JP2013231140A - Flame retardant masterbatch and thermoplastic resin composition produced by melt-kneading the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retardant masterbatch superior in productivity and quality stability, and also superior in workability when the masterbatch is melt-kneaded with resin.SOLUTION: A flame retardant masterbatch is obtained by melt-kneading 100 pts.mass of the total of 85 to 20 mass% of an aromatic polycarbonate resin (A) and 15 to 80 mass% of an aromatic phosphazene compound (B) with 0.005 to 2 pts.mass of a fluoropolymer (C).

Description

  The present invention relates to a flame retardant masterbatch. More specifically, the present invention relates to a flame retardant master batch that is excellent in productivity and quality stability, and also excellent in workability when melt kneaded with a resin.

Conventionally, halogen-based flame retardants containing chlorine atoms or bromine atoms have been widely used to impart flame retardancy to thermoplastic resins. However, in recent years, there are concerns about the environmental impact of incinerated ash and the impact on the human body in the event of a fire, and the use of halogenated flame retardants has been regulated.

On the other hand, organophosphate ester-based flame retardants have been studied extensively as flame retardants to replace halogen-based ones. However, the use of organophosphates has also been limited in part due to concerns about the impact on aquatic organisms.

  In contrast, phosphazene compounds have attracted attention as phosphorus-based flame retardants that replace organic phosphate esters. In particular, by using a specific aromatic phosphazene compound, the flame retardancy of the thermoplastic resin can be effectively increased, and mechanical properties and heat resistance can be improved as compared with the organic phosphate compound. .

  However, since the above-mentioned aromatic phosphazene compound has a property of solidifying against compression and shearing, the compound is fixed and handled at an industrial level when it is melted and kneaded with a thermoplastic resin. The problem was that it was extremely difficult. Moreover, since the compatibility with the thermoplastic resin is poor and the dispersibility is inferior, the thermoplastic resin composition having high flame retardancy and mechanical properties cannot be stably obtained.

In order to solve the above-mentioned problems, a flame retardant master batch (see Patent Document 1) in which a phosphazene compound is blended with a polyester resin, a polycarbonate resin, and a polyester elastomer, or a flame retardant master batch composed of a phosphazene compound and a phenol resin. (See Patent Document 2).

However, when trying to add the flame retardant masterbatch as described above to the thermoplastic resin, the polyester resin such as polyethylene terephthalate resin, polyester elastomer and phenolic resin component contained in the flame retardant masterbatch have flame retardancy. Therefore, the flame retardancy of the thermoplastic resin composition could not be effectively expressed.

JP 2006-307178 A Japanese Laid-Open Patent Publication No. 2008-101035

  The present invention was devised in view of the above-mentioned problems, is excellent in productivity, excellent in workability when melt-kneaded with a resin, and further, when blended with a thermoplastic resin, provides flame retardancy and mechanical properties. The object is to provide an excellent flame retardant masterbatch.

As a result of intensive investigations to solve the above problems, the inventors of the present invention have excellent productivity by blending a specific amount of fluoropolymer when melt kneading a specific aromatic polycarbonate resin and an aromatic phosphazene compound, The present inventors have found that a flame retardant masterbatch having excellent workability when melt-kneading with a resin and further having excellent flame retardancy and mechanical properties can be obtained when blended with a thermoplastic resin.

  That is, the first gist of the present invention is that a total of 100 parts by mass of 85 to 20% by mass of the aromatic polycarbonate resin (A) and 15 to 80% by mass of the aromatic phosphazene compound (B), and 0.1% of the fluoropolymer (C). It exists in the flame retardant masterbatch characterized by being obtained by melt-kneading 005-2 mass parts.

  At this time, the weight average molecular weight of the aromatic polycarbonate resin (A) is preferably 15000 to 55000, and the aromatic phosphazene compound is an aromatic phosphazene compound represented by the following formula (1) and / or (2). It is preferable that

［式（１）中、ａ は３〜２５の整数であり、Ｒ^１、及びＲ^２は、同一又は異なっていてもよく、アリール基又はアルキルアリール基を示す。］

Wherein (1), a is an integer of 3 to 25, ^{R 1,} and ^{R 2} may be the same or different, an aryl group or an alkylaryl group. ]

［式（２）中、ｂは３〜１０，０００の整数であり、Ｒ^３及びＲ^４は、同一又は異なっていてもよく、アリール基又はアルキルアリール基を示す。Ｒ^５は、−Ｎ＝Ｐ（ＯＲ^３）_３基、−Ｎ＝Ｐ（ＯＲ^４）_３基、−Ｎ＝Ｐ（Ｏ）ＯＲ^３基、−Ｎ＝Ｐ（Ｏ）ＯＲ^４基から選ばれる少なくとも１種を示し、Ｒ^６は、−Ｐ（ＯＲ^３）_４基、−Ｐ（ＯＲ^４）_４基、−Ｐ（Ｏ）（ＯＲ^３）_２基、−Ｐ（Ｏ）（ＯＲ^４）_２基から選ばれる少なくとも１種を示す。］

[In Formula (2), b is an integer of ^{3 to} 10,000, R ³ and R ⁴ may be the same or different and each represents an aryl group or an alkylaryl group. R ⁵ is selected from -N = P (OR ³ ) ₃ groups, -N = P (OR ⁴ ) ₃ groups, -N = P (O) OR ³ groups, and -N = P (O) OR ⁴ groups. It represents at least one, ^{R 6} is, -P ^(OR _{3) 4} group, -P ^(OR ₄₎ 4 ^{group, -P (O) (OR 3} ) 2 ^{group, -P (O) (OR 4} ) 2 At least one selected from the group is shown. ]

Moreover, the 2nd summary of this invention is obtained by melt-kneading 100 mass parts of thermoplastic resins (C), and 1-100 mass parts of said flame retardant masterbatch, The thermoplastic resin composition characterized by the above-mentioned It exists in things.

Moreover, the 3rd summary of this invention exists in the thermoplastic resin composition characterized by the above-mentioned thermoplastic resin (C) being aromatic polycarbonate resin.

  Since the flame retardant masterbatch of the present invention is excellent in productivity and excellent in phosphazene dispersibility, it can stably impart flame retardancy when blended with a thermoplastic resin. In addition, phosphazene is blended in a high concentration in an aromatic polycarbonate resin with excellent heat resistance and flame retardancy, so it is superior in handling workability compared to conventionally proposed masterbatches, and the flame resistance of thermoplastic resins Sexually can be enhanced effectively. Therefore, it is useful when imparting flame retardancy to engineering plastics such as polycarbonate resin, polyester resin, polyamide resin, and polyphenylene ether resin, and among them, it can be suitably used for polycarbonate resin.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the embodiments and examples described below, and may be arbitrarily selected without departing from the scope of the present invention. You can change it to

Overview]
The flame retardant masterbatch of the present invention comprises 100 parts by mass of 85 to 20% by mass of the aromatic polycarbonate resin (A) and 15 to 80% by mass of the aromatic phosphazene compound (B), and 0.005 of the fluoropolymer (C). It is obtained by melt-kneading ˜1 part by mass.

[2. Aromatic polycarbonate resin (A)]
There is no restriction | limiting in the kind of aromatic polycarbonate resin used for the flame retardant masterbatch of this invention. Moreover, aromatic polycarbonate resin may use 1 type and may use 2 or more types together by arbitrary combinations and arbitrary ratios.

  In addition, the aromatic polycarbonate resin in this invention is a polymer of the basic structure which has a carbonic acid bond represented by following General formula (3).

In formula (3), X ¹ is generally a hydrocarbon, but for imparting various properties, X ¹ into which a hetero atom or hetero bond is introduced may be used. In the aromatic polycarbonate resin of the present invention, carbons directly bonded to the carbonic acid bond of X ¹ are each aromatic carbon.

  Although there is no restriction | limiting in the specific kind of aromatic polycarbonate resin, For example, the aromatic polycarbonate polymer formed by making a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Alternatively, a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used. The aromatic polycarbonate polymer may be linear or branched. Furthermore, the aromatic polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer. Normally, such an aromatic polycarbonate polymer is a thermoplastic resin.

  Among monomers used as raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds include:

Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene;

Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl;

2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, , 7-dihydroxynaphthalene, dihydroxynaphthalene such as 2,7-dihydroxynaphthalene;

2,2′-dihydroxydiphenyl ether, 3,3′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) Dihydroxy diaryl ethers such as benzene and 1,3-bis (4-hydroxyphenoxy) benzene;

2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A),
1,1-bis (4-hydroxyphenyl) propane,
2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-methoxy-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane,
1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane,
2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane,
2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane,
α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene,
1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene,
Bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) (4-propenylphenyl) methane,
Bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) naphthylmethane,
1-bis (4-hydroxyphenyl) ethane,
2-bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-naphthylethane,
1-bis (4-hydroxyphenyl) butane,
2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
1-bis (4-hydroxyphenyl) octane,
2-bis (4-hydroxyphenyl) octane,
1-bis (4-hydroxyphenyl) hexane,
2-bis (4-hydroxyphenyl) hexane,
4,4-bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
10-bis (4-hydroxyphenyl) decane,
1-bis (4-hydroxyphenyl) dodecane,
Bis (hydroxyaryl) alkanes such as;

1-bis (4-hydroxyphenyl) cyclopentane,
1-bis (4-hydroxyphenyl) cyclohexane,
4-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

Cardostructure-containing bisphenols such as 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

Dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide;

Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide;

Dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone;

Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane (ie, from the viewpoint of impact resistance and heat resistance). Bisphenol A) is preferred.
In addition, 1 type may be used for an aromatic dihydroxy compound and it may use 2 or more types together by arbitrary combinations and a ratio.

  Among the monomers used as the raw material for the aromatic polycarbonate resin, carbonyl halides, carbonate esters and the like are used as examples of the carbonate precursor. In addition, 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.

  Specific examples of carbonyl halides include phosgene; haloformates such as bischloroformate of dihydroxy compounds and monochloroformate of dihydroxy compounds.

  Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate bodies of dihydroxy compounds, monocarbonate bodies of dihydroxy compounds, and cyclic carbonates. And carbonate bodies of dihydroxy compounds such as

-Manufacturing method of aromatic polycarbonate resin The manufacturing method of aromatic polycarbonate resin is not specifically limited, Arbitrary methods are employable. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Hereinafter, a particularly preferable one of these methods will be specifically described.

.. Interfacial polymerization method First, the case of producing an aromatic polycarbonate resin by the interfacial polymerization method will be described. In the interfacial polymerization method, a dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, usually at a pH of 9 or higher. Polycarbonate resin is obtained by interfacial polymerization in the presence. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present as necessary, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.

  The dihydroxy compound and the carbonate precursor are as described above. Of the carbonate precursors, phosgene is preferably used, and a method using phosgene is particularly called a phosgene method.

  Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene; It is done. In addition, 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate, among which sodium hydroxide and water Potassium oxide is preferred. In addition, an alkali compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  Although there is no restriction | limiting in the density | concentration of the alkali compound in alkaline aqueous solution, Usually, in order to control pH in the alkaline aqueous solution of reaction to 10-12, it is used at 5-10 mass%. For example, when phosgene is blown, the molar ratio of the bisphenol compound and the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. Among these, it is preferable that the ratio is 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

  Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine. Formula tertiary amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. Pyridine; guanine; guanidine salt; and the like. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the molecular weight regulator include aromatic phenols having a monohydric phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides and the like. Of these, aromatic phenols are preferred. Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropanyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as 0-oxine benzoic acid and 2-methyl-6-hydroxyphenylacetic acid; In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The usage-amount of a molecular weight regulator is 0.5 mol or more normally with respect to 100 mol of dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of a polycarbonate resin composition can be improved.

In the reaction, the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set. For example, when phosgene is used as the carbonate precursor, the molecular weight regulator can be mixed at any time as long as it is between the reaction (phosgenation) of the dihydroxy compound and phosgene and the start of the polymerization reaction.
In addition, reaction temperature is 0-40 degreeC normally, and reaction time is normally several minutes (for example, 10 minutes)-several hours (for example, 6 hours).

-Melt transesterification method Next, the case where an aromatic polycarbonate resin is manufactured by the melt transesterification method is demonstrated. In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.

The dihydroxy compound is as described above.
On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate, and the like. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is more preferable. In addition, 1 type may be used for carbonic acid diester, and it may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired aromatic polycarbonate resin is obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound. More preferably, it is used. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

  In an aromatic polycarbonate resin, the amount of terminal hydroxyl groups tends to have a great influence on thermal stability, hydrolysis stability, color tone, and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method. In the transesterification reaction, an aromatic polycarbonate resin in which the terminal hydroxyl group amount is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound; the degree of vacuum during the transesterification reaction, and the like. In addition, this operation can also adjust the molecular weight of the aromatic polycarbonate resin obtained normally.

When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

  When producing an aromatic polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, it is preferable to use, for example, an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the above-mentioned conditions while removing a by-product such as an aromatic hydroxy compound.

  The melt polycondensation reaction can be performed by either a batch method or a continuous method. When performing by a batch type, the order which mixes a reaction substrate, a reaction medium, a catalyst, an additive, etc. is arbitrary as long as a desired aromatic polycarbonate resin is obtained, What is necessary is just to set an appropriate order arbitrarily.

  In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, a catalyst deactivator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to aromatic polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.

-Other matters regarding aromatic polycarbonate resin The weight average molecular weight [Mw] of the aromatic polycarbonate resin (A) used in the present invention is usually 15000 or more, preferably 20000 or more, more preferably 25000 or more, and usually 55000. Hereinafter, it is preferably 53000 or less, more preferably 50000 or less.
Setting the weight average molecular weight to be equal to or higher than the lower limit of the above range is preferable because the productivity and handling workability of the flame retardant masterbatch of the present invention are improved and the dispersibility of phosphazene is also improved. On the other hand, by making the weight average molecular weight not more than the upper limit of the above range, the productivity of the flame retardant masterbatch of the present invention is improved and the dispersibility of phosphazene is also improved.
In addition, two or more types of aromatic polycarbonate resins having different weight average molecular weights may be mixed and used. In this case, an aromatic polycarbonate resin having a weight average molecular weight outside the above preferred range may be mixed. Good.

The weight average molecular weight [Mw] is GPC (WATERS 2695), column (Shodex KF-805L × 3, 800D, KF-G Guard Column), polystyrene developing molecular weight under conditions of developing solvent THF, temperature 25 ° C. This is a value obtained as (weight average molecular weight [Mw]).

  The terminal hydroxyl group concentration of the aromatic polycarbonate resin is arbitrary and may be appropriately selected and determined, but is usually 1000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. Thereby, the residence heat stability of the flame retardant masterbatch of this invention can be improved more. The lower limit is usually 10 ppm or more, preferably 30 ppm or more, and more preferably 40 ppm or more, particularly in the case of an aromatic polycarbonate resin produced by the melt transesterification method.

  The unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm relative to the weight of the aromatic polycarbonate resin. The measurement method is colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method.

  The aromatic polycarbonate resin is an aromatic polycarbonate resin alone (the aromatic polycarbonate resin alone is not limited to an embodiment containing only one kind of the aromatic polycarbonate resin. For example, a plurality of aromatic resins having different monomer compositions and molecular weights are used. It may be used in the meaning including an embodiment including a polycarbonate resin. For example, for the purpose of further improving the flame retardancy and impact resistance, an aromatic polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy A monomer, oligomer or polymer having a monomer; for the purpose of improving thermal oxidation stability, a copolymer with a monomer, oligomer or polymer having a dihydroxyanthraquinone structure; You may comprise as a copolymer.

Furthermore, the aromatic polycarbonate resin may be not only a virgin raw material but also an aromatic polycarbonate resin regenerated from a used product (a so-called material recycled aromatic polycarbonate resin). Examples of the used products include: optical recording media such as optical disks; light guide plates; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include architectural members such as glass windows and corrugated sheets. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
However, the regenerated aromatic polycarbonate resin is preferably 80% by mass or less, and more preferably 50% by mass or less, among the aromatic polycarbonate resins contained in the flame retardant masterbatch of the present invention.

[3. Aromatic phosphazene compound (B)]
The aromatic phosphazene compound (B) used in the present invention is an organic compound having a —P═N— bond and an aromatic group in the molecule, and preferably a cyclic fragrance represented by the following general formula (1). Phosphazene compounds, chain aromatic phosphazene compounds represented by the following general formula (2), and at least one aromatic phosphazene compound selected from the group consisting of the following general formulas (1) and (2) Is at least one compound selected from the group consisting of crosslinked aromatic phosphazene compounds crosslinked by a crosslinking group.

In formula (1), a is an integer of 3 to 25, and R ¹ and R ² may be the same or different and each represents an aryl group or an alkylaryl group.

In formula (2), b is an integer of ^{3 to} 10,000, and R ³ and R ⁴ may be the same or different and each represents an aryl group or an alkylaryl group.
R ⁵ is selected from -N = P (OR ³ ) ₃ groups, -N = P (OR ⁴ ) ₃ groups, -N = P (O) OR ³ groups, and -N = P (O) OR ⁴ groups. It represents at least one, ^{R 6} is, -P ^(OR _{3) 4} group, -P ^(OR ₄₎ 4 ^{group, -P (O) (OR 3} ) 2 ^{group, -P (O) (OR 4} ) 2 At least one selected from the group is shown.

  Examples of the aryl group include aryl groups having 6 to 20 carbon atoms such as a phenyl group, a methylphenyl (ie, tolyl) group, a dimethylphenyl (ie, xylyl) group, a trimethylphenyl group, and a naphthyl group. Among them, an aryl group having 6 to 10 carbon atoms is preferable, and a phenyl group is particularly preferable.

Examples of the alkylaryl group include aralkyl groups having 6 to 20 carbon atoms such as benzyl group, phenethyl group, and phenylpropyl group. Among them, aralkyl groups having 7 to 10 carbon atoms are preferable, and benzyl group is particularly preferable. .

Among these, R ¹ , R ² , R ³ and R ⁴ are preferably aryl groups, and most preferably phenyl groups. By using such an aromatic phosphazene, the flame retardancy and heat resistance of the thermoplastic resin containing the flame retardant master batch of the present invention can be effectively increased.

Examples of the cyclic and / or chain aromatic phosphazene compounds represented by the general formulas (1) and (2) include, for example, phenoxyphosphazene,
poly) tolyloxyphosphazenes such as o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene,
(poly) xylyloxyphosphazenes such as o, m-xylyloxyphosphazene, o, p-xylyloxyphosphazene, m, p-xylyloxyphosphazene,
o, m, p-trimethylphenyloxyphosphazene,
(Poly) phenoxytolyloxyphosphazenes such as phenoxy o-tolyloxyphosphazene, phenoxy m-tolyloxyphosphazenes, phenoxy p-tolyloxyphosphazenes,
(Poly) phenoxytolyloxyxyloxyphosphazene, such as phenoxyo, m-xylyloxyphosphazene, phenoxyo, p-xylyloxyphosphazene, phenoxym, p-xylyloxyphosphazene,
Phenoxy o, m, p-trimethylphenyloxyphosphazene and the like can be exemplified, and cyclic and / or chain phenoxyphosphazene and the like are preferable.

As the cyclic aromatic phosphazene compound represented by the general formula (1), cyclic phenoxyphosphazene in which R ¹ is a phenyl group is particularly preferable. Examples of such a cyclic phenoxyphosphazene compound include hexachlorocyclotriphosphazene, octachlorocyclohexane, and a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Examples include compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffenoxycyclopentaphosphazene obtained by removing a cyclic chlorophosphazene such as cyclotetraphosphazene and decachlorocyclopentaphosphazene and then substituting with a phenoxy group. . The cyclic phenoxyphosphazene compound is preferably a compound in which m in the general formula (1) is an integer of 3 to 8, and may be a mixture of compounds having different m.

The average m is preferably 3 to 5, and more preferably 3 to 4.
In particular, a mixture of compounds in which m = 3 is 50% by mass or more, m = 4 is 10 to 40% by mass, and m = 5 or more is 30% by mass or less in total.

As the chain aromatic phosphazene compound represented by the general formula (2), chain phenoxyphosphazene in which R ¹ is a phenyl group is particularly preferable. Such a chain phenoxyphosphazene compound is obtained by, for example, subjecting hexachlorocyclotriphosphazene obtained by the above-mentioned method to reversion polymerization at a temperature of 220 to 250 ° C., and obtaining a linear dichlorophosphazene having a polymerization degree of 3 to 10,000. Examples include compounds obtained by substitution with a phenoxy group. N of general formula (2) of this linear phenoxyphosphazene compound becomes like this. Preferably it is 3-1000, More preferably, it is 3-100, More preferably, it is 3-25.

Examples of the crosslinked aromatic phosphazene compound include a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (bisphenol S residue) and a crosslinked structure of 2,2- (4,4′-diphenylene) isopropylidene group. Compounds having a crosslinked structure of 4,4′-diphenylene group, such as compounds having a crosslinked structure of 4,4′-oxydiphenylene group, compounds having a crosslinked structure of 4,4′-thiodiphenylene group, etc. Etc.
In addition, as the crosslinked aromatic phosphazene compound, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound in which R ¹ is a phenyl group in the general formula (1) with the above-mentioned crosslinking group, or R in the above general formula (2) ^A cross-linked phenoxyphosphazene compound in which a chain phenoxyphosphazene compound in which ¹ is a phenyl group is cross-linked by the cross-linking group is preferable from the viewpoint of flame retardancy, and a cross-linked phenoxyphosphazene compound in which a cyclic phenoxy phosphazene compound is cross-linked by the cross-linking group Is more preferable.
Further, the content of the phenylene group in the cross-linked phenoxyphosphazene compound is such that the cyclic phenoxyphosphazene compound represented by the general formula (1) and / or the all phenyl groups in the chain phenoxyphosphazene compound represented by the general formula (2) And based on the number of phenylene groups, it is usually 50 to 99.9%, preferably 70 to 90%. The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

  In the present invention, the aromatic phosphazene compound (B) is obtained by crosslinking the cyclic phenoxyphosphazene compound represented by the general formula (1) and the cyclic phenoxyphosphazene compound represented by the general formula (1) with a crosslinking group. In view of flame retardancy and mechanical properties, at least one selected from the group consisting of crosslinked phenoxyphosphazene compounds formed is preferable.

Content of this aromatic phosphazene compound (B) is 15-80 mass% with respect to 85-20 mass% of aromatic polycarbonate resin (A). When the ratio is less than the above lower limit, the ratio of the aromatic phosphazene compound in the flame retardant master batch is small, and the effect of improving the flame retardancy to the thermoplastic resin blended therewith is small.
On the other hand, when the above upper limit is exceeded, the dispersibility of the aromatic phosphazene compound in the flame retardant masterbatch of the present invention is lowered, and the flame retardancy of the thermoplastic resin is unstable when blended with the thermoplastic resin. In addition, the workability of the flame retardant master batch itself is remarkably lowered, which is not preferable.
From such a viewpoint, the content of the aromatic phosphazene compound (B) is more preferably 20 to 70% by mass, and still more preferably 80 to 30% by mass with respect to the aromatic polycarbonate resin (A). It is 35-60 mass parts with respect to 40-65 mass% of aromatic polycarbonate resin (A), Most preferably, it is 40-55 mass% with respect to 45-60 mass% of aromatic polycarbonate resin (A).

[4. Fluoropolymer]
The flame retardant masterbatch of the present invention contains 0.005 to 2 parts by mass of the fluoropolymer (C) with respect to a total of 100 parts by mass of the aromatic polycarbonate resin (A) and the aromatic phosphazene compound (B). By blending the fluoropolymer (D) in this way, the production amount can be increased and productivity can be dramatically improved without causing strand breakage when producing the flame retardant masterbatch of the present invention. .
One type of fluoropolymer (D) may be used, or two or more types may be used in any combination and in any ratio.

  Examples of the fluoropolymer (D) include a fluoroolefin resin. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure. Specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer resin, and the like. Of these, tetrafluoroethylene resin and the like are preferable. Examples of the fluoroethylene resin include a fluoroethylene resin having a fibril forming ability.

  Examples of the fluoroethylene resin having a fibril-forming ability include “Teflon (registered trademark) 6J” and “Teflon (registered trademark) 640J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd. F103 "," Polyfluorocarbon FA500B "," Polyfluorocarbon FA500H "and the like. Furthermore, as a commercial item of the aqueous dispersion liquid of fluoroethylene resin, "Teflon (registered trademark) 31-JR" by Mitsui DuPont Fluorochemical Co., Ltd., "Fluon D-1" by Daikin Chemical Industries, etc. are mentioned, for example. Furthermore, a fluoroethylene polymer having a multilayer structure obtained by polymerizing vinyl monomers can also be used. Examples of such a fluoroethylene polymer include polystyrene-fluoroethylene composites, polystyrene-acrylonitrile-fluoroethylene. Examples include composites, polymethyl methacrylate-fluoroethylene composites, polybutyl methacrylate-fluoroethylene composites, etc. Specific examples include “Metablene A-3800” manufactured by Mitsubishi Rayon Co., Ltd., “Blendex” manufactured by GE Specialty Chemical Co., Ltd. 449 "and the like. In addition, 1 type may contain the dripping inhibitor and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the fluoropolymer (C) is 0.005 parts by mass or more, preferably 0.0075 parts by mass or more with respect to 100 parts by mass in total of the aromatic polycarbonate resin (A) and the aromatic phosphazene compound (B). More preferably 0.01 parts by mass or more, particularly preferably 0.03 parts by mass or more, and 2 parts by mass or less, preferably 1 part by mass or less, more preferably 0.75 parts by mass or less, particularly preferably 0. .5 parts by mass or less. When the content of the fluoropolymer (C) is less than or equal to the lower limit of the above range, the effect of improving the productivity of the flame retardant masterbatch of the present invention is small, and when the content exceeds the upper limit of the above range, the flame retardant It is not preferable because lumps tend to occur in the masterbatch and the productivity tends to decrease.

[5. Flame retardant masterbatch]
The flame retardant masterbatch of the present invention may contain other components in addition to those described above as necessary as long as desired physical properties are not significantly impaired. Examples of other components include resins other than aromatic polycarbonate resins, various resin additives, and the like. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

  Various resin additives include heat stabilizers, antioxidants, mold release agents, lubricants, flow modifiers, and the like.

[6. Flame retardant masterbatch production method]
The flame retardant masterbatch of the present invention is obtained by melt-kneading the aromatic polycarbonate resin (A) and the aromatic phosphazene compound (B). There is no restriction | limiting in particular as the method of melt-kneading, The manufacturing method of a well-known resin composition can be employ | adopted widely.
For example, the aromatic polycarbonate resin (A), the aromatic phosphazene compound (B), and other components to be blended as necessary are premixed using various mixers such as a tumbler or a Henschel mixer. Then, a method of melt kneading with a mixer such as a Banbury mixer, a roll, a Brabender, a single screw kneading extruder, a twin screw kneading extruder, or a kneader can be mentioned. Among them, a production method in which melt kneading is performed using an extruder is more preferable, and a production method using a twin screw extruder is more preferable because production efficiency is good and good dispersibility of the aromatic phosphazene compound is obtained.

  Also, for example, without mixing each component in advance, or only a part of the components are mixed in advance, and supplied to an extruder using a feeder and melt-kneaded to produce the flame retardant master batch of the present invention. You can also.

[7. Thermoplastic resin composition]
The thermoplastic resin composition of the present invention is obtained by melt-kneading the thermoplastic resin (C) and the flame retardant master batch of the present invention.

Although there is no restriction | limiting in particular about the kind of thermoplastic resin (C), For example, Polycarbonate resin; Polyester-polycarbonate copolymer resin; Thermoplastic polyester resin, such as polyethylene terephthalate resin, polytrimethylene terephthalate, polybutylene terephthalate resin; Polystyrene resin , AS resins, ABS resins, MS resins and other styrene resins, polyethylene resins, polypropylene resins and other polyolefin resins; polyamide resins; polyimide resins; polyether imide resins; polyurethane resins; Examples include polymethacrylate resins.
In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and ratios.

    The thermoplastic resin (C) of the present invention is preferably a polycarbonate resin and more preferably an aromatic polycarbonate resin because of its high compatibility with the flame retardant masterbatch of the present invention. By blending the flame retardant master batch of the present invention with the polycarbonate resin, a thermoplastic resin composition having high flame retardancy, that is, a polycarbonate resin composition is obtained.

In the thermoplastic resin composition of the present invention, the content of the flame retardant masterbatch is not particularly limited and can be appropriately selected within a range in which a desired physical property balance is obtained. The thermoplastic resin (C) 100 mass The amount is usually 1 part by mass or more, preferably 3 parts by mass or more, more preferably 5 parts by mass or more based on parts. Moreover, it is 100 mass parts or less normally, Preferably it is 50 mass parts or less, More preferably, it is 30 mass parts or less.
By setting it as such a range, the flame retardance of the thermoplastic resin composition of this invention can be improved effectively, and productivity will also become favorable.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated more concretely, this invention is limited to a following example and is not interpreted.

[Example 1]
Polyfluoro having a fibril-forming ability with respect to a total of 100 parts by mass of 50% by mass of a bisphenol-type aromatic polycarbonate resin having a weight average molecular weight of 47800 and an aromatic phosphazene compound (Fushimi Pharmaceutical Co., Ltd., trade name: Ravitor FP110). After blending 0.01 parts by mass of ethylene resin (Daikin Kogyo Co., Ltd., trade name: Polyflon FA500H) and mixing with a tumbler for 20 minutes, a twin screw extruder (TEX30HSST) made by Nippon Steel Works, equipped with 1 vent. Supplied, kneaded under the conditions of screw rotation speed 250 rpm, discharge rate 20 kg / hour, barrel temperature 240 ° C., die hole number 3 places, the molten resin extruded in a strand shape is rapidly cooled in a water tank, and using a pelletizer Pelletized to obtain flame retardant master batch pellets. At this time, the strand breakage was only once in 1 hour of production, and the production was stable.

[Example 2]
Polyfluoro having a fibril-forming ability with respect to a total of 100 parts by mass of 40% by mass of a bisphenol type aromatic polycarbonate resin having a weight average molecular weight of 47800 and 60% by mass of an aromatic phosphazene compound (Fushimi Pharmaceutical Co., Ltd., trade name: Ravitor FP110). A flame retardant masterbatch was produced under the same conditions as in Example 1 except that 0.5 part by mass of ethylene resin (manufactured by Daikin Industries, trade name: Polyflon FA500H) was blended. At this time, strand breakage did not occur once in the production time of 1 hour, and stable production was possible.

[Example 3]
Polyfluoro having a fibril-forming ability with respect to a total of 100 parts by mass of 80% by mass of a bisphenol type aromatic polycarbonate resin having a weight average molecular weight of 58000 and 20% by mass of an aromatic phosphazene compound (Fushimi Pharmaceutical Co., Ltd., trade name: Ravitor FP110). Flame retardant masterbatch under the same conditions as in Example 1 except that 0.3 parts by mass of ethylene resin (Daikin Kogyo Co., Ltd., trade name: Polyflon FA500H) is blended and the barrel temperature of the twin screw extruder is 280 ° C. Produced. At this time, strand breakage occurred three times in one hour of production, but production was relatively stable.

[Comparative Example 1]
In the same conditions as in Example 1, only a total of 100 parts by mass of 50% by mass of a bisphenol type aromatic polycarbonate resin having a weight average molecular weight of 47800 and 50% by mass of an aromatic phosphazene compound (Fushimi Pharmaceutical Co., Ltd., trade name: Ravitor FP110) was used. A flame retardant masterbatch was produced. Although pelletization was possible, strand breakage occurred 17 times during the production time of 1 hour, and stable production was not possible.

[Comparative Example 2]
Polyfluoro having a fibril-forming ability with respect to a total of 100 parts by mass of 40% by mass of a bisphenol type aromatic polycarbonate resin having a weight average molecular weight of 47800 and 60% by mass of an aromatic phosphazene compound (Fushimi Pharmaceutical Co., Ltd., trade name: Ravitor FP110). A flame retardant masterbatch was produced under the same conditions as in Example 1 except that 3 parts by mass of ethylene resin (trade name: Polyflon FA500H, manufactured by Daikin Industries, Ltd.) was blended. Although pelletization was possible, strand breakage occurred 11 times during the production time of 1 hour, and vent-up occurred, making it impossible to produce stably.

[Example 4]
After mixing 25 parts by mass of the flame retardant masterbatch of Example 1 with a tumbler for 20 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin, it is supplied to a twin-screw extruder (TEX30HSST) manufactured by Nippon Steel Works, equipped with 1 vent. The molten resin composition kneaded under the conditions of a screw rotation speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 260 ° C., rapidly cooled in a water tank, pelletized using a pelletizer, and aromatic polycarbonate A pellet of the resin composition was obtained. The flame retardancy of the obtained resin composition was stable (no variation was found in the burning time of the molded product).

[Example 5]
After mixing 30 parts by mass of the flame retardant master batch of Example 2 with a tumbler for 20 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin, it is supplied to a twin screw extruder (TEX30HSST) manufactured by Nippon Steel Works, equipped with 1 vent. The molten resin composition kneaded under the conditions of a screw rotation speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 260 ° C., rapidly cooled in a water tank, pelletized using a pelletizer, and aromatic polycarbonate A pellet of the resin composition was obtained. The flame retardancy of the obtained resin composition was stable (no variation was found in the burning time of the molded product).

  According to the flame retardant masterbatch of the present invention, the thermoplastic resin composition is excellent in productivity, quality stability, handling workability, and has a high flame retardant effect with no variation in flame retardancy when blended with a thermoplastic resin. In particular, it is suitable for use in casings such as electric / electronic devices and OA devices, and has very high industrial applicability.

Claims (5)

  A total of 100 parts by mass of the aromatic polycarbonate resin (A) 85 to 20% by mass and the aromatic phosphazene compound (B) 15 to 80% by mass and 0.005 to 2 parts by mass of the fluoropolymer (C) are melt-kneaded. A flame retardant masterbatch obtained by   The flame retardant masterbatch according to claim 1, wherein the aromatic polycarbonate resin (A) has a weight average molecular weight of 15,000 to 55,000. The flame retardant masterbatch according to claim 1 or 2, wherein the aromatic phosphazene compound (B) is an aromatic phosphazene compound represented by the following formula (1) and / or (2).

Wherein (1), a is an integer of 3 to 25, ^{R 1,} and ^{R 2} may be the same or different, an aryl group or an alkylaryl group. ]

[In Formula (2), b is an integer of ^{3 to} 10,000, R ³ and R ⁴ may be the same or different and each represents an aryl group or an alkylaryl group. R ⁵ is selected from -N = P (OR ³ ) ₃ groups, -N = P (OR ⁴ ) ₃ groups, -N = P (O) OR ³ groups, and -N = P (O) OR ⁴ groups. It represents at least one, ^{R 6} is, -P ^(OR _{3) 4} group, -P ^(OR ₄₎ 4 ^{group, -P (O) (OR 3} ) 2 ^{group, -P (O) (OR 4} ) 2 At least one selected from the group is shown. ] A thermoplastic resin composition obtained by melt-kneading 100 parts by mass of a thermoplastic resin (C) and 1 to 100 parts by mass of the flame retardant masterbatch according to any one of claims 1 to 3. object.   The thermoplastic resin composition according to claim 4, wherein the thermoplastic resin (C) is an aromatic polycarbonate resin.