the rubber-modified styrenic resin refers to all rubber-modified styrenic resins containing a rubbery polymer and one or more vinyl compounds as components.
As the rubbery polymer of the rubber-modified styrene resin, any rubber polymer having a glass transition temperature of 0 ° C. or lower can be used. Specifically, polybutadiene, styrene / butadiene copolymer rubber, butadiene / butyl acrylate copolymer rubber, diene rubber such as acrylonitrile / butadiene copolymer rubber, acrylic rubber such as polybutyl acrylate, silicon / acrylic composite rubber , Block copolymers such as polyisoprene, polychloroprene, ethylene / propylene rubber, ethylene / propylene / diene terpolymer rubber, styrene / butadiene block copolymer rubber, styrene / isoprene block copolymer rubber, and hydrogenation thereof Things can be used. Among these polymers, polybutadiene, styrene / butadiene copolymer rubber, acrylonitrile / butadiene copolymer rubber, and polybutyl acrylate are preferable.

The ratio of the rubbery polymer in the rubber-modified styrenic resin is used in the range of 1 to 95% by weight, and is determined according to the required mechanical strength, rigidity, and moldability. Preferably, it is 5-45 weight%, More preferably, it is 10-40 weight%.
Examples of vinyl compounds used in rubber-modified styrene resins include aromatic vinyl compounds such as styrene, α-methylstyrene, and paramethylstyrene, and alkyl (meth) acrylates such as methyl methacrylate, methyl acrylate, butyl acrylate, and ethyl acrylate. , (Meth) acrylic acids such as acrylic acid and methacrylic acid, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, α, β-unsaturated carboxylic acids such as maleic anhydride, N-phenylmaleimide, N-methylmaleimide , Maleimide monomers such as N-cyclohexylmaleimide, glycidyl group-containing monomers such as glycidyl methacrylate, etc., preferably aromatic vinyl compounds, alkyl (meth) acrylates, vinyl cyanide monomers , Malemi A system monomer, more preferably, styrene, acrylonitrile, N- phenylmaleimide, butyl acrylate. These vinyl compounds can be used alone or in combination of two or more.

Preferably, it is a combination of an aromatic vinyl compound and a vinyl compound other than aromatic. In this case, the aromatic vinyl compound and the non-aromatic vinyl compound are used in an arbitrary ratio, but the preferred ratio of the non-aromatic vinyl compound is 5 to 80% by weight based on the total amount of the vinyl compound alone. It is a range.
Examples of the rubber-modified styrene resin include ABS resin (acrylonitrile / butadiene / styrene resin), AAS resin (acrylonitrile / butyl acrylate / styrene resin), HIPS (high impact polystyrene resin), and the like.
The method for producing the rubber-modified styrene resin is not particularly limited, and examples thereof include generally known production methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.
Among them, rubber-modified styrene resins produced by bulk polymerization or solution polymerization can obtain rubber-modified styrene resins without using an emulsifier, so that fatty acids or fatty acid metal salts derived from emulsifiers are rubber-modified. Since it is not substantially contained in the styrenic resin, it can be particularly suitably used as the component (B).

  Furthermore, in the present invention, it is also effective to use two or more different rubber-modified styrenic resins having different structures and molecular weights as a component (B). For example, by using a combination of ABS resin and MBS resin (methyl methacrylate / butadiene / styrene resin) as component (B), excellent melt fluidity and impact resistance can be improved at the same time. Specific examples of such MBS include “Metablene C-223A” and “Metablene C-323A” manufactured by Mitsubishi Rayon Co., Ltd., and “Kane Ace M-” manufactured by Kaneka Chemical Co., Ltd. 511 ”and“ Kane Ace B-564 ”,“ M-51 ”manufactured by Taiwan Plastic Co., Ltd., and the like.

The amount of component (B) in the composition of the present invention is 50 to 5 parts by weight, preferably 40 to 10 parts by weight, more preferably 30 to 100 parts by weight with respect to the total of 100 parts by weight of component (A) and component (B). 15 parts by weight. If the component (B) exceeds 50 parts by weight, the heat resistance and flame retardancy of the thin molded article will be insufficient, while if it is less than 5 parts by weight, the melt fluidity will be insufficient.
Component (C) used in the present invention is at least one organic phosphorus compound, and is an organic phosphorus compound oligomer that is a compound having two or more phosphorus atoms in its structure.

Particularly preferred examples of the organophosphorus compound oligomer used in the present invention include those selected from the group of compounds represented by the following formula (1).

The substituents R ^a , R ^b , R ^c , and R ^d in the above formula (1) each independently represent an aryl group having 6 to 12 carbon atoms, and one or more hydrogen atoms may be substituted. May be. When one or more hydrogen atoms are substituted, examples of the substituent include alkyl groups having 1 to 30 carbon atoms, alkoxy groups, alkylthio groups, halogens, aryl groups, aryloxy groups, arylthio groups, and halogenated aryl groups. And a group in which these substituents are combined (for example, an arylalkoxyalkyl group) or a group in which these substituents are combined by an oxygen atom, a sulfur atom, a nitrogen atom, or the like (for example, an arylsulfonylaryl group) Etc.) may be used as a substituent.

Particularly preferred aryl groups as the substituents R ^a , R ^b , R ^c and R ^d are a phenyl group, a cresyl group, a xylyl group, a propylphenyl group, and a butylphenyl group. When the substituents R ^a , R ^b , R ^c , and R ^d in the compound of the above formula (1) are alkyl groups or cycloalkyl groups, the thermal stability generally decreases, and decomposition tends to occur during melt-kneading.
X in the above formula (1) representing a group of compounds as an example of an organic phosphorus compound is a diphenyldimethylmethane group as described above. As the oligomeric phosphate ester, there are those in which X is a resorcinol group or a hydroquinone group. Compared with these, from the group of compounds represented by the above formula (1) (X is a diphenyldimethylmethane group) When using what is chosen as an organic phosphorus compound, the hydrolysis resistance and thermal stability of the organic phosphorus compound are improved, which is preferable.

The organophosphorus compound oligomer represented by the formula (1) is usually often used as a mixture of a plurality of different organophosphorus compound oligomers having different values of n in the formula (1) (n is a natural number). Under the present circumstances, it is preferable that the weight average condensation degree (N) of a several different organophosphorus compound oligomer is less than 1-1.2. N calculates | requires the weight fraction (An) of each component which has different n by a gel permeation chromatography or a liquid chromatography, and is calculated by a following formula.
N = Σ (n · An) / Σ (An)
Here, in order to obtain An, a UV detector or an RI detector is usually used as a detector. However, in the calculation of N, a structure having n of 0 in the above formula (1) is used in combination or included (that is, an organic phosphorus compound having only one phosphorus atom in one molecule is used or included) In the case), compounds with n = 0 are excluded from the calculation of N. The weight average condensation degree N is usually from 1 to 5, preferably from 1 to 2, more preferably from 1 to 1.5, and particularly preferably from 1 to less than 1.2. The smaller N, the better the compatibility with the resin, the better the melt fluidity, and the higher the flame retardancy. In particular, the compound of N = 1 is particularly excellent in the balance between flame retardancy and melt fluidity in the resin composition. When N of the compound of the formula (1) as the organophosphorus compound is 5 or more, the viscosity of the compound tends to increase, and the melt fluidity tends to decrease particularly in a high shear rate region. Tend to decrease.

Furthermore, the organic phosphorus compound used in the present invention preferably has an acid value of 0.1 mgKOH / g or less, more preferably 0.08 mgKOH / g or less, still more preferably 0.05 mgKOH / g or less, Especially preferably, it is 0.01 mgKOH / g or less. By using an organophosphorus compound having a low acid value, a polycarbonate flame retardant resin composition that is superior in heat and moisture resistance can be obtained.
The organophosphorus compounds represented by the general formula (1) are disclosed in US Pat. No. 2,520,090, Japanese Examined Patent Publication No. 62-25706, Japanese Unexamined Patent Publication No. 63-227632, and the like. By reacting phosphorus oxychloride with bisphenol A and monohydric phenols in the presence of a Lewis acid catalyst such as magnesium chloride or aluminum chloride, and then washing and purifying the crude organophosphorus compound and drying. The organophosphorus compound used in the present invention contains magnesium, aluminum mainly derived from the catalyst, and metal ions such as alkali and alkaline earth for cleaning and purification. The total amount of metals such as sodium, potassium and calcium that may be introduced when using an aqueous solution is preferably 3 ppm or less, more preferably 20ppm or less, more preferably 10ppm or less, particularly preferably 5ppm or less, it is desirable for obtaining excellent polycarbonate flame retardant resin composition by wet heat resistance is.

Further, the chlorine content contained in the organophosphorus compound is preferably 20 ppm or less, more preferably 10 ppm or less, still more preferably 5 ppm or less, and particularly preferably 1 ppm or less. It is desirable for obtaining a resin composition.
The amount of the component (C) in the composition of the present invention is 5 to 30 parts by weight, preferably 8 to 20 parts by weight, more preferably 10 to 10 parts by weight with respect to the total of 100 parts by weight of the component (A) and the component (B). 17 parts by weight. If the component (C) is less than 5 parts by weight, the flame retardancy of the thin molded article is insufficient, while if it exceeds 30 parts by weight, the impact resistance of the resin composition is insufficient.

Component (D) used in the present invention is a fluoropolymer and is used for the purpose of preventing dripping of combustion products. In the present invention, a fluoropolymer having a fibril-forming ability can be used, such as a fine powder-like fluoropolymer, an aqueous dispersion of the fluoropolymer, and a powdery mixture with a second resin such as AS or PMMA. Any form of fluoropolymer can be used.
In the present invention, an aqueous dispersion of a fluoropolymer can be suitably used as the component (D). The aqueous dispersion of the fluoropolymer is a tetrafluoroethylene such as polytetrafluoroethylene or a tetrafluoroethylene / propylene copolymer. An ethylene polymer, a perfluoroalkane polymer other than polytetrafluoroethylene, preferably a tetrafluoroethylene polymer, particularly preferably polytetrafluoroethylene, is described in, for example, “Fluorine Resin Handbook” (published by Nikkan Kogyo Shimbun, 1990). These are produced by suspension polymerization or emulsion polymerization, and further used as an aqueous dispersion.

  That is, a milky white aqueous dispersion stabilized by a surfactant after concentration of a dispersion of fluoropolymer fine particles obtained by suspension polymerization or emulsion polymerization to a concentration of 40 to 70 wt% is shown. The concentration of the fluoropolymer in the aqueous dispersion of the fluoropolymer can be diluted with water as long as the dispersion state is stable, but is preferably 5 to 70 wt%, more preferably 20 to 65 wt%, particularly preferably. 30 to 60 wt%. The average primary particle diameter of the fluoropolymer in the aqueous dispersion is preferably 0.01 to 0.60 μm, more preferably 0.10 to 0.40 μm, and particularly preferably 0.18 to 0.30 μm. .

  Further, as the surfactant for stabilizing the aqueous dispersion of the fluoropolymer, nonionic surfactants such as ethoxylated alkylphenols and ethoxylated higher alcohols are preferably used, and the compounding amount is usually 1 to 15 wt%. It is preferably 2 to 10 wt%, more preferably 3 to 7 wt%. Furthermore, as the aqueous dispersion of the fluoropolymer, those whose pH value is usually adjusted to 9 to 10 are preferably used. When the concentration of the fluoropolymer is 60 wt%, the liquid specific gravity of the aqueous dispersion is about 1.5, and the viscosity (25 ° C.) is in the range of 15 to 30 cp (centipoise). As an aqueous dispersion of a fluoropolymer that can be preferably used in the present invention, “Teflon 30J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Polyflon D-1”, “Polyflon D-2”, “Polyflon D” manufactured by Daikin Industries, Ltd. -2C "and" Polyflon D-2CE ".

  Furthermore, in the present invention, as the component (D), a fluoropolymer made into a powdery mixture with a second resin such as AS or PMMA can also be suitably used. The technology relating to the fluoropolymer in the form of a powder mixture with these second resins is disclosed in JP-A-9-95583, JP-A-11-49912, JP-A-2000-143966, and JP-A-2000-297189. Etc. are disclosed. Examples of fluoropolymers in a powdery mixture with these second resins that can be preferably used in the present invention include “Blendex 449” manufactured by GE Specialty Chemicals and “Metablene A-3000” manufactured by Mitsubishi Rayon Co., Ltd. Can do.

  The compounding amount of the component (D) in the present invention is 0.05 to 1 part by weight, preferably 0.1 to 0.8 part by weight based on 100 parts by weight of the total of the component (A) and the component (B). More preferably, it is 0.15-0.6 weight part, More preferably, it is 0.2-0.5 weight part. When the blending amount of the fluoropolymer is less than 0.05 parts by weight, the effect of preventing the dripping of the combustion product is insufficient, and it becomes difficult to maintain high flame retardancy particularly in a thin molded article. Moreover, when the compounding quantity of a fluoropolymer exceeds 1 weight part, melt fluidity | liquidity and impact resistance will fall.

Component (E) used in the present invention is a silicone oil, which is a polymer of an organosilicon compound that is liquid at room temperature.
In the present invention, the component (E) is used as a dispersant or a spreading agent for the colorant (F) when coloring the “uncolored polycarbonate-based flame retardant resin composition” composed of the components (A) to (D). It is used as a component that gives the effects of

Particularly preferred examples of the silicone oil used in the present invention include those selected from the group of compounds represented below.
(In the formula, each R _x independently represents a hydrogen atom, an aryl group having 6 to 30 carbon atoms, an aliphatic group or alicyclic group having 1 to 50 carbon atoms, and n is an integer of 0 or 1 or more. is there.)

Among the compound groups shown above, particularly preferable examples of the component (E) used in the present invention include methyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, and cyclic dimethyl silicone oil.
Furthermore, the component (E) used in the present invention has a viscosity at 25 ° C. of preferably 0.1 to 1,000 cs (centistokes), more preferably 1 to 700 cs, and particularly preferably 5 to 500 cs. When the viscosity of the component (E) is less than 0.1 cs, since the viscosity is low, the effect as a spreading agent for spreading the colorant (F) on the pellet surface of the uncolored polycarbonate-based flame retardant resin composition On the other hand, when the viscosity of the component (E) exceeds 1,000 cs, since the viscosity is high, the action of the component (E) as a dispersant is reduced, and coloring in the resin composition The dispersibility of the agent tends to decrease.

The component (E) used in the present invention is a modified silicone oil modified by introducing various chemical structures other than R _x into a part of the structure represented by the above formula (Chemical Formula 17). It may be. Examples of the modified silicone oil used in the present invention include amino-modified silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, carbinol-modified silicone oil, methacryl-modified silicone oil, mercapto-modified silicone oil, and polyether-modified silicone oil. And methylstyryl-modified silicone oil, alkyl-modified silicone oil, higher fatty acid ester-modified silicone oil having 8 to 30 carbon atoms, hydrophilic specially modified silicone oil, higher alkoxy-modified silicone oil, fluorine-modified silicone oil, and the like.

The amount of the component (E) used in the present invention is 0.001 to 3 parts by weight with respect to 100 parts by weight of the “uncolored polycarbonate-based flame retardant resin composition” comprising the components (A) to (D). Yes, preferably 0.01 to 0.5 parts by weight, more preferably 0.05 to 0.3 parts by weight. When the amount is less than 0.001 part by weight, the dispersibility of the colorant is lowered. On the other hand, when the amount exceeds 3 parts by weight, the heat resistance of the resin composition is lowered or the component (E) oozes onto the surface of the molded body. This is not preferable because of the occurrence of rash.
Component (F) used in the present invention is a colorant. The colorant is a pigment or dye used for coloring a resin, for example, an inorganic pigment such as titanium white (titanium oxide), titanium yellow, bengara, ultramarine blue, spinel green, condensed azo organic pigment, quinacridone Organic pigments, isoindolinone organic pigments, perylene organic pigments, anthraquinone organic pigments, phthalocyanine organic pigments and other organic pigments, carbon black, perylene dyes, perinone dyes, anthraquinone dyes, heterocyclic dyes And the like.

  Among the colorants, titanium oxide is not limited by the production method and crystal structure, but titanium oxide produced by the chlorine method and having a rutile crystal structure is preferred. The average particle size of the titanium oxide used is not particularly limited, but is preferably 0.01 to 0.5 μm, and particularly preferably 0.1 to 0.3 μm. Moreover, as long as the objective of this invention is not impaired, you may process beforehand with the processing agent normally used as a surface treatment agent of a titanium oxide. Examples of such a treating agent include alumina and silica, and they may be used alone or in combination. Further, as the surface treatment agent, an organic dispersant, a stabilizer and the like are included, and the organic dispersant and the stabilizer may correspond to the component (G) of the present invention, but these are used within the scope of the present invention. Is possible.

  The component (F) in the present invention is usually used in combination with a plurality of components (F) in order to achieve the desired color development, but the blending amount is the component (A) as the total amount of the component (F). And 0.0001 to 10 parts by weight based on 100 parts by weight of the total of component (B). If it is less than 0.0001 part by weight, it will be difficult to keep the product color constant. On the other hand, if it exceeds 10 parts by weight, the mechanical properties of the resin composition may be lowered, or the flame retardancy may be lowered. is there. Although the compounding quantity of a component (F) changes with the desired color tone or the color tone of base resin, the usage-amount is the range of 0.1-3 weight part normally as the total amount.

The lubricant (G) in the present invention refers to a compound selected from a compound group such as aliphatic hydrocarbon, polyolefin wax, higher carboxylic acid, higher carboxylic acid metal salt, fatty acid amide, fatty acid ester, and higher alcohol.
Some of these lubricants (G) are already contained in the resin raw material, but as a processing aid when producing the resin composition or as a dispersant for the colorant when coloring the resin composition. Some of them are blended into the resin composition as a spreading agent and as a mold release agent for improving the mold release of the molded body during molding.
Among the components (G), the aliphatic hydrocarbon is an aliphatic hydrocarbon compound having 5 to 100 carbon atoms, and examples thereof include ligroin, paraffin oil, mineral oil, and liquid paraffin.

The polyolefin wax is a low molecular weight polyolefin having an olefin as a basic structural unit and a weight average molecular weight of 500 to 10,000, paraffin wax, polyethylene wax, polypropylene wax, ethylene / vinyl acetate copolymer wax, Examples thereof include polyolefin ionomer waxes.
The higher carboxylic acid is a fatty acid having a saturated or unsaturated bond having 5 to 50 carbon atoms, such as stearic acid, valeric acid, caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, arachin. Examples thereof include acid, behenic acid, lignoceric acid, serotic acid, mellic acid, tetratriacontanoic acid, glutaric acid, adipic acid, azelaic acid, naphthenic acid, rosin acid, oleic acid, linoleic acid, and linolenic acid.

The higher carboxylic acid metal salt is a metal salt of the higher carboxylic acid, and examples thereof include alkali metal stearate, calcium stearate, zinc stearate, magnesium stearate, and lead stearate.
The fatty acid amide is a compound having 12 to 150 carbon atoms having one or more acid amide bonds in the molecule, and is stearic acid amide, oleic acid amide, erucic acid amide, ethylene bis stearic acid amide, methylene bis stearin. Examples thereof include acid amides and ethylene bisoleic acid amides.

The fatty acid ester is a compound having 10 to 200 carbon atoms having one or more ester bonds in the molecule. For example, an ester of a higher carboxylic acid such as butyl stearate and a monohydric alcohol, ethylene glycol monostearate , Glycerol monostearate, trimethylolpropane monostearate, pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol distearate, glycerol dilaurate, glycerol tristearate, trimethylolpropane distearate, glycerol distearate Glycerin tribehenate, pentaerythritol tristearate, trimethylolpropane tricaprate, trimethylolpropanediolate, pentaerythritol tetrastearate It can be mentioned esters of the higher carboxylic acids rate, etc. and polyhydric alcohol.
Moreover, a higher alcohol is a C5-C50 compound which has a 1 or more hydroxyl group in a molecule | numerator, For example, a stearyl alcohol can be mentioned.

In the present invention, the total amount of the lubricant (G) contained in the polycarbonate-based colored flame-retardant resin composition, that is, the total amount of the lubricant component contained in the polycarbonate-based colored flame-retardant resin composition of the present invention is 3,000. Weight ppm or less, preferably 0.01 to 2,000 ppm by weight, more preferably 0.1 to 1,500 ppm by weight, and particularly preferably 1 to 1,000 ppm by weight. Even in the case of a molded body, high flame retardancy can be achieved.
The content of the component (G) in the polycarbonate-based colored flame retardant resin composition according to the present invention is determined by separating or extracting the components (G) from the composition by a combination of good solvent / poor solvent, proton NMR method, GC / MS. Quantification can be performed by a combination of analytical methods such as LC method and LC / MS method.
Furthermore, in the polycarbonate-based colored flame-retardant resin composition of the present invention, mainly due to oxygen in the air when the melt-blending process, melt residence in the molding machine during molding, or when the molded body is exposed to a high temperature environment. For the purpose of preventing the progression of heat aging, heat stabilizers such as hindered phenol antioxidants, phosphite heat stabilizers, and sulfur heat stabilizers can be preferably used.

  The hindered phenol-based antioxidant is an antioxidant composed of a compound having one or more hindered phenol structures in the molecule. For example, pentaerythritol tetrakis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate], thiodiethylene-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diyl-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionamide], benzenepropanoic acid, 3,5-bis- (1,1-dimethylethyl) -4-hydroxy, C 7-9 side chain alkyl ester, 2,4-dimethyl-6 1-methylpentadecyl) phenol, diethyl [[3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ′, 3 ″, 5,5 ′, 5 ",-hexa-t-butyl-a, a ', a",-(mesitylene-2,4,6-triyl) tri-p-cresol, calcium ethylene-bis-[[[3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis- (octylthiomethyl) -o-cresol, ethylene-bis- (oxyethylene) -bis- [3- ( 5-t-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-tri (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-t-butyl- 4- (4,6-bis- (octylthio) -1,3,5-triazin-2-ylamino) phenol, 2,6-di-t-butyl-4-methylphenol, styrene-phenol, 2,2 '-Methylene bistrene-bis- (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4- Methyl phenyl acrylate, 4,4′-butylidene-bis- (3-methyl-6-tert-butylphenol), 4,4′-thio-bis- (3-methyl-6-tert-butylphenol), 1, 3,5-tris (4-t-butyl -3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,9-bis- [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1, 1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5 ′] undecane, and the like. In the present invention, those having a molecular weight of 500 or more are heat aging. Therefore, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate is particularly preferable.

The phosphite heat stabilizer is an antioxidant composed of a compound having one or more trivalent phosphite structures in the molecule, for example, tris (2,4-di-t-butylphenyl). ) Phosphite, bis- [2,4-bis- (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid, tetrakis (2,4-di-t-butylphenyl) [1,1 -Biphenyl] -4,4'-diyl-bis-phosphonite, bis- (2,4-di-t-butylphenyl) pentaerythritol diphosphite. In the present invention, tris (2, 4-di-t-butylphenyl) phosphite and bis- (2,4-di-t-butylphenyl) pentaerythritol diphosphite are preferred.
Furthermore, the sulfur-based heat stabilizer is an antioxidant composed of a compound having one or more sulfur atoms in the molecule, for example, a dialkyl-3,3′-thiodipropinate having 12 to 18 carbon atoms, Mention may be made of tetrakis [methylene-3- (alkylthio) propionate] methane, bis [2-methyl-4- (3-alkyl-thiopropionyloxy) -5-tertiarybutylphenyl] sulfide.

In the present invention, the above heat stabilizer may be used as a single component, or a plurality of components may be used in combination.
In this invention, the usage-amount in the case of using the said heat stabilizer is 0.01-1 weight part as a total amount of this heat stabilizer with respect to a total of 100 weight part of a component (A) and a component (B). The range is preferably 0.05 to 0.5 parts by weight, more preferably 0.1 to 0.3 parts by weight.
In the polycarbonate-based colored flame retardant resin composition of the present invention, an inorganic filler such as glass fiber, glass flake, glass bead, calcium carbonate, talc, mica is used for the purpose of modifying the resin composition as necessary. Further, reinforcing materials such as carbon fiber and charcoal, or other thermoplastic resins can be added.
Furthermore, in the polycarbonate-based colored flame retardant resin composition of the present invention, an ultraviolet absorber, an epoxy compound, an antistatic agent, and the like can be added as necessary within the range not impairing the gist of the present invention.

Next, the method for producing the polycarbonate-based colored flame retardant resin composition of the present invention will be described in detail.
The method for producing a polycarbonate-based colored flame-retardant resin composition of the present invention is applied to pellets of an uncolored polycarbonate-based flame-retardant resin composition comprising the components (A), (B), (C), and the component (D). The component (E) and the component (F) are mixed and melt-kneaded by an extruder to produce a polycarbonate-based colored flame-retardant resin composition, the polycarbonate-based colored flame-retardant resin composition In this method, the total amount of the lubricant (G) contained in the product is 3,000 ppm by weight or less.
Here, the production of the uncolored polycarbonate-based flame retardant composition is performed by melting the components (A), (B), (C), and the component (D) using a melt-kneading apparatus, preferably a twin-screw extruder. Manufactured by kneading.

  In the production of the uncolored polycarbonate-based flame retardant composition, the components (A) to (D) as raw materials are mixed in advance using a premixing device such as a tumbler or ribbon blender, and then mixed in an extruder. It is possible to obtain the uncolored polycarbonate-based flame retardant composition by supplying and melt-kneading, but by supplying each raw material component to the extruder independently and performing melt-kneading, uncolored It is also possible to obtain a polycarbonate-based flame retardant composition. In particular, when the component (C) is in a liquid state, the component (C) is preferably supplied directly to an extruder using a gear pump or a plunger pump, and melt-kneaded. Moreover, when using the aqueous dispersion of a fluoropolymer as a component (D), it is also possible to supply a component (D) to an extruder after mixing with a component (A) or a component (B) previously. However, it is also possible to supply the component (D) independently to the extruder and perform melt kneading.

In the production of the uncolored polycarbonate-based flame retardant composition, the extruder has a cylinder set temperature of 200 to 300 ° C, preferably 220 to 270 ° C, more preferably 230 to 250 ° C, and an extruder screw. Melting while kneading with a rotation speed of 100 to 700 rpm, preferably 200 to 500 rpm, and an average residence time in the extruder of 10 to 100 seconds, so as not to give excessive heat to the resin during the crossing Kneading is performed. The melt-kneaded uncolored polycarbonate-based flame retardant resin composition is extruded as a strand from a die attached to the tip of the extruder and pelletized to obtain pellets of the uncolored polycarbonate-based resin composition.
In the method for producing a colored polycarbonate flame retardant resin composition of the present invention, the component (E) and the component (F) are mixed with the “uncolored polycarbonate flame retardant resin composition” pellets obtained by the method exemplified above. The mixed mixture is put into an extruder having a vent port and melt kneaded to produce a polycarbonate-based colored flame retardant resin composition.

  As a preferred method of mixing the component (E) and the component (F) into the pellets of the uncolored polycarbonate flame retardant resin composition, a mixing device such as a tumbler or ribbon blender is used. The component (E) is blended with the pellets of the “flammable resin composition”, and is usually mixed and stirred for 1 to 60 minutes, preferably 5 to 40 minutes. Thereafter, the component (F) is added and mixed and stirred for 1 to 60 minutes, preferably 5 to 40 minutes. In the mixing, the temperature is not particularly limited, but is usually performed at room temperature. The mixture prepared from the “uncolored polycarbonate-based flame retardant resin composition” pellets and the component (E) and the component (F) thus prepared has the component (F) as the colorant “uncolored polycarbonate-based flame retardant”. A resin composition "is preferable because it can be uniformly spread on the surface of the pellet.

As the extruder used in the production of the polycarbonate-based colored flame retardant resin composition of the present invention, a single-screw or twin-screw extruder is preferably used. When a single-screw extruder is used as the extruder, it has an extruder screw configuration with an enhanced kneading and dispersing function, for example, 3 to 6 stages of dalmage screw parts, preferably a single-melt part further attached thereto. It is preferred to use a screw extruder. On the other hand, when a twin screw extruder is used as the extruder, the amount of the colorant dispersant and the colorant spreading agent can be reduced because the kneading function is generally superior to that of the single screw extruder. Alternatively, it is more preferable because the colorant can be well dispersed in the resin composition without using them.
In the production of the polycarbonate-based colored flame-retardant resin composition of the present invention, it is more preferable to perform devolatilization while performing melt-kneading for coloring with an extruder in order to increase the flame retardancy of the resin composition.

Here, “devolatilization” refers to removal of volatile components generated in the melt-kneading process through release of atmospheric pressure or reduced pressure through a vent port provided in the extruder.
The vent port attached to the extruder for performing the devolatilization is an extrusion that is in a molten state containing substantially no unmelted portion of the uncolored polycarbonate-based flame retardant resin composition pellets as a raw material inside the extruder. When the machine position is a reference position, the machine is installed at the reference position or at an extruder position further downstream in the extrusion direction than the reference position. In addition, confirmation that the attachment position of the vent port is in a molten state in which the unmelted portion of the raw material resin composition pellets is substantially not included is obtained by visually observing the state of the molten resin at the vent port position. Easy to judge.
Further, the shape of the screw of the extruder at the vent port position is preferably a deep groove type full flight screw shape. When the screw shape of the extruder at the vent port position is a deep groove type full flight screw shape, the surface area of the molten resin can be increased, so that devolatilization can be effectively performed and venting up from the vent port of the molten resin can be performed. Since it can prevent, it is especially preferable in this invention.

In the present invention, when devolatilization is performed, it is preferable to open the vent port attached to the extruder to the atmosphere, but it is more effective to increase the flame retardant effect by performing devolatilization under reduced pressure through the vent port, The vacuum devolatilization is preferably performed at 0.01 to 400 mmHg-G (gauge pressure), more preferably 0.1 to 300 mmHg-G, and still more preferably 1 to 150 mmHg-G.
Upon coloring, the extruder is set to an extruder cylinder set temperature of 180 to 260 ° C, more preferably 200 to 250 ° C, still more preferably 220 to 240 ° C, and an extruder screw rotation speed of 30 to 500 rpm, preferably 50 to 300 rpm. More preferably, coloring is performed at 70 to 200 rpm.
Moreover, the residence time of the resin in an extruder is normally selected suitably in the range of 10 to 100 seconds.

In the present invention, the lubricant (G) can be blended as necessary within the range described in the present invention. In this case, the lubricant (G) is used at any stage of melt-kneading. It is possible to mix with. In particular, when coloring is performed using a single screw extruder, an appropriate amount of the component (G) as a dispersant or a spreading agent is used in order to improve the dispersibility and color uniformity of the colorant (F). It may be preferable. In this case, in this invention, it is necessary to consider the range whose total amount of a component (G) is 3,000 weight ppm or less with respect to a polycarbonate-type colored flame-retardant resin composition.
A molding method for obtaining a molded article made of a polycarbonate-based colored flame retardant resin composition obtained by the present invention is not particularly limited, and examples thereof include injection molding, gas assist molding, extrusion molding, and compression molding. Of these, injection molding is preferably used.

The polycarbonate-based colored flame retardant resin composition of the present invention has excellent flame retardancy even in a thin molded article, and has excellent melt fluidity and impact resistance, so that a molded article having a thin part is obtained. Preferably, the molded product has a part with a thickness of 2 mm or less in the thickness of 30% by weight or more, more preferably a part with a thickness of 2 mm or less in the thickness of 50% by weight or more. Can be suitably used in the case of obtaining a molded product having a thickness of 2 mm or less, more preferably 70% by weight or more of the entire molded product.
Examples of molded articles using the polycarbonate-based colored flame retardant resin composition of the present invention include PC monitors, notebook computers, copiers, printers and other office equipment housings, office equipment chassis, mobile phone housings, etc. Is mentioned.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
In Examples or Comparative Examples, a polycarbonate-based colored resin using the following components (A), (B), (C), (D), (E), (F) and, if necessary, the component (G) A composition was prepared. However, although the component (C) used in the comparative example does not satisfy the requirement of the component (C) in the present invention, it is classified as (C) for convenience.

1. Component (A): Aromatic polycarbonate (PC1)
A bisphenol A-based polycarbonate produced from bisphenol A and diphenyl carbonate by the melt transesterification method and containing no lubricant component (G).
Weight average molecular weight (Mw) = 23,000
Phenolic end group ratio (ratio of phenolic end groups to the total number of end groups) = 38 mol%
Lubricant component (component (G)) content = 0 ppm by weight

2. Component (B): Rubber-modified styrenic resin (ABS1)
An ABS graft copolymer obtained by polymerizing by emulsion polymerization and coagulating by sulfate precipitation, followed by washing and drying, has a weight average molecular weight (Mw) of 110,000, and has an acrylonitrile unit. Emulsion polymerization acrylonitrile, having a butadiene rubber content of 22 wt% and a rubber weight average particle size of 0.26 μm, obtained by dilution and kneading with an AS resin (styrene acrylonitrile resin) comprising 27 wt% and styrene units 73 wt% 1,500 ppm by weight of lubricant component (component (G): rosin acid) as an emulsifier residue, hindered phenol antioxidant: octadecyl-3- (3,5-di-t-) Butyl-4-hydroxyphenyl) propionate) at 2,000 ppm by weight and tris as a phosphite heat stabilizer (2,4-di -t- butyl-phenyl) phosphite those containing 500 weight ppm.
Rosin acid content (component (G)) = 1,500 ppm by weight
Hindered phenolic antioxidant (octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) = 2,000 ppm by weight
Phosphite heat stabilizer (Tris (2,4-di-t-butylphenyl) phosphite) = 500 ppm by weight

(ABS2)
Polymerized by emulsion polymerization, coagulated by sulfate precipitation, washed and dried to obtain butadiene rubber content of 55 wt%, rubber weight average particle size of 0.31 μm, acrylonitrile unit of 25 wt% % And styrene unit 75 wt% copolymerized powder acrylonitrile butadiene styrene resin containing 2,000 ppm by weight of a lubricant component (rosin acid) as an emulsifier residue.
Rosin acid content (component (G)) = 2,000 ppm by weight

(AS)
An AS resin (styrene acrylonitrile resin) having a weight average molecular weight (Mw) of 130,000 comprising 27 wt% of acrylonitrile units and 73 wt% of styrene units and containing no lubricant component.
Weight average molecular weight (Mw) = 130,000
Lubricant component (component (G)) content = 0 ppm by weight

3. Component (C): Organophosphorus compound oligomer (phosphate 1)
An organophosphorus compound oligomer represented by the formula (1), wherein the substituents R ^a , R ^b , R ^c and R ^d are all phenyl groups, and the weight average condensation degree (N) is 1.12. The magnesium content is 1.5 ppm, the chlorine content is 1 ppm or less, and the acid value is 0.008 mgKOH / g.
(Phosphate 2)
Made by Daihachi Chemical Co., Ltd., resorcinol-diphosphate (CR733S)
A weight average condensation degree (N) of 1.48, a magnesium content of 5.6 ppm, a chlorine content of 1 ppm or less, and an acid value of 0.01 mg / KOH.
(Phosphate 3)
Made by Daihachi Chemical Co., Ltd., triphenyl phosphate (TPP)
Monophosphate compound

4). Component (D): Fluoropolymer (PTFE)
Made by GE Specialty Chemicals, mixed powder of polytetrafluoroethylene and acrylonitrile / styrene copolymer (trade name Blendex 449)
PTFE content = 50wt%
5. Ingredient (E): Silicone oil Shin-Etsu Chemical Co., Ltd., dimethyl silicone oil (trade name: KF96-50), viscosity 50 ± 2.5 cs (25 ° C.), specific gravity 0.955 to 0.965 (25 ° C.), fluid Point -50 ° C or lower, flash point 300 ° C or higher

6). Ingredient (F): Colorant (white)
Titanium oxide manufactured by DuPont (trade name Ti-Ture R103-08)
(black)
Carbon black (trade name: Carbon Black 7550F) manufactured by Tokai Carbon Co., Ltd.
(yellow)
Titanium Yellow (trade name Yellow 29) manufactured by Shepherd

7. Ingredient (G): Lubricant (release agent)
Stearic acid monoglyceride release agent (trade name EXCEL T-95) (dispersant) manufactured by Kao Corporation
Ethylene bisstearyl amide manufactured by Kao Corporation (trade name Kao Wax EB-P)
(Spreading agent)
Paraffin oil manufactured by Esso Oil Co., Ltd. (trade name: Christol J-352)

8). Other components: heat resistance stabilizer (I-1076: hindered phenol antioxidant)
Ciba Specialty Chemicals (trade name: IRGANOX1076)
Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (P-168: phosphite heat stabilizer)
Ciba Specialty Chemicals (trade name: IRGAFOS168)
Tris (2,4-di-t-butylphenyl) phosphite

(Production Examples 1-9)
[Production of Uncolored Polycarbonate Flame Retardant Resin Composition (Uncolored Composition)]
Ingredients (A), (B), (C), (D) and other ingredients in the amounts shown in Table 1 (units are parts by weight) are melt kneaded using a twin screw extruder and include a colorant. No pellets of uncolored polycarbonate-based flame retardant resin composition (described as uncolored composition in Tables 1 to 4) were obtained. In Table 1, the number of parts of component (D) indicates the number of parts as a fluoropolymer.

In the production of the uncolored polycarbonate flame retardant resin composition, the melt kneading apparatus uses a twin screw extruder (ZSK-25, L / D = 37, manufactured by Werner & Pfleiderer), cylinder set temperature 245 ° C, screw rotation speed Melt kneading was performed under the conditions of 250 rpm, a kneading resin discharge speed of 10 to 23 kg / Hr, and a resin residence time of 30 to 70 seconds inside the extruder. During the melt kneading, the temperature of the molten resin measured by a thermocouple at the extruder die was 250 to 260 ° C. The raw materials are charged into the twin-screw extruder by pre-blending the components (A), (B), (D) and other components in advance with a tumbler for 30 minutes, and then charged into the extruder through a weight feeder. The organophosphorus compound oligomer (C) was preliminarily heated to 80 ° C. and blended by press-fitting through an injection nozzle from the middle of the extruder with a gear pump. Further, devolatilization under reduced pressure was performed at 10 mmHg-G (gauge pressure) in the latter part of the extruder.
The melt-kneaded composition was extruded as a strand from a die and pelletized to prepare uncolored polycarbonate-based flame retardant resin compositions 1-9.

Examples 1-5

  The pellets of the uncolored polycarbonate-based flame retardant resin compositions 1 and 2 obtained in the production examples are dried, and the pellets, silicone oil (component (E)), and colorant in the amounts shown in Table 2 (units are parts by weight). (Component (F)) and a lubricant (component (G)) were mixed by a tumbler. In mixing, first, after blending component (E) and pellets of uncolored polycarbonate-based flame retardant resin composition for 10 minutes, a mixture of component (F) and component (G) mixed in advance is further blended, Mix for 30 minutes. A mixture comprising the uncolored polycarbonate flame retardant resin composition thus obtained and the components (E), (F) and (G) was put into an extruder to obtain a polycarbonate colored flame retardant resin composition. .

Here, as the extruder, a single-screw extruder (manufactured by Tanabe Plastics Machinery Co., Ltd., 65-mmφ vented single-screw extruder, 5-stage dull image + 1-stage unimelt mounted), or twin-screw extruder (ZSK-25, L / D = 37, manufactured by Werner & Pfleiderer).
The cylinder set temperature of the extruder was 235 ° C., and a strand was extruded from an extruder die and pelletized to obtain pellets of a polycarbonate-based colored flame-retardant resin composition.
The obtained pellets were molded by an injection molding machine (Autoshot 50D, manufactured by FANUC), and the following tests were performed.

(1) Flame Retardancy Test The obtained pellets were dried and molded with an injection molding machine set at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C., and a strip-shaped molded body (thickness 2.0 mm, 1.5 mm and 1.4 mm), and UL94 standard 20MM vertical combustion test was conducted and classified into V-0, V-1 and V-2. The symbol NC in the table means non-classification. (Degree of flame retardancy: V-0>V-1>V-2> NC)

(2) Colorant dispersibility Using 10 g of the obtained pellets, a press film was prepared with a press molding machine heated to 210 ° C. so that the thickness would be in the range of 0.25 to 0.35 mm. The dispersibility was visually observed.
○: Colorant aggregates having a diameter of 0.2 mmφ or more or streaks of the colorant are not observed at all, and the dispersibility of the colorant is good.
X: A colorant aggregate having a diameter of 0.2 mmφ or more or a streak pattern of the colorant is present, and the dispersibility of the colorant is poor.

(3) Evaluation of mold contamination The injection pressure (905 kgf / cm ²⁾ and injection time (3 seconds) were set using an injection molding machine (NIIGATA / CN75, manufactured by Niigata Steel) with a cylinder temperature of 260 ° C and a mold temperature of 40 ° C. A molded article having a test piece weight of 4 g was continuously molded under the conditions of a cooling time of 1.2 seconds, a mold opening / closing time of 2.1 seconds, a rest time of 2 seconds, and a molding cycle of 8.3 seconds, and 100, 500, 1,000 The surface condition of the mold after 2,000 shots was visually observed.
A: Generation of MD is not observed after 2,000 shots.
O: Generation of MD is observed in 101 to 2,000 shots.
X: Generation of MD is observed at 100 shots or less.
Here, the MD includes both solid and liquid deposits attached to the mold surface.

(4) MFR
According to ASTM-D1238, the measurement was performed at 220 ° C. under a load of 10 kg.
(Unit: g / 10min)
(5) Izod impact test The obtained pellets were dried, and a 1/8 inch thick strip was formed by an injection molding machine set at a cylinder temperature of 240 ° C and a mold temperature of 60 ° C, in accordance with ASTM-D256. The Izod impact strength was measured with a 1/8 inch thickness and a notch. The measurement temperature is 23 ° C. (Unit: kgf · cm / cm)
The results are shown in Table 2.

The total amount of the component (G) in the colored composition shown in Table 2 is a calculated value, and includes the component (A) and the component (G) contained in the component resin (B). Value.
Although Examples 1 to 5 are the results for the present invention, it can be seen that they are excellent in thin flame retardancy, colorant dispersibility, low mold contamination, melt fluidity, and impact resistance.

Comparative Examples 1-5

The uncolored polycarbonate-based flame-retardant resin compositions 1 and 3 obtained in the production examples were dried, and the polycarbonate-based colored flame-retardant resin composition in the same manner as in Examples 1 to 5 in the amounts shown in Table 3 (units are parts by weight). Got.
It evaluated similarly to Examples 1-5 using the obtained pellet.
The results are shown in Table 3.

The total amount of the component (G) in the colored composition shown in Table 3 is a calculated value, which is a value obtained in the same manner as in Table 2.
Comparative Example 1 is an example lacking the component (E), but the colorant dispersibility was insufficient.
Comparative Example 2 lacks component (E) and uses paraffin oil (component (G), boiling point of 300 ° C. or higher) as a spreading agent instead of component (E), but has insufficient flame retardancy. there were.
Comparative Example 3 is an example in which the component (E) exceeds the upper limit of the use range of the present invention, but the flame retardancy is insufficient and mold contamination is seen.
Comparative Example 4 is an example in which the total amount of component (G) exceeds the upper limit of the use range of the present invention, but the flame retardancy was insufficient.
Comparative Example 5 is an example in which TPP, which is a mono-type phosphorus compound flame retardant, was used instead of the organic phosphorus compound oligomer, but the mold contamination was remarkable.

Comparative Examples 6-11

The uncolored polycarbonate-based flame retardant resin compositions 4 to 9 obtained in Production Examples 4 to 9 are dried, and in the amounts shown in Table 4 (units are parts by weight), the polycarbonate-based colored flame retardant resin compositions are the same as in Example 1. I got a thing.
It evaluated similarly to Examples 1-5 using the obtained pellet.
The results are shown in Table 4.

The total amount of the component (G) in the colored composition shown in Table 4 is a calculated value, and is a value obtained in the same manner as in Table 2.
Comparative Example 6 is an example lacking component (B), but the melt fluidity and impact resistance were insufficient.
Although the comparative example 7 is an example in which a component (B) exceeds the upper limit of the use range of this invention, the flame retardance was inadequate.
Although the comparative example 8 is an example whose component (C) is below the minimum of the use range of this invention, a flame retardance and melt fluidity | liquidity were inadequate.
Comparative Example 9 is an example in which the component (C) exceeds the upper limit of the use range of the present invention, but the flame retardancy was insufficient and mold contamination was observed. Furthermore, the impact resistance was insufficient.
Comparative Example 10 is an example lacking component (D), but the flame retardancy was insufficient.
Although the comparative example 11 is an example in which a component (D) exceeds the upper limit of the use range of this invention, the flame retardance and impact resistance were inadequate.

Effect of the invention

  The polycarbonate-based colored flame-retardant resin composition of the present invention is a polycarbonate-based colored flame-retardant resin excellent in flame retardancy, colorant dispersibility, low mold contamination, fluidity, and impact resistance at the same time in a thin molded article. Since it is a composition, it is useful as a housing material for computer monitors, notebook computers, printers, word processors, copiers, mobile phones, etc., and is particularly useful when obtaining molded articles having thin portions. It is.

Claims (7)

50 to 95 parts by weight of the aromatic polycarbonate resin (A), 50 to 5 parts by weight of the rubber-modified styrene resin (B), and 100 parts by weight of the total of the component (A) and the component (B). 5 to 30 parts by weight of the phosphorus compound oligomer (C), 0.05 to 1 part by weight of the fluoropolymer (D), 100 parts by weight in total of the components (A), (B), (C) and the component (D) , A polycarbonate-based colored flame-retardant resin composition containing 0.001 to 10 parts by weight of silicone oil (E) and 0.0001 to 10 parts by weight of a colorant (F), an aliphatic hydrocarbon and a polyolefin-based wax , higher carboxylic acids, higher carboxylic acid metal salts, higher fatty acid amides, Oh in total amount 171～ 3,000 weight pp m of lubricant (G) is a compound selected from higher fatty acid esters and higher alcohols, , Polycarbonate colored flame retardant resin composition characterized by containing no inorganic filler. The polycarbonate-based colored flame-retardant resin composition according to claim 1 , wherein at least one organophosphorus compound oligomer (C) is selected from the group of compounds represented by the following formula (1).
[Chemical 1]
50 to 95 parts by weight of the aromatic polycarbonate resin (A), 50 to 5 parts by weight of the rubber-modified styrene resin (B), and 100 parts by weight of the total of the component (A) and the component (B). Silicone oil (E) 0 with respect to 100 parts by weight of uncolored polycarbonate flame retardant resin composition pellets comprising phosphorus compound oligomer (C) 5-30 parts by weight and fluoropolymer (D) 0.05-1 part by weight 0.001 to 3 parts by weight and a colorant (F) 0.0001 to 10 parts by weight, and melt-kneading using an extruder to obtain a polycarbonate-based colored flame retardant resin composition, Compounds selected from aliphatic hydrocarbons, polyolefin waxes, higher carboxylic acids, higher carboxylic acid metal salts, higher fatty acid amides, higher fatty acid esters, and higher alcohols There total amount of lubricant (G) is the 171～ 3,000 weight pp m, the production method of the polycarbonate-based coloring flame retardant resin composition characterized by containing no inorganic filler. The method for producing a polycarbonate-based colored flame retardant resin composition according to claim 3 , wherein the at least one organic phosphorus compound oligomer (C) is selected from the group of compounds represented by the following formula (1).
[Chemical 2]
The method for producing a polycarbonate-based colored flame-retardant resin composition according to claim 3 or 4 , wherein the extruder is a twin-screw extruder.
A molded article obtained by molding the polycarbonate-based colored flame retardant resin composition according to claim 1 .
The molded product according to claim 6 , wherein a portion having a thickness of 2 mm or less is 30% by weight or more of the entire molded product.