JP2003049078A - Colored flame-retardant resin composition and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a colored flame-retardant resin composition having excellent flame retardancy and excellent dispersibility of a coloring agent in a thin-walled molded body, and to provide a manufacturing method therefor. SOLUTION: The colored flame-retardant resin composition comprises 100 pts.wt. of a thermoplastic resin (A), 0.01-40 pts.wt. of a flame retardant (B), 0.001-3 pts.wt. of a silicone oil (C) whose viscosity at 25 deg.C is 0.1-1,000 cs, based on 100 pts.wt. of the total of the components (A) and (B), and 0.0001-10 pts.wt. of a coloring agent (D). The composition contains lubricants (E) of <=3,000 ppm by weight in total. The method for manufacturing the same is also provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored flame-retardant resin composition having excellent flame retardancy in a thin-walled molded product and excellent dispersibility of a colorant, and a method for producing the same.

[0002]

2. Description of the Related Art A flame-retardant resin material containing a flame-retardant thermoplastic resin is inexpensive, lightweight and easy to mold, so that it can be used as a structural member for various electric and electronic devices requiring flame retardancy. Widely used as a housing material for computer monitors, notebook computers, printers, word processors, copiers, etc. Further, recent flame-retardant resin materials used in electric and electronic devices are strongly required to be lightweight, and even thin molded products are required to have high flame retardancy.

In general, the flame-retardant performance of a flame-retardant resin material decreases as the molded product becomes thinner. Furthermore, recently, due to increasing awareness of environmental protection, flame-retardant resin materials using non-bromine / non-chlorine flame retardants have been attracting attention. When an organic phosphorus compound or an organopolysiloxane is used, these flame retardants tend to be inferior in flame retardant effect compared to the case where conventionally used bromine / chlorine flame retardants are used. Therefore, the flame retardant performance is generally insufficient in response to the strong demand for thin-walled molded products.

By the way, in coloring the flame-retardant resin composition, in order to meet various color needs, an uncolored flame-retardant resin composition containing no colorant in advance (hereinafter referred to as "uncolored flame-retardant resin composition") is used. A method is widely used in which a colorant is mixed with a pellet of the “uncolored flame-retardant resin composition” and then the mixture is melt-kneaded. In this method, the dispersibility of the colorant is increased,
Further, for the purpose of eliminating uneven color tone, a dispersant for a colorant or a spreading agent for favorably spreading the colorant on the resin pellet surface may be used.

However, the use of these dispersants and spreading agents often causes a problem that the flame retardancy of the colored composition is lowered. On the other hand, when a dispersant or a spreading agent is not used, poor dispersion of the colorant or uneven color tone may occur, and in coloring the flame-retardant resin composition, high flame retardancy and preferable dispersibility of the colorant are required. It was not always easy to make them compatible. That is, as a molding material having a high degree of flame retardancy in a thin-walled molded product and a good dispersibility of a colorant at the same time, a colored flame-retardant resin composition and a method for easily producing it industrially are strong. Despite the demand, it is the current situation that no effective solution has been found.

The flame-retardant resin material usually contains various "lubricants". The term "lubricant" used in the present specification improves processing lubricity of a resin, dispersibility of a dye / pigment as a colorant of a resin, and further, releasability of a molded product from a mold. Compounds having an effect, which are generally referred to as “lubricant”, “processing aid”, “dispersant”, “release agent”, “spreading agent”, etc., are included, and aliphatic hydrocarbons, polyolefins A compound selected from the group of compounds 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.

The above-mentioned lubricant may be already contained in the resin as a raw material, or may be added in the processing such as compounding and coloring of the resin. For example,
A flame-retardant resin material is often molded into various molded products by injection molding. In injection molding, a lubricant (release agent) is added to the flame-retardant resin material in order to improve the releasability of the molded product from the molding die. ) May be added. Furthermore, in the process of coloring the flame-retardant resin material with a colorant (mainly dye / pigment), a lubricant (colorant dispersant) is used to enhance the dispersibility of the colorant in the resin, or the surface of the resin pellet is Lubricants (spreading agents) are often used to improve the spread of the colorant and improve the uniformity of color tone.

In the flame-retardant resin material used as a molding material as described above, particularly in the colored flame-retardant resin material, the above-mentioned lubricant component is generally contained. And, the above-mentioned lubricant component contained in the flame-retardant resin material is generally contained in the flame-retardant resin material as a total amount thereof in the order of several thousand to several tens of thousands ppm by weight. Since is a trace amount component, the effect of these lubricant components on the flame retardancy of the flame-retardant resin material has not been studied so far.

[0009]

DISCLOSURE OF THE INVENTION The present invention provides a colored flame-retardant resin composition having excellent flame retardancy in a thin-walled molded product and excellent dispersibility of a colorant, and a method for producing the same in an industrially easy manner. Is to provide.

[0010]

DISCLOSURE OF THE INVENTION The present inventors have made thin-wall molding of a flame-retardant resin composition used as a flame-retardant resin material, especially a flame-retardant resin composition using a non-bromine / non-chlorine flame retardant. As a result of earnestly studying the improvement of flame retardancy in the body, it was found that a lubricant component contained in a minute amount in the resin composition has a great influence on the flame retardancy of the resin composition.

Furthermore, in coloring the pellets of the uncolored flame-retardant resin composition in a desired color, the pellets of the uncolored flame-retardant resin composition are coated with a silicone oil having a viscosity in a specific range. Is used as a dispersant and / or a spreading agent, and melt-kneaded using an extruder,
Furthermore, by controlling the total amount of the lubricant component contained in the flame-retardant resin composition to be colored to a specific amount or less, it has excellent flame retardancy even in a thin molded article, and dispersibility of the colorant. The inventors have found that a colored flame-retardant resin composition having good quality can be obtained, and have completed the present invention.

That is, the present invention relates to [1] 100 parts by weight of the thermoplastic resin (A), 0.01 to 40 parts by weight of the flame retardant (B), and 100 parts by weight of the total of the components (A) and (B). Silicone oil (C) having a viscosity of 0.1 to 1,000 cs (centistokes) at 25 ° C. of 0.001
To 3 parts by weight and 0.0001 to 10 parts by weight of the colorant (D), wherein the total amount of the lubricant (E) is 3,000 ppm by weight or less. A colored flame-retardant resin composition,

[2] The lubricant (E) is an aliphatic hydrocarbon, a polyolefin wax, a higher carboxylic acid, a higher carboxylic acid metal salt, a higher fatty acid amide, a higher fatty acid ester,
And a colored flame-retardant resin composition according to the above [1], which is a compound selected from higher alcohols,
[3] The colored flame-retardant resin composition according to [1] or [2], wherein the thermoplastic resin (A) is an aromatic polycarbonate resin or a resin mainly containing an aromatic polycarbonate resin,

[4] The colored flame-retardant resin composition according to the above [1] or [2], wherein the thermoplastic resin (A) is a polyphenylene ether resin or a resin mainly composed of a polyphenylene ether resin. And [5] the flame retardant (B) is selected from the group of compounds represented by the organophosphorus compound oligomers of the following formula (1): [1]-[4] Flame retardant resin composition,

[0015]

[Chemical 5]

[6] Coloring according to any one of the above [1] to [4], wherein the flame retardant (B) is selected from compounds represented by the organopolysiloxane of the following formula (2). Flame retardant resin composition,

[0017]

[Chemical 6]

[7] Further, the fluoropolymer (F) is added to 100 parts by weight of the total of the components (A) and (B).
[1], which contains 0.05 to 2 parts by weight.
To the colored flame-retardant resin composition according to any one of [6],

[8] 100 parts by weight of the thermoplastic resin (A),
Silicone oil having a viscosity of 0.1 to 1,000 cs (centistokes) at 25 ° C. with respect to 100 parts by weight of an uncolored flame-retardant resin composition consisting of 0.01 to 40 parts by weight of the flame retardant (B). C) 0.001 to 3 parts by weight,
And a method for obtaining a colored flame-retardant resin composition by mixing 0.0001 to 10 parts by weight of the colorant (D) and melt-kneading with an extruder, wherein the total amount of the lubricant (E) is 3.
000 weight ppm or less, a method for producing a colored flame-retardant resin composition,

[9] The lubricant (E) is an aliphatic hydrocarbon, a polyolefin wax, a higher carboxylic acid, a higher carboxylic acid metal salt, a higher fatty acid amide, a higher fatty acid ester,
And a compound selected from higher alcohols, the method for producing a colored flame-retardant resin composition according to the above [8], and [10] the thermoplastic resin (A) is an aromatic polycarbonate resin or an aromatic polycarbonate. A method of producing a colored flame-retardant resin composition according to the above [8] or [9], which is a resin mainly composed of a resin.

[11] The colored flame-retardant resin composition according to the above [8] or [9], wherein the thermoplastic resin (A) is a polyphenylene ether resin or a resin mainly composed of a polyphenylene ether resin. Manufacturing method [1
2] The flame retardant (B) is selected from the group of compounds represented by the organophosphorus compound oligomers of the following formula (1), wherein the colored flame retardant according to any of [8] to [11]. A method for producing a resin composition,

[0022]

[Chemical 7]

[13] Coloring according to any one of the above [8] to [11], wherein the flame retardant (B) is selected from compounds represented by the organopolysiloxane of the following formula (2). Method for producing flame-retardant resin composition,

[0024]

[Chemical 8]

[14] Further, the component (A) and the component (B)
Of 100 parts by weight of fluoropolymer (F)
[8], which contains 0.05 to 2 parts by weight.
[15] The method for producing a colored flame-retardant resin composition according to any one of [13] to [13], wherein [15] the extruder is a twin-screw extruder.
To a method for producing a colored flame-retardant resin composition according to any one of [14],

[16] A molded product obtained by molding the colored flame-retardant resin composition according to any one of [1] to [7] above.
[17] The above-mentioned [1] wherein the molded product has a thickness of 2 mm or less in an amount of 30% by weight or more of the entire molded product.
6] is a molded article.

The present invention will be described in detail below. The component (A) of the composition of the present invention is a thermoplastic resin, for example, polystyrene resin, polyphenylene ether resin, polyolefin resin, polyvinyl chloride resin, polyamide resin, polyester resin, polyphenylene sulfide resin. Polycarbonate-based resin, polymethacrylate-based resin, etc., or a mixture of two or more thereof may be used.

In the present invention, as the component (A), an aromatic polycarbonate resin or a resin mainly containing an aromatic polycarbonate, or a polyphenylene ether resin or a resin mainly containing a polyphenylene ether resin can be preferably used. The aromatic polycarbonate resin which can be preferably used as the component (A) of the present invention has a main chain composed of a repeating unit represented by the following formula.

[0029]

[Chemical 9] (In the formula, Ar is a divalent aromatic residue, for example, phenylene, naphthylene, biphenylene, pyridylene,
Examples include those represented by the following formula. )

[0030]

[Chemical 10] (In the formula, Ar ¹ and Ar ² are each an arylene group. For example, a group such as phenylene, naphthylene, biphenylene, and pyridylene is represented, and Y is an alkylene group or a substituted alkylene group represented by the following formula.)

[0031]

[Chemical 11]

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a C 1-6 lower alkyl group, a C 5-10 cycloalkyl group, a C 6-30 aryl group. , A C7-31 aralkyl group, which may be optionally substituted with a halogen atom or a C1-10 alkoxy group, k is an integer of 3-11, and R ⁵ and R ⁶
Are independently selected for each X and independently of each other a hydrogen atom, or a lower alkyl group having 1 to 6 carbon atoms, or a lower alkyl group having 6 to 6 carbon atoms.
A 30 aryl group, which may be optionally substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms;
Represents a carbon atom. ) Further, a divalent aromatic residue represented by the following formula may be contained as a copolymer component.

[0033]

[Chemical 12] (In formula, Ar < ¹ >, Ar < ² > is the same as said Chemical formula 10. Z is a mere bond or -O-, -CO-, -S-, -SO.
_{2 -, - CO 2 -,} - CON (R 1) - (R 1 is as defined above formula) is a divalent group such as. ) Examples of these divalent aromatic residues include those represented by the following formula.

[0034]

[Chemical 13]

[0035]

[Chemical 14]

(In the formula, R ⁷ and R ⁸ are each independently
Hydrogen, halogen, C1-10 alkyl group, C1
It is a C-10 alkoxy group, a C5-C10 cycloalkyl group, or a C6-C30 aryl group. m and n are 1
In to 4 integer, m is may be different in each of R ⁷ is the same in the case of 2-4, there is n is different in each of the same each R ⁸ in the case of 2-4 May be. Among these, one represented by the following formula is a preferable example.

[0037]

[Chemical 15]

Particularly preferred is a polycarbonate containing 85 mol% or more (based on all the monomer units in the polycarbonate) of a repeating unit having Ar represented by the above formula as Ar. The polycarbonate that can be used in the present invention may have a branched structure having a trivalent or higher valent 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.

[0039]

[Chemical 16] (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. .

[0040]

[Chemical 17] The alkyl carbonate end group is represented by the following formula.

[0041]

[Chemical 18] (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.

[0042]

[Chemical 19]

Of these, phenol group, phenyl carbonate group, 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 resistance stability, the ratio of the phenol group terminal is 20% or more of the total number of terminal groups. 20 to 20 are preferable.
It is more preferably in the range of 80%. When the ratio of the phenol end groups exceeds 80% of the total number of end groups, the thermal stability at the time of melting tends to be slightly lowered.

The amount of phenol group ends is generally measured by using NMR (NMR method), using titanium (titanium method), UV or IR.
Can be determined by a method of measuring (UV method or IR method).

The weight average molecular weight (Mw) of the polycarbonate resin preferably used in the present invention is generally 5,000.
It is preferably in the range of 0 to 50,000, more preferably 10,000 to 40,000, still more preferably 15,000 to 30,000, and particularly preferably 18,000 to 25,000. is there. 5,000
If it is less than 5, impact resistance tends to be insufficient, and if it is 5
If it exceeds 10,000, the melt fluidity tends to be insufficient.

The weight average molecular weight (Mw) of the polycarbonate resin preferably used in the present invention is measured by gel permeation chromatography (GPC).
The measurement conditions are as follows. That is, using tetrahydrofuran as a solvent and polystyrene gel, the conversion molecular weight calibration curve according to the following equation is used to determine from the constitutional curve of standard monodisperse polystyrene. ^{_{M PC = 0.3591M PS 1.0388 (M}} PC is the weight average molecular weight of the polycarbonate, M _PS weight average molecular weight of polystyrene)

The aromatic polycarbonate resin preferably used in the present invention may be one produced by a known method. 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. Interfacial polymerization method (eg phosgene method), aromatic dihydroxy compound and carbonic acid diester (eg diphenyl carbonate)
A solid-state polymerization of a crystallized carbonate prepolymer obtained by a transesterification method (melting method), a phosgene method or a melting method of reacting, for example (JP-A-1-15803).
3 (corresponding to U.S. Pat. No. 4,948,871), Japanese Unexamined Patent Publication No. 1-271426, Japanese Unexamined Patent Publication No. 3-6862.
7 (corresponding to US Pat. No. 5,204,377) and the like are used.

The preferred polycarbonate resin is
A polycarbonate resin containing substantially no chlorine atom, which is produced from a dihydric phenol (aromatic dihydroxy compound) and a carbonic acid diester by a transesterification method can be used. In the present invention, two or more different polycarbonates having different structures and molecular weights may be combined and used as the component (A).

As the resin containing aromatic polycarbonate as a main component, which is preferably used as the component (A) of the present invention, there can be mentioned the resins comprising the aromatic polycarbonate resin and the rubber-modified styrene resin.

Here, the rubber-modified styrenic resin means a rubber-like polymer and all rubber-modified styrenic resins containing one or more vinyl compounds as components. As the rubbery polymer of the rubber-modified styrene resin, any one 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, silicone / acrylic composite rubber, polyisoprene, polychloroprene, ethylene / propylene rubber, ethylene / propylene / diene terpolymer rubber, Block copolymers such as styrene / butadiene block copolymer rubber, styrene / isoprene block copolymer rubber, and hydrogenated products thereof can be used. Among these polymers,
Preferably, polybutadiene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber,
Examples thereof include polybutyl acrylate.

The proportion of the rubbery polymer in the rubber-modified styrene resin is used in the range of 1 to 95% by weight, and it is determined according to the required mechanical strength, rigidity and moldability. It is preferably 5 to 45% by weight, more preferably 10 to 40% by weight.

Examples of the vinyl compound used in the rubber-modified styrene resin include aromatic vinyl compounds such as styrene, α-methylstyrene and paramethylstyrene, alkyl (meth) acrylates such as methyl methacrylate, methyl acrylate, butyl acrylate and ethyl acrylate. ) Acrylates, (meth) acrylic acids such as acrylic acid and methacrylic acid, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and α and β such as maleic anhydride
-Unsaturated carboxylic acid, N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide and other maleimide-based monomers, and glycidyl group-containing monomers such as glycidylmethacrylate.

Of these, aromatic vinyl compounds, alkyl (meth) acrylates, vinyl cyanide monomers and maleimide monomers are preferable, and styrene, acrylonitrile, N-phenylmaleimide, and Butyl acrylate. These vinyl compounds may be used alone or in combination of two or more. A combination of an aromatic vinyl compound and a vinyl compound other than aromatic is preferable.

In this case, the aromatic vinyl compound and the non-aromatic vinyl compound are used in arbitrary ratios, but the preferable ratio of the non-aromatic vinyl compound is 5 to 80 relative to the total amount of the vinyl compound alone. It is in the range of% by weight. Examples of the rubber-modified styrene resin include ABS resin (acrylonitrile / butadiene / styrene resin), AAS resin (acrylonitrile / butyl acrylate / styrene resin), and HIPS (high impact polystyrene resin).

The method for producing the rubber-modified styrene resin is not particularly limited, and bulk polymerization, solution polymerization, suspension polymerization,
A commonly known production method such as emulsion polymerization can be mentioned. Among them, the rubber-modified styrene resin produced by bulk polymerization or solution polymerization can obtain a rubber-modified styrene resin without using an emulsifier, and therefore, a fatty acid or a fatty acid metal salt derived from the emulsifier is rubber-modified. Since it is not substantially contained in the styrene resin, it can be particularly preferably used as a rubber-modified styrene resin used in combination with an aromatic polycarbonate resin.

Further, in the present invention, it is also effective to use the aromatic polycarbonate resin in combination with two or more different rubber-modified styrenic resins having different structures and molecular weights. For example, ABS as rubber-modified styrene resin
By using resin and MBS resin (methyl methacrylate, butadiene, styrene resin) in combination,
Excellent melt flowability and impact resistance can be simultaneously improved. A specific example of such an MBS is "METABLEN C- manufactured by Mitsubishi Rayon Co., Ltd. of Japan.
"223A" and "Metablene C-323A", "Kane Ace M-511" and "Kane Ace B-564" manufactured by Kanegafuchi Chemical Industry Co., Ltd., and "M" manufactured by Taiwan Plastics Co., Ltd. -5
1 ”and the like.

In the present invention, when the rubber-modified styrene resin is used in combination with the aromatic polycarbonate resin, the amount of the rubber-modified styrene resin is 100 parts by weight based on 100 parts by weight of the total amount of the aromatic polycarbonate resin and the rubber-modified styrene resin. , 50 to 5 parts by weight, more preferably 40 to 10 parts by weight, still more preferably 30 to 15 parts by weight. If the rubber-modified styrene-based resin exceeds 50 parts by weight, the heat resistance and the flame retardancy in a thin-walled molded product will be insufficient, while if it is less than 5 parts by weight, the melt fluidity tends to decrease.

Further, as the component (A) in the present invention, a polyphenylene ether resin or a resin mainly composed of a polyphenylene ether resin can be particularly preferably used. Here, the polyphenylene ether resin is a polyether having an aromatic ring in the main chain, such as poly (2,6-dimethyl-1,4-phenylene ether),
A copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferable, and poly (2,6-dimethyl-1,4-phenylene ether) can be preferably used.

The reduced viscosity η _sp / C (0.5 g / dl, chloroform solution, measured at 30 ° C.) of the above polyphenylene ether resin used in the present invention is 0.20 to 0.70.
It is preferably in the range of dl / g, and 0.30 to 0.
More preferably, it is in the range of 60 dl / g. As a means for satisfying the above requirement regarding the reduced viscosity η _sp / C of the polyphenylene ether resin, it can be carried out by adjusting the amount of catalyst in the production of the polyphenylene ether resin.

As the component (A) preferably used in the present invention, a resin mainly composed of a polyphenylene ether resin is a resin composed of the polyphenylene ether resin and a styrene resin, and the styrene resin is styrene. The polymer mainly composed of the components or the rubber-modified styrene resin is shown, but polystyrene and high-impact polystyrene can be preferably used.

The styrenic resin used in combination with the polyphenylene ether resin may be blended in any proportion, but the polyphenylene ether resin may be used in order to obtain high flame retardancy in a thin molded article. 30 to 99 parts by weight of styrene resin 70 to
A proportion of 1 part by weight is preferred.

The component (B) in the present invention is a flame retardant, and the flame retardant (B) according to the present invention means a flame retardant aid which accelerates the flame retardant action in combination with the conventionally known flame retardant and flame retardant. That is. Examples of the component (B) used in the present invention include organic phosphorus compounds, organopolysiloxanes, halogen-containing compounds, metal oxides, metal hydroxides,
Examples thereof include triazine compounds, red phosphorus, zirconium compounds, polyphosphate compounds, sulfamic acid compounds, organic sulfonic acid alkali metal salts, and the like.

Among the components (B) listed above, the organic phosphorus compound and the organopolysiloxane can be preferably used in the present invention. Among the above organophosphorus compounds, in the present invention, since the volatile component at the time of molding can be reduced, an organophosphorus compound oligomer which is a compound having two or more phosphorus atoms in its structure can be preferably used. Those selected from the group of compounds represented by the following formula (1) can be particularly preferably used.

[0064]

[Chemical 20]

Substituents R ^a , R ^b and R in the above formula (1)
^c and R ^d each independently represent an aryl group having 6 to 12 carbon atoms, and one or more hydrogen atoms thereof may or may not be substituted. When one or more hydrogen atoms are substituted, the substituent is an alkyl group having 1 to 30 carbon atoms, an alkoxy group, an alkylthio group, a halogen, an aryl group, an aryloxy group, an arylthio group, a halogenated aryl group, etc. Or a group in which these substituents are combined (for example, an arylalkoxyalkyl group or the like) or a group in which these substituents are bonded 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. Substituents R ^a , R ^b and R in the compound of the above formula (1)
^{When c} and R ^d are an alkyl group or a cycloalkyl group, the thermal stability is generally lowered and decomposition is likely to occur during melt kneading.

X in the above formula (1), which represents a group of compounds as an example of the organic phosphorus compound, is a diphenyloldimethylmethane residue as described above. As the oligomeric phosphoric acid ester, there are those in which X is a resorcinol residue or a hydroquinone residue, and in comparison with these, the compound represented by the above formula (1) (where X is a diphenyloldimethylmethane residue) is used. It is preferable to use, as the organic phosphorus compound, a compound selected from the group of compounds mentioned above, since the hydrolysis resistance and thermal stability of the organic phosphorus compound are improved.

The organophosphorus compound oligomer represented by the formula (1) is usually used as a mixture of a plurality of different organophosphorus compound oligomers having different values of n (n is a natural number) in the formula (1). Many. At this time, it is preferable that the plurality of different organophosphorus compound oligomers have a weight average condensation degree (N) of 1 to less than 1.2. N is obtained by gel permeation chromatography or liquid chromatography to obtain the weight fraction (A _n ) of each component having different n, and is calculated by N = Σ (n · A _n ) / Σ (A _n ). It

Here, in _order to obtain A _n , a UV detector or RI detector is usually used as a detector. However, in the calculation of N, a compound having a structure in which n in the above formula (1) is 0 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), a compound in which n is 0 is excluded from the calculation of N. The weight average condensation degree N is
It is usually 1 or more and 5 or less, preferably 1 or more and 2 or less, and 1
It is more preferably 1.5 or more and 1.5 or less, and particularly preferably 1 or more and less than 1.2. The smaller N is, the better the compatibility with the resin is, the better the melt fluidity is, and the higher the flame retardancy is. In particular, the compound of N = 1 has a particularly excellent balance between flame retardancy and melt fluidity in the resin composition. When N of the compound of the formula (1) as the organic phosphorus compound is 5 or more, the viscosity of the compound becomes large, and the melt fluidity tends to be lowered particularly in a high shear rate region, and the flame retardancy is high. Sex tends to decrease.

Further, the acid value of the organic phosphorus compound used in the present invention is preferably 0.1 mgKOH / g or less, more preferably 0.08 mgKOH / g or less, and further preferably 0.05 mgKOH / g. g or less, and particularly preferably 0.01 mgKOH / g or less. By using an organic phosphorus compound having a low acid value, it is possible to obtain a flame-retardant resin composition having more excellent resistance to moist heat.

Further, the organic phosphorus compound represented by the above general formula (1) is disclosed in US Pat. No. 2,520,090,
JP-B-62-25706, JP-A-63-2276
According to the method described in Japanese Unexamined Patent Publication No. 32, etc., phosphorus oxychloride is reacted with bisphenol A and monohydric phenol in the presence of a Lewis acid catalyst such as magnesium chloride or aluminum chloride to synthesize, and thereafter, a crude organophosphorus compound The product can be obtained by washing, purifying, and drying, but in the organophosphorus compound used in the present invention, mainly catalyst-derived magnesium and aluminum contained in the organophosphorus compound, alkali for washing and purifying, and alkali When using an aqueous solution containing a metal ion such as earth, the total amount of metal components such as sodium, potassium and calcium that may be introduced is preferably 30 ppm or less, more preferably 20 ppm or less, further preferably 10 ppm or less, Particularly preferably, it is 5 ppm or less, and the flame retardancy is superior to the moist heat resistance. Desirable in obtaining the resin composition.

Furthermore, the chlorine concentration contained in the organic phosphorus compound is preferably 20 ppm or less, more preferably 1 ppm or less.
It is preferably 0 ppm or less, more preferably 5 ppm or less, and particularly preferably 1 ppm or less in order to obtain a flame-retardant resin composition having more excellent moist heat resistance.

Further, as the component (B) which can be preferably used in the present invention, an organopolysiloxane can be mentioned. The organopolysiloxane preferably used as the component (B) in the present invention is known per se. For example, it is represented by the following formula (2).

[0074]

[Chemical 21] (In the formula, each R _X independently represents a hydrogen atom, an aromatic group, an aliphatic group, an alicyclic group, or a reactive functional group.
m and n are each independently an integer of 0 or 1 or more. )

Specific examples of R _X include aromatic groups
Examples thereof include aryl groups such as phenyl group, xylyl group and tolyl group, halogenated aryl groups such as chlorophenyl group, aralkyl groups such as phenylethyl group and benzyl group. Examples of the aliphatic group include an alkyl group such as a methyl group, an ethyl group and a propyl group, an alkenyl group such as a vinyl group, a propenyl group and a butynyl group, and a halogenated alkyl group such as a chlorobutyl group. Examples of the alicyclic group include a cyclohexyl group and the like. Examples of the reactive functional group include a hydroxyl group and an alkoxy group, and further, an epoxy group, an amino group, a carboxylic acid group,
Examples thereof include an aliphatic group, an aromatic group, and an alicyclic group partially substituted with a reactive group such as a carboxylic acid ester group, a hydroxyl group, and an alkoxy group. Among these, in the present invention,
A methyl group, a phenyl group, a hydroxyl group and an alkoxy group are preferably used.

In the present invention, the ratio of hydrogen atom, aromatic group, aliphatic group, alicyclic group and reactive functional group in the organopolysiloxane is not particularly limited. Generally, the more aromatic groups there are, the more excellent the heat resistance is, and the better the compatibility with the resin tends to be. In addition, l, m, and n in the formula shown in formula (2)
The ratio of is also not particularly limited. It becomes liquid as l becomes larger, and becomes rubbery as n becomes larger. Preferably,
The molar ratio of 1: m: n is from 1: 0 to 8: 0-5. Further, the weight average molecular weight of the organopolysiloxane is generally 5,000 to 300,000 and is not particularly limited.

Further, in the present invention, as the component (B),
It is also possible to use an alkali metal salt of an aromatic sulfonic acid and / or an alkali metal salt of a perfluoroalkane sulfonic acid, and to further improve the flame retardancy by using these in combination with the organopolysiloxane. Is possible. The alkali metal salt of aromatic sulfonic acid is represented by the following formula, for example.

[0078]

[Chemical formula 22] (In the formula, R is a phenyl group or a naphthyl group, A is one or more selected from a halogen atom, an alkyl group, an aryl group, a vinyl group, an alkoxy group, an amino group, a methyl ester group and an ethyl ester group. The substituent, M represents an alkali metal, and when R is a phenyl group, m and n are integers (m + n ≦ 6) of 0 to 5 and 1 to 2, respectively, and when R is a naphthyl group, m and n.
Represents an integer of 0 to 7 and 1 to 2 (m + n ≦ 8). )

Examples of the alkali metal salt of aromatic sulfonic acid satisfying the above formula include p-toluenesulfonic acid and p-toluenesulfonic acid.
-Styrene sulfonic acid, 1-naphthalene sulfonic acid,
Dimethyl isophthalate-5-sulfonic acid, 2,6-naphthalenedisulfonic acid, benzenesulfonic acid, benzenedisulfonic acid, dimethyl 2,4,6-trichloro-5-sulfoisophthalate, 2,5-dichlorobenzenesulfonic acid, 2 , 4,5-Trichlorobenzenesulfonic acid, p-
Alkali metal salts such as iodobenzene sulfonic acid and 7-amino-1,3-naphthalene disulfonic acid are mentioned,
These can be used alone or in combination. The alkali metal salt of perfluoroalkanesulfonic acid is represented by the following formula, for example.

[0080]

[Chemical formula 23] (In the formula, M represents an alkali metal and n represents an integer of 1 to 8.)

Examples of the alkali metal salt of perfluoroalkanesulfonic acid satisfying the above formula include, for example, perfluoromethanesulfonic acid, perfluoroethanesulfonic acid,
Alkali metal salts such as perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, and perfluorooctanesulfonic acid are listed, and these may be used alone or It can be used in combination with more than that.

In the present invention, when an alkali metal salt of aromatic sulfonic acid and / or an alkali metal salt of perfluoroalkane sulfonic acid represented by the formulas (22) and (23) is used, the compounding amount is A) 100
0.01 to 2 parts by weight is preferable with respect to parts by weight. 0.0
If it is less than 1 part by weight, the effect of improving the flame retardancy is insufficient, and if it exceeds 2 parts by weight, the thermal stability is poor, which is not preferable. The range is more preferably 0.01 to 1 part by weight, still more preferably 0.02 to 0.4 part by weight.

The amount of the component (B) in the resin composition of the present invention depends on the kind of the component (B), the combination of the component (A) and the component (B), etc., but is 100 parts by weight of the component (A). On the other hand, it is 0.01 to 40 parts by weight, preferably 0.1 to 30 parts by weight, and more preferably 1 to 20 parts by weight. If the amount of component (B) is less than 0.01 parts by weight, the flame retardancy of the thin-walled molded product will be insufficient, while if it exceeds 40 parts by weight, the impact resistance of the resin composition will be insufficient.

The component (C) used in the present invention is a silicone oil, which is a polymer of an organosilicon compound which is liquid at room temperature and has a viscosity at 25 ° C. of 0.1 to 1,000 cs (centistokes). .

In the present invention, the component (C) is an "uncolored flame-retardant resin composition" mainly composed of the above components (A) and (B).
When colored, the coloring agent (D) acts as a dispersant or a spreading agent, and high flame retardancy can be maintained even in a thin molded product. Further, the component (C) can simultaneously obtain an effect as a release agent at the time of molding in the colored flame-retardant resin composition of the present invention. Examples of the silicone oil used in the present invention include those selected from the compound group represented by the following formula.

[0086]

[Chemical formula 24] (In the formula, each R _X is independently a hydrogen atom and a carbon number of 6
To 30 aryl groups, C1 to C50 aliphatic groups or alicyclic groups, and n is 0 or an integer of 1 or more. )

Among the compounds shown above, particularly preferable examples of the component (C) used in the present invention are methyl silicone oil, methyl hydrogen silicone oil, methylphenyl silicone oil and cyclic dimethyl silicone oil. You can

The component (C) used in the present invention is 25 ° C.
Has a viscosity of 0.1 to 1,000 cs, preferably 1 to 700 cs, more preferably 5 to 500 cs.
Is. When the viscosity of the component (C) is less than 0.1 cs, the viscosity is low and the effect as a spreading agent for spreading the colorant (D) on the pellet surface of the uncolored flame-retardant resin composition is unsatisfactory. Sufficient, while the viscosity of component (D) is 1,000
When it exceeds cs, since the viscosity is high, the permeability to the component (D) is insufficient, and the dispersibility of the colorant in the resin composition tends to decrease.

In the present invention, the component (C) is the organopolysiloxane (component (B)) represented by the above formula (2).
In the above formula (2), m = n =
0 (that is, the one represented by Chemical Formula 24) and the viscosity at 25 ° C. is 0.1 to 1,000.
The component having 0 cs is the component (C).

The component (C) used in the present invention is
The so-called modified silicone oil in which R _X shown in the chemical formula 24 is replaced with various functional groups or a chemical structure different from R _X may be used. 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, polyether-modified silicone oil. , Methyl styryl modified silicone oil, alkyl modified silicone oil, C8-30 higher fatty acid ester modified silicone oil, hydrophilic special modified silicone oil, higher alkoxy modified silicone oil, fluorine modified silicone oil and the like.

The amount of the component (C) used in the present invention is 0.001 to 3 with respect to 100 parts by weight of the "uncolored flame-retardant resin composition" mainly containing the components (A) and (B). Parts by weight, preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1 part by weight. When it is less than 0.001 part by weight, the dispersibility of the colorant is lowered, while when it exceeds 3 parts by weight, the heat resistance of the resin composition is lowered,
Undesirably, the component (C) oozes out onto the surface of the molded product.

The content of the component (C) contained in the colored flame-retardant resin composition can be determined by gas chromatography / mass spectrometry (GC / MS method) or liquid chromatography / mass spectrometry (LC / MS method). It is possible to quantify.

The component (D) used in the present invention is a colorant. The colorant in the present invention is a pigment or dye used for coloring a resin, for example, titanium white (titanium oxide), titanium yellow, red iron oxide, ultramarine blue, spinel green and other inorganic pigments, condensed azo organic pigments, Quinacridone-based organic pigments, isoindolinone-based organic pigments, perylene-based organic pigments, anthraquinone-based organic pigments, organic pigments such as phthalocyanine-based organic pigments, carbon black, perylene-based dyes, perinone-based dyes, anthraquinone-based dyes,
Examples of the heterocyclic dyes include dyes.

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 preferable. The average particle size of titanium oxide used is not particularly limited, but it is from 0.01 to
The thickness of 0.5 μm is preferable, and the thickness of 0.1 to 0.3 μm is particularly preferable. Further, it may be pre-treated with a treating agent which is usually used as a surface treating agent for titanium oxide, as long as the object of the present invention is not impaired. Examples of such treating agents include alumina and silica,
Each may be used alone or in combination.
Further, as the surface treatment agent, an organic dispersant, a stabilizer and the like are contained, and the organic dispersant and the stabilizer may correspond to the component (E) of the present invention, but these are used within the scope of the present invention. It is possible to

The component (D) in the present invention is usually used in combination of a plurality of components (D) in order to achieve the desired color development, and the amount of the component (D) used is the desired color tone or the color tone of the base resin. The total amount of the component (D) is 0.0001 to 1 with respect to 100 parts by weight of the uncolored flame-retardant resin composition mainly composed of the components (A) and (B).
0 parts by weight, preferably 0.001 to 7 parts by weight, more preferably 0.01 to 5 parts by weight, and further preferably
It is 0.1 to 3 parts by weight. When the amount of the component (D) is less than 0.0001 parts by weight, it is difficult to keep the product color tone constant, while when it exceeds 10 parts by weight, the mechanical properties of the resin composition are deteriorated and the flame retardancy is deteriorated. There is something to do.

The lubricant (E) in the present invention means an aliphatic hydrocarbon, a polyolefin wax, a higher carboxylic acid,
A compound selected from the group of compounds such as higher carboxylic acid metal salt, fatty acid amide, fatty acid ester, and higher alcohol is shown. Further, as a general concept, the component (C) (silicone oil) shown in the present specification is included in the category of “lubricant”, but in the present specification, the component (C) is referred to in the present specification. It is excluded from "lubricant".

Although some of these lubricants (E) are already contained in the resin raw material, they are used as a processing aid when producing the resin composition or as a coloring agent when coloring the resin composition. As a dispersant or spreading agent, and as a mold release agent for improving mold release of a molded body during molding,
Some are blended with the resin composition.

Among the components (E), the aliphatic hydrocarbon is an aliphatic hydrocarbon compound having 5 to 100 carbon atoms,
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, and is a paraffin wax, polyethylene wax, polypropylene wax, ethylene / vinyl acetate copolymer wax, Examples include polyolefin ionomer waxes.

The higher carboxylic acid has 5 to 5 carbon atoms.
A fatty acid having 50 saturated or unsaturated bonds, for example, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, melicinic acid. , Tetratriacontanoic acid, glutaric acid, adipic acid, azelaic acid, naphthenic acid, rosin acid, oleic acid, linoleic acid, linolenic acid and the like.

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. it can. The fatty acid amide has 12 to 150 carbon atoms having at least one acid amide bond in the molecule.
Examples thereof include stearic acid amide, oleic acid amide, erucic acid amide, ethylenebisstearic acid amide, methylenebisstearic acid amide, and ethylenebisoleic acid amide.

The fatty acid ester is a compound having at least one ester bond in the molecule and having 10 to 200 carbon atoms, and is, for example, an ester of a higher carboxylic acid such as butyl stearate and a monohydric alcohol, or ethylene glycol. Monostearate, glycerin monostearate, trimethylolpropane monostearate, pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol distearate, glycerin dilaurate, glycerin tristearate, trimethylolpropane distearate, glycerin Distearate, glycerin tribehenate, pentaerythritol tristearate, trimethylolpropane tricaprate, trimethylolpropane dioleate, pentaerythritol Can be mentioned esters of higher carboxylic acids tetrastearate and the like with a polyhydric alcohol.

The higher alcohol is a compound having one or more hydroxyl groups in the molecule and having 8 to 50 carbon atoms,
For example, stearyl alcohol can be mentioned.

In the present invention, the total amount of the lubricant (E) contained in the colored flame-retardant resin composition, that is, the total amount of the lubricant components contained in the colored flame-retardant resin composition according to the present invention is 3,000 weight. ppm or less, preferably 0.01
To 2,000 ppm by weight, more preferably 0.1
˜1,500 ppm by weight, particularly preferably 1 to 1.00
By setting the content to 0 ppm by weight, a high degree of flame retardancy can be achieved even in the case of a thin molded product.

The content of the component (E) in the colored flame-retardant resin composition according to the present invention is such that it is a good solvent / solvent from the composition.
Separation or extraction can be performed by combining poor solvents, and quantification can be performed by combining analytical techniques such as a proton NMR method, a GC / MS method, and an LC / MS method.

The colored flame-retardant resin composition according to the present invention may further contain a fluoropolymer (F) for the purpose of preventing dropping of combustion products. In the present invention, a fluoropolymer having a fibril forming ability can be preferably used, and a fine powder fluoropolymer, an aqueous dispersion of fluoropolymer, AS
Various forms of fluoropolymer can be used, such as a powdered mixture with a second resin such as PMMA or PMMA.

In the present invention, in particular, an aqueous dispersion of a fluoropolymer can be preferably used as the component (F), and the aqueous dispersion of the fluoropolymer means polytetrafluoroethylene, tetrafluoroethylene / propylene copolymer A tetrafluoroethylene polymer such as a coalesced polymer, a perfluoroalkane polymer other than polytetrafluoroethylene, preferably a tetrafluoroethylene polymer, and particularly preferably polytetrafluoroethylene is described in, for example, “Fluorine Resin Handbook” (Nikkan Kogyo Shimbun, 1990) Manufactured by suspension polymerization or emulsion polymerization as described in 1., and further used as a form of an aqueous dispersion.

That is, the dispersion liquid of fine particles of fluoropolymer obtained by suspension polymerization or emulsion polymerization is 40 to 7
1 shows a milky white aqueous dispersion stabilized with a surfactant after being concentrated to a concentration of 0 wt%. The concentration of the fluoropolymer in the aqueous dispersion of the fluoropolymer can be diluted with water as long as the concentration is such that the dispersion state is stable, but 5 to 70 wt% is preferable,
More preferably 20 to 65 wt%, particularly preferably 30
~ 60 wt%. The average primary particle diameter of the fluoropolymer in the aqueous dispersion is 0.01 to 0.6.
0 μm is preferable, and 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 alkylphenol and ethoxylated higher alcohol are preferably used, and the compounding amount thereof is usually 1 -15 wt%, preferably 2-10
wt%, and more preferably 3 to 7 wt%. further,
The aqueous dispersion of the fluoropolymer has a pH
Those whose values are usually adjusted to 9 to 10 are preferably used. When the fluoropolymer concentration 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. As an aqueous dispersion of a fluoropolymer that can be preferably used in the present invention, "Teflon (R) 30J" manufactured by Mitsui DuPont Fluorochemical Co., Ltd., "Polyflon D-1", "Polyflon D-" manufactured by Daikin Industries, Ltd.
2 "," Polyflon D-2C "," Polyflon D-2C
E ”can be illustrated.

As the component (F), a fluoropolymer prepared as a powdery mixture with a second resin such as AS or PMMA can also be preferably used. Techniques relating to fluoropolymers made into a powdery mixture with these second resins are disclosed in JP-A-9-95583, JP-A-11-49912, JP-A-2000-143966, and JP-A-2000.
It is disclosed in Japanese Patent Publication No.-297189. Examples of fluoropolymers that can be preferably used in the present invention as a powdery mixture with these second resins include "Blendex 449" manufactured by GE Specialty Chemicals, and "Metabrene A-3000" manufactured by Mitsubishi Rayon Co., Ltd. You can

When the component (F) is used in the colored flame-retardant resin composition according to the present invention, its blending amount is preferably 0.05 to 2 parts by weight relative to 100 parts by weight of the component (A), 0.1 to 1.5 parts by weight is more preferable, 0.15 to 1.0 parts by weight is still more preferable, and 0.1 to 1.0 part by weight is particularly preferable.
2 to 0.8 parts by weight. When the amount of the fluoropolymer is less than 0.05 part by weight, the effect of preventing the dropping of the combustion product may be insufficient, while when it exceeds 2 parts by weight, melt flowability and impact resistance are insufficient. There is a tendency. Furthermore, in the colored flame-retardant resin composition of the present invention, the melt-kneading step of the flame-retardant resin composition, melt retention inside the molding machine at the time of molding, or when the molded body is exposed to a high temperature environment, mainly air Heat resistant stabilizers such as hindered phenolic antioxidants, phosphite heat stabilizers, and sulfur heat stabilizers can be preferably used for the purpose of preventing the progress of heat aging due to oxygen in the interior.

The hindered phenol antioxidant is an antioxidant composed of a compound having at least one hindered phenol structure in the molecule, and examples thereof include 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, a C7-9 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-
Tris (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-triazine-2
-Ylamino) phenol, 2,6-di-t-butyl-
4-methylphenol, styrenated phenol,
2,2'-methylenebistrene-bis- (4-methyl-
6-t-butylphenol), 2-t-butyl-6-
(3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 4,
4'-butylidene-bis- (3-methyl-6-t-butylphenol), 4,4'-thio-bis- (3-methyl-6-t-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, etc. may be mentioned, and in the present invention, among them, the molecular weight is 5
Those of 00 or more can be preferably used because they have little heat aging resistance and little bleed-out to a molded body, and 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 at least one trivalent phosphite structure in the molecule, and is, 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 and bis- (2,4-di-t-butylphenyl) pentaerythritol diphosphite can be mentioned, and in the present invention, particularly tris (2,4-di-t- Butylphenyl)
Phosphite and bis- (2,4-di-t-butylphenyl) pentaerythritol diphosphite are preferred.

Further, the sulfur-based heat stabilizer is an antioxidant composed of a compound having at least one sulfur atom in the molecule, and is, for example, a dialkyl group having 12 to 18 carbon atoms.
3,3′-thiodipropionate, tetrakis [methylene-3- (alkylthio) propionate] methane, bis [2-methyl-4- (3-alkyl-thiopropionyloxy) -5-tertiarybutylphenyl] sulfide are mentioned. You can In the present invention, the above heat resistance stabilizer may be used as a single component, or a plurality of components may be used in combination.

In the present invention, the amount of the heat stabilizer used is 100 parts by weight of the component (A).
The total amount of the heat resistance stabilizer is preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.5 part by weight,
It is more preferably 0.1 to 0.3 parts by weight.

In the colored flame-retardant resin composition of the present invention,
For the purpose of modifying the resin composition as necessary, glass fiber, glass flakes, glass beads, calcium carbonate,
It is also possible to add an inorganic filler such as talc or mica, a carbon fiber, a reinforcing material such as charcoal, or another thermoplastic resin. Further, in the 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 colored flame-retardant resin composition of the present invention will be described in detail. The method for producing a colored flame-retardant resin composition of the present invention comprises the step of adding the component (C) to the pellets of the uncolored flame-retardant resin composition containing the components (A) and (B) as main components.
And a component (D) are mixed and melt-kneaded with an extruder to produce a colored flame-retardant resin composition, which comprises a lubricant (E) contained in the colored flame-retardant resin composition. This is a manufacturing method in which the total amount is 3,000 ppm by weight or less.

Here, the uncolored flame-retardant composition is produced by melt-kneading the components (A), (B) and other components using a melt-kneading device, preferably a twin-screw extruder. To be done. In the production of the uncolored flame-retardant composition, the components (A), (B) and other components which are raw materials are extruded after previously mixing the components using a pre-mixing device such as a tumbler or a ribbon blender. It is also possible to obtain the uncolored flame-retardant composition by supplying it to a machine and melt-kneading it, but by supplying each raw material component to an extruder independently and performing melt-kneading, it is uncolored. It is also possible to obtain a flame-retardant composition.

In particular, when the flame retardant (B) is liquid,
It is preferable that the component (B) is directly supplied to the extruder using a gear pump, a plunger pump or the like for melt kneading. When an aqueous dispersion of a fluoropolymer is used as the component (F), the component (F) can be mixed with the component (A) in advance and then supplied to the extruder. It is also possible to melt-knead by independently supplying () to the extruder.

In the production of the uncolored flame-retardant composition, the extruder has a cylinder set temperature of 200 to 400 ° C.
Preferably 220-350 ° C, more preferably 230-
300 ° C, and the extruder screw rotation speed is 100
To 700 rpm, preferably 200 to 500 rpm, and the average residence time in the extruder is 10 to 150 seconds for melt kneading, and the melt kneading is performed so as not to give an excessive heat to the resin during kneading. The melt-kneaded uncolored 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 resin composition.

In the method for producing a colored flame-retardant resin composition of the present invention, the "uncolored flame-retardant resin composition" pellets obtained by the above-mentioned method are added to the components (C), (D) and other components. The colored flame-retardant resin composition is produced by introducing the mixture in which the components are mixed, preferably into an extruder having a vent port, and melt-kneading the mixture.

A preferred method of mixing the component (C) and the component (D) into the pellets of the uncolored flame-retardant resin composition is to use a mixing device such as a tumbler or a ribbon blender. The component (C) is blended with the pellets of the "resin composition", and the mixture is generally stirred for 1 to 60 minutes, preferably 5 to 40 minutes. Thereafter, the component (D) 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 it is usually performed at room temperature. "Uncolored flame-retardant resin composition" pellets thus prepared, and the components (C) and (D)
The mixture consisting of (1) and (2) is preferable because the colorant (D) can be uniformly spread on the surface of the "uncolored flame-retardant resin composition" pellets.

As an extruder used in the production of the 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 having an enhanced kneading and dispersing function, for example, 3 to 6 stages of Dalmaged screw parts, preferably a unimelt 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, since the kneading function is generally superior to that of the single-screw extruder, it is possible to reduce the amount of the colorant dispersant or the colorant spreader used. Alternatively, it is more preferable that the colorant can be satisfactorily dispersed in the resin composition without using them. In the production of the colored flame-retardant resin composition of the present invention, it is more preferable to carry out melt-kneading for coloring with an extruder and devolatilize the resin composition in order to enhance the flame retardancy.

Here, "devolatilization" means to remove the volatile components generated in the melt-kneading step through atmospheric pressure opening or reduced pressure through a vent port provided in the extruder. The vent port attached to the extruder for performing the devolatilization is an extruder position where the unmelted portion of the raw material uncolored flame-retardant resin composition pellets is substantially not contained in the extruder inside. Is set as a reference position, it is installed at the reference position or at an extruder position further downstream than the reference position in the extrusion direction. Incidentally, the installation position of the vent port, the unmelted portion of the raw material resin composition pellets is confirmed to be in a molten state substantially not included, by visually observing the state of the molten resin at the vent port position. , You can easily make a decision.

Further, the shape of the screw of the extruder at the vent position is preferably a deep groove type full flight screw shape. When the screw shape of the extruder at the vent 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 performed effectively and vent up of the molten resin from the vent port is possible. It is particularly preferable in the present invention because it can be prevented.

In the present invention, when devolatilization is performed, it is preferable to open the vent port attached to the extruder to the atmosphere.
It is more effective to carry out depressurization devolatilization through the vent port in order to enhance the flame retardant effect, and preferably 0.01 to 40.
0 mmHg-G (gauge pressure), more preferably 0.1
300 mmHg-G, more preferably 1-150 mmH
Volatilization under reduced pressure is performed with g-G. When coloring, the extruder preferably sets the extruder cylinder set temperature to 180 to 3
00 ° C., more preferably 200 to 280 ° C., further preferably 220 to 250 ° C., and the extruder screw rotation speed is 30 to 500 rpm, preferably 50 to 300 rpm,
More preferably, kneading for coloring is performed at 70 to 200 rpm.

The residence time of the resin in the extruder is usually properly selected within the range of 10 to 150 seconds. Further, in the present invention, the lubricant (E) can be blended, if necessary, within the range of the amount described in the present invention. In this case, the lubricant (E) is used in all stages of melt kneading. It is possible to mix. In particular, when coloring is performed using a single-screw extruder, in order to improve the dispersibility and coloring uniformity of the colorant (D), the component (E) as a dispersant or a spreading agent is used.
It may be preferable to use an appropriate amount. In this case, in the present invention, it is necessary to consider the total amount of the component (E) in the range of 3,000 weight ppm or less based on the colored flame-retardant resin composition.

The molding method for obtaining a molded article comprising the colored flame-retardant resin composition of the present invention is not particularly limited, and examples thereof include injection molding, gas assist molding, extrusion molding, compression molding and the like. Molding is preferably used.

Since the colored flame-retardant resin composition of the present invention has excellent flame retardancy even in a thin molded product, it is suitable for obtaining a molded product having a thin portion, and the molded product is preferably thick. A molded product in which a portion having a thickness of 2 mm or less is 30% by weight or more of the entire molded product, more preferably a portion having a thickness of 2 mm or less is 50% by weight or more of the entire molded product,
More preferably, it can be suitably used in the case of obtaining a molded product in which the portion having a wall thickness of 2 mm or less is 70% by weight or more of the entire molded product.

Examples of molded articles using the colored flame-retardant resin composition of the present invention include personal computer monitors, notebook computers, copiers, printers, and other OA equipment housings, OA equipment chassis, mobile phone housings, Etc.

[0133]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be specifically described below with reference to Examples and Comparative Examples. In Examples or Comparative Examples, the following components (A), (B),
A colored resin composition was produced using (C), (D), (E), (F) and optionally other components. Although some of the components (C) do not satisfy the requirements of the present invention, they are classified as the components (C) for convenience.

1. Component (A): Thermoplastic resin (PC1) A bisphenol A-based polycarbonate produced from bisphenol A and diphenyl carbonate by a melt transesterification method and containing no lubricant (E). Weight average molecular weight (Mw) = 24,500 Phenolic end group ratio (ratio of phenolic end groups to the total number of end groups) = 29 mol% Lubricant (E) content = 0 weight ppm

(PC2) A bisphenol A-based polycarbonate obtained by the phosgene method, containing no lubricant (E). Weight average molecular weight (Mw) = 26,000 Phenolic end group ratio (ratio of phenolic end groups to the total number of end groups) = 8 mol% Lubricant (E) content = 0 weight ppm

(ABS) The ABS graft copolymer obtained by polymerizing by emulsion polymerization and coagulating by sulfate salting out, followed by washing and drying was used as acrylonitrile unit 2
7 wt%, styrene unit 73 wt%, obtained by diluting and kneading with AS resin (styrene-acrylonitrile resin) having a weight average molecular weight (Mw) of 110,000, butadiene rubber content content is 25 wt%, rubber weight An emulsion polymerization acrylonitrile-butadiene-styrene resin having an average particle diameter of 0.26 μm, which contains 1,200 ppm by weight of a lubricant component (component (E): rosin acid) as an emulsifier residue. Rosin acid content (component (E)) = 1,200 ppm by weight

(MBS) Polymerized by emulsion polymerization, coagulated by sulfate salting out, washed and dried to obtain a butadiene rubber content of 80 wt%,
Styrene unit 50 wt% and methyl methacrylate unit 5
It is a powdery methylmethacrylate-butadiene-styrene (MBS) resin having 0 wt% of a copolymerization component of 20 wt% and a rubber weight average particle diameter of 0.21 μm, and a lubricant component (component (E ): Those containing 2,500 parts by weight of rosin acid). Rosin acid content (component (E)) = 2,500 ppm by weight

(PPE) Oxidative coupling polymerization of 2,6-xylenol in the presence of dibutylamine according to the method described in US Pat. No. 4,788,277 (Japanese Patent Application No. 62-77570). Manufactured by η _sp
/C=0.40 (0.5 g / dl, chloroform solution, measured at 30 ° C.), poly (2,6-dimethyl-)
1,4-phenylene ether).

(HIPS) High-impact polystyrene having a butadiene rubber component of 12% by weight and a styrene unit of 88% by weight.

2. Component (B): flame retardant (organopolysiloxane), which is produced by a known method and has a molar ratio of 1: m: n of 1:
An organopolysiloxane having a molecular weight of 50,000, which is 3.8: 0, 98% or more of R _X is composed of a phenyl group and a methyl group, and the ratio thereof is 60:40.

(Sulfonic acid metal salt) Perfluorobutanesulfonic acid potassium salt (trade name F114) manufactured by Dainippon Ink and Chemicals, Inc.

(Phosphate 1) An organophosphorus compound oligomer represented by the chemical formula 20, wherein substituents R ^a , R ^b ,
R ^c and R ^d are all phenyl groups, the weight average condensation degree (N) is 1.08, and the magnesium content is 7.2.
ppm, a chlorine content of 1 ppm or less, and an acid value of 0.01 mgKOH / g.

(Phosphate 2) manufactured by Daihachi Chemical Co., Ltd.
Resorcinol-di-phosphate (CR733S) weight average condensation degree (N) is 1.52, magnesium content is 5.2 ppm, chlorine content is 1 ppm or less, and acid value is 0.01 mg / KOH. some stuff.

3. Component (C) (Silicone oil 1) Shin-Etsu Chemical Co., Ltd. dimethyl silicone oil (trade name KF96-50) Viscosity 50 ± 2.5 cs (25 ° C.), specific gravity 0.955-0.9
65 (25 ° C), pour point -50 ° C or less, flash point 300 ° C
that's all

(Silicone oil 2) Shin-Etsu Chemical Co., Ltd. dimethyl silicone oil (trade name: KF9
6-3000) Viscosity 3,000 ± 150 cs (25
℃), specific gravity 0.965 to 0.975 (25 ℃), pour point -50 ℃ or less, flash point 315 ℃ or more

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

5. Ingredient (E): lubricant (release agent) pentaerythritol tetrastearate (dispersant) polyethylene oxide wax having a molecular weight (Mw) of 4,000 (spreading agent) paraffin oil manufactured by Esso Oil Co., Ltd. Stall J-352)

6. Ingredient (F): Fluoropolymer (PTFE) GE Specialty Chemicals Co. mixed powder of polytetrafluoroethylene and acrylonitrile-styrene copolymer (Blendex 449)
PTFE content = 50 wt%

7. Other components (I-1076: hindered phenolic antioxidant)
Ciba Specialty Chemicals (trade name IR
GANOX 1076) Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (P-168: phosphite heat stabilizer) manufactured by Ciba Specialty Chemicals (trade name IRGAFOS1
68) Tris (2,4-di-t-butylphenyl) phosphite

(Talc) Talc manufactured by Nippon Talc Co., Ltd. (trade name: Microace P)
-3) Average particle size = 0.4 µm, L / D = 8, bulk specific volume = 2.3
ml / g (GFL) Glass flakes manufactured by Nippon Sheet Glass Co., Ltd. (trade name REFG-101) Average particle diameter D = 40 μm, L / D = 8

(Uncolored flame-retardant resin composition (uncolored composition)
Production Examples 1 to 7) Components (A), (B), (F) and other components in the amounts (units are parts by weight) shown in Table 1 are melt-kneaded using a twin-screw extruder and colored. Pellets of an uncolored flame-retardant resin composition containing no agent (described as uncolored composition in Tables 1 to 3) were obtained. However, in Table 1, the number of parts of the component (F) indicates the number of parts as a fluoropolymer.

[0152]

[Table 1]

In the production of the uncolored compositions 1 to 4, the melt-kneading device was a twin-screw extruder (ZSK-25, L / D = 37, Wern.
er & Pfleiderer), and melt-kneading under the conditions that the cylinder temperature is 245 ° C, the screw rotation speed is 300 rpm, the kneading resin discharge speed is 15 to 20 kg / Hr, and the residence time of the resin inside the extruder is 35 to 100 seconds. I went. During the melt kneading, the temperature of the molten resin measured by a thermocouple in the extruder die part was 255 to 260 ° C.

In the production of the uncolored compositions 1 to 3, the raw materials were charged into the twin-screw extruder by pre-blending the components (A), (B), (F) and other components with a tumbler to prepare a pre-blended mixture of 30 parts. The mixture was added to the extruder through a weight feeder, and the component (B) was preliminarily heated to 80 ° C. in advance and pressed by an injection nozzle from the middle of the extruder by a gear pump to mix the component (B). In the production of the uncolored composition 4, all components were premixed and then charged into a twin-screw extruder. Moreover, in the production of the uncolored compositions 1 to 4, 10 mmHg-G (gauge pressure) was applied in the latter part of the extruder.
Vacuum devolatization was performed at. The melt-kneaded composition was extruded as a strand from a die and pelletized to produce uncolored flame-retardant resin compositions 1 to 4.

In the production of the uncolored compositions 5 to 7, the melt-kneading device was a twin-screw extruder (ZSK-25, L / D = 37, Wern.
er & Pfleiderer), melt kneading under the conditions that the cylinder temperature is 310 ° C, the screw speed is 300 rpm, the kneading resin discharge speed is 15 to 20 kg / Hr, and the resin residence time in the extruder is 35 to 150 seconds. I went.

In the production of the uncolored compositions 5 and 7, the raw materials were introduced into the twin-screw extruder by preliminarily blending the components (A), (B) and other components with a tumbler for 30 minutes. Put into the extruder through the feeder,
Further, the component (B) was preheated to 80 ° C. in advance, and was blended by press-fitting through a injection nozzle from the middle of the extruder by a gear pump. In the production of the uncolored composition 6, all components were premixed and then charged into a twin-screw extruder. Further, in the production of uncolored compositions 5 to 7, devolatization under reduced pressure was performed at 10 mmHg-G (gauge pressure) in the latter part of the extruder. The melt-kneaded composition is extruded as a strand from a die and pelletized,
Uncolored flame-retardant resin compositions 5 to 7 were produced.

[0157]

Examples Examples 1 to 10 The pellets of the uncolored flame-retardant resin composition obtained in Production Examples 1 to 7 were dried, and the pellets and silicone oil 1 (in the amounts shown in Table 2 (unit: parts by weight)) were used. Component (C)), colorant (component (D)), and lubricant (component (E)) and other components were mixed by a tumbler. Upon mixing, first, the component (C) is blended into the pellets of the uncolored flame-retardant resin composition and mixed for 10 minutes, and then the components (D), component (E) and other components which have been mixed in advance are mixed. The mixture was blended and mixed for 30 minutes. The thus obtained uncolored flame-retardant resin composition, the mixture of the components (C), (D), (E) and other components is charged into an extruder to obtain a colored flame-retardant resin composition. It was

Here, as the extruder, a single-screw extruder (manufactured by Tanabe Plastics Co., Ltd., 65 mmφ vented single-screw extruder, 5-stage dullage + 1-stage unimelt attachment), or twin-screw extruder (ZSK-25, L / D = 37, Werner
& Pfleiderer). In the production of the colored flame-retardant resin composition, the cylinder set temperature of the extruder is set to 230 to 31.
The temperature is set to 0 ° C, and a vent port is provided in the latter part of the extruder to 10 m.
Vacuum devolatization was performed with mHg-G (gauge pressure), strands were extruded from the extruder die and pelletized to obtain pellets of the colored flame-retardant resin composition. Injection molding machine from the obtained pellets (Autoshot 50D, manufactured by FANUC)
Was molded, and the following tests were carried out.

(1) Flame Retardancy Test The obtained pellets were dried, and strip-shaped compacts (thickness 2.0 mm, 1.5 mm and 1.4 mm) for combustion test were molded using an injection molding machine. . Each molded body is heated at 23 ° C, 50
After being kept in an environment of RH% for 2 days, UL94 standard 20M
M vertical burning test was performed and classified into V-0, V-1 or V-2. The symbol NC in the table is non-classifiable (non-classifi
cation). (Flame retardancy: V-0> V-1
>V-2> NC)

(2) Change in Flame Retardancy with Time The strip-shaped molded article for a combustion test having a thickness of 1.5 mm obtained by the above method was subjected to 5 ° C. in an environment of 23 ° C. and 50 RH%.
After holding for 30 days and 30 days, UL94 standard 20MM vertical burning test was performed and classified into V-0, V-1 or V-2.

(3) Dispersion of Colorant Using 10 g of the obtained pellets, a press molding machine heated to 210 to 320 ° C. was used to obtain a thickness of 0.25 to 0.35.
The press film was prepared so as to be in the range of mm, and the dispersibility of the colorant was visually observed. ◯: No colorant aggregate having a diameter of 0.2 mmφ or more, or no stripe pattern of the colorant is observed, and the dispersibility of the colorant is good. X: Colorant aggregates having a diameter of 0.2 mmφ or more or streak patterns of the colorant are present, and the dispersibility of the colorant is poor.

(4) Izod Impact Test The obtained pellets are dried, and a 1/8 inch thick strip is molded by an injection molding machine to have an Izod impact strength of 1/8 inch thick according to ASTM D256. It was measured with a notch. The measurement temperature is 23 ° C. (Unit: kgf · cm
/ Cm)

(5) Appearance of molded product 100 mm × 100 mm × 2 mm by injection molding machine
A (thickness) square shaped body was prepared, and the surface appearance was visually observed. The gate for injection molding was a pin gate having a diameter of 2 mm. The molded product was visually evaluated by passing (∘) when there were no molding defects such as peeling of the surface layer, silver, burns, sink marks, and stickiness on the surface, and rejecting (x) when there was. The results are shown in Table 2.

[0164]

[Table 2]

In Table 2, the component (E) in the coloring composition
Is a calculated value, and is a value obtained by calculation including the component (E) contained in the component (A) which is the raw material resin. Although Examples 1 to 10 are results for the present invention, the thin-wall flame retardancy is excellent, and the flame retardant performance is not deteriorated with time.
Further, it can be seen that the dispersibility of the colorant is excellent.

Comparative Examples 1 to 9 The uncolored flame-retardant resin compositions obtained in Production Examples 1 to 7 were dried and the amounts shown in Table 3 (unit: parts by weight) were the same as in Examples 1 to 10. To obtain a colored flame-retardant resin composition. The obtained pellets were used and evaluated in the same manner as in Examples 1-10. The results are shown in Table 3.

[0167]

[Table 3]

In Table 3, the component (E) in the coloring composition
The total amount of is the value obtained in the same manner as in Table 2. Comparative Example 1 is an example lacking the component (C), but the colorant dispersibility was insufficient. In Comparative Example 2, paraffin oil was used as a spreading agent instead of the component (C) (corresponding to the component (E), boiling point 300 ° C. or higher).
However, the flame retardance was insufficient. Comparative Example 3 is an example in which the silicone oil 1 was replaced with the silicone oil 2 (different from the component (C) of the present invention), but the dispersibility of the colorant was insufficient. Comparative Example 4 is an example in which the content of the component (E) in the coloring composition exceeds the upper limit of the range of the present invention, but the flame retardancy was insufficient. Comparative Example 5 is an example lacking the component (C), but the colorant dispersibility was insufficient.

Comparative Examples 6 and 7 are examples in which the total amount of the component (E) exceeds the upper limit of the range of the present invention, but the flame retardancy was insufficient. Comparative Example 8 is an example in which the total amount of the component (E) exceeds the upper limit of the range of the present invention, but the flame retardancy was insufficient. Comparative Example 9 is an example in which the total amount of the component (E) exceeds the upper limit of the range of the present invention, but the flame retardancy was insufficient. Further, Comparative Examples 4, 7, 8 and 9 showed a decrease in flame retardance over time.

[0170]

The colored flame-retardant resin composition of the present invention has excellent flame retardancy and colorant dispersibility in a thin-walled molded product, and therefore can be used in computer monitors, notebook computers, printers,
It is extremely useful as a material for housings of word processors, copiers, mobile phones, etc., and is particularly useful when obtaining a molded product having a thin portion.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/51 C08K 5/51 // (C08L 101/00 C08L 83:04 83:04) F term (reference) ) 4F071 AA14 AA22 AA24 AA33 AA43 AA50 AA51 AA54 AA63 AA67 AE07 AE09 AE11 AF47 AH05 AH16 BC04 4J002 BB001 BC021 BD031 BG061 CF001 CG001 CH071 CL001 CN011 CP032 EW026 FD01 FD06 FD07 FD09 FD13 FD17 FD31 GG00 GQ00

Claims (17)

[Claims] 1. A viscosity at 25 ° C. with respect to 100 parts by weight of a thermoplastic resin (A), 0.01 to 40 parts by weight of a flame retardant (B), and 100 parts by weight of a total of components (A) and (B). Is a colored flame-retardant resin composition containing 0.001 to 3 parts by weight of a silicone oil (C) of 0.1 to 1,000 cs (centistokes) and 0.0001 to 10 parts by weight of a colorant (D). And a total amount of the lubricant (E) is 3,000 ppm by weight or less, a colored flame-retardant resin composition. 2. The lubricant (E) is a compound 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 colored flame-retardant resin composition according to claim 1. 3. The colored flame-retardant resin composition according to claim 1, wherein the thermoplastic resin (A) is an aromatic polycarbonate resin or a resin mainly containing an aromatic polycarbonate resin. 4. The colored flame-retardant resin composition according to claim 1 or 2, wherein the thermoplastic resin (A) is a polyphenylene ether resin or a resin mainly composed of a polyphenylene ether resin. 5. The colored flame retardant according to any one of claims 1 to 4, wherein the flame retardant (B) is selected from the group of compounds represented by the organophosphorus compound oligomers of the following formula (1). Resin composition. [Chemical 1] 6. The colored flame-retardant resin composition according to claim 1, wherein the flame-retardant agent (B) is selected from compounds represented by organopolysiloxanes of the following formula (2). object. [Chemical 2] 7. A fluoropolymer (F) of 0.0 to 100 parts by weight of the component (A) and the component (B) in total.
The colored flame-retardant resin composition according to claim 1, which comprises 5 to 2 parts by weight. 8. The viscosity at 25 ° C. is 100 parts by weight of an uncolored flame-retardant resin composition comprising 100 parts by weight of a thermoplastic resin (A) and 0.01 to 40 parts by weight of a flame retardant (B). 0.1 to 1,000 cs (centistokes)
0.001 to 10 parts by weight of the silicone oil (C) and the colorant (D) are mixed,
A method for obtaining a colored flame-retardant resin composition by melt-kneading using an extruder, wherein the total amount of lubricant (E) is 3,000.
It is 0 weight ppm or less, The manufacturing method of the colored flame-retardant resin composition characterized by the above-mentioned. 9. The lubricant (E) is a compound 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 method for producing the colored flame-retardant resin composition according to claim 8. 10. The production of a colored flame-retardant resin composition according to claim 8 or 9, wherein the thermoplastic resin (A) is an aromatic polycarbonate resin or a resin mainly containing an aromatic polycarbonate resin. Method. 11. The method for producing a colored flame-retardant resin composition according to claim 8, wherein the thermoplastic resin (A) is a polyphenylene ether resin or a resin mainly composed of a polyphenylene ether resin. 12. The colored flame retardant according to claim 8, wherein the flame retardant (B) is selected from the group of compounds represented by the organophosphorus compound oligomers of the following formula (1). A method for producing a resin composition. [Chemical 3] 13. The colored flame-retardant resin composition according to claim 8, wherein the flame-retardant agent (B) is selected from compounds represented by organopolysiloxanes of the following formula (2). Method of manufacturing things. [Chemical 4] 14. Further, the fluoropolymer (F) is added to 100 parts by weight of the component (A) and the component (B) in total.
05 to 2 parts by weight are included.
A method for producing a colored flame-retardant resin composition according to any one of 1. 15. The extruder according to claim 8, which is a twin-screw extruder.
15. The method for producing a colored flame-retardant resin composition according to any one of 14. 16. A molded product obtained by molding the colored flame-retardant resin composition according to any one of claims 1 to 7. 17. The molded product according to claim 16, wherein the molded product has a thickness of 2 mm or less in an amount of 30% by weight or more of the entire molded product.