JP2019073735A - Method for producing thermoplastic resin composition - Google Patents

Abstract

To provide a method for producing a thermoplastic resin composition having reduced variations in flame retardancy and impact resistance and being excellent in flame retardancy and impact resistance safely without any problem of health damage.SOLUTION: In a method for producing a thermoplastic resin composition incorporating an antimony compound into a thermoplastic resin, the method for producing a thermoplastic resin composition comprises blending, into a thermoplastic resin (I), a master batch comprising an antimony compound contained in 70 to 90 mass% and a thermoplastic resin (II) of the same kind as or different kind from the thermoplastic resin (I), a boron-based flame retardant and a glass fiber and melt kneading by supplying the master batch from a dedicated feeder provided separately from other raw materials into an extruder and supplying the glass fiber from a side feeder.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a thermoplastic resin composition, and more specifically, a thermoplastic resin containing an antimony compound, having less variation in flame retardancy and impact resistance, and having excellent flame retardancy and impact resistance. The present invention relates to a method for safely producing a composition without causing health problems.

  Thermoplastic resins such as polyester resin, polyamide resin, polycarbonate resin, polystyrene resin, acrylonitrile-styrene copolymer resin, polyolefin resin and the like are easy to burn, so in order to impart flame retardancy, various flame retardants are mainly compounded Things have been done.

In particular, when used for electric and electronic parts, automobile parts and other electric parts and machine parts, etc., a higher degree of flame retardancy is required, and also from recent trends of downsizing and weight reduction of various devices, Thin-walled and miniaturized, and in many cases, flame resistance corresponding to the thinnest portion is required, and as flame resistance, the flame retardancy of rank V-0 specified in UL-94 is used as an index. Ru.
Therefore, in order to achieve high flame retardancy, various resin compositions in which a halogen-based flame retardant (especially a bromine-based flame retardant) or a phosphorus-based flame retardant and an antimony compound are blended are proposed (see Patent Documents 1 to 4). ).

  Antimony compounds are widely used because they exert a high effect on the flame retardancy of various resin materials as in the above-mentioned example, while antimony compounds are suspected of having carcinogenicity, It tends to be regulated. The International Cancer Research Institute has classified antimony trioxide as a class 2B carcinogen and is suspected to be carcinogenic, based primarily on animal studies.

  From this problem, the demand for reduction and reduction of antimony compounds is increasing. Therefore, there is a demand for thermoplastic resin materials that do not contain antimony compounds and satisfy flame retardancy UL94V-0, but high flame retardants that do not contain halogen-based flame retardants and antimony compounds and that meet UL94V-0. The fact is that the sex resin composition has not been successful. For this reason, there is a strong demand for a method of manufacturing without using any problem of health while using antimony compounds.

  In addition, since the antimony compound has a large specific gravity and is easily aggregated, variations in flame retardancy and impact resistance are likely to occur.

JP 2004-263174 A Unexamined-Japanese-Patent No. 2006-45544 Unexamined-Japanese-Patent No. 2006-56997 JP 2011-84666 A

  An object (problem) of the present invention is to safely use a thermoplastic resin composition which is less in variation in flame retardancy and impact resistance and is excellent in flame retardancy and impact resistance while containing an antimony compound without causing any problem of health damage. The purpose is to provide a method of manufacturing.

The present inventors have intensively studied to solve the above problems, and as a result, the above problems are solved by blending a masterbatch containing a specific amount of an antimony compound into a thermoplastic resin and melt-kneading it. The present invention has been achieved.
That is, the present invention provides the following method for producing a thermoplastic resin composition.

[1] A method for producing a thermoplastic resin composition comprising an antimony compound in a thermoplastic resin, wherein the thermoplastic resin (I) contains 20 to 90% by mass of the antimony compound and the thermoplastic resin (I) A method for producing a thermoplastic resin composition comprising blending a masterbatch composed of the same or different types of thermoplastic resins (II) and melt kneading.
[2] The method for producing a thermoplastic resin composition according to the above [1], wherein the masterbatch is supplied to the extruder from a dedicated feeder provided separately from other raw materials.
[3] In the above [1] or [2], the thermoplastic resin (I) is a mixture of a thermoplastic polyester resin, a thermoplastic polyester resin and a polycarbonate resin, or a mixture of a thermoplastic polyester resin, a polycarbonate resin and a styrenic resin The manufacturing method of the thermoplastic resin composition as described.
[4] The above-mentioned [1] to [3] wherein the thermoplastic resin (II) is selected from thermoplastic polyester resins, polyamide resins, polystyrene resins, high impact polystyrene resins (HIPS), acrylonitrile-styrene copolymers and polyolefin resins The manufacturing method of the thermoplastic resin composition in any one of-.
[5] The thermoplastic resin (I) contains a polybutylene terephthalate resin, and the thermoplastic resin (II) is a polybutylene terephthalate resin having an intrinsic viscosity of 0.7 to 1.2 dl / g [1] The manufacturing method of the thermoplastic resin composition in any one of-[4].
[6] The content of the antimony compound in the obtained thermoplastic resin composition is 0.5 to 20 parts by mass with respect to 100 parts by mass in total of the thermoplastic resins (I) and (II). The manufacturing method of the thermoplastic resin composition in any one of [5].
[7] The thermoplastic resin according to any one of the above [1] to [6], which contains 1 to 30 parts by mass of a brominated flame retardant with respect to a total of 100 parts by mass of the thermoplastic resins (I) and (II) Method for producing a resin composition.

  The method for producing a thermoplastic resin composition of the present invention produces a thermoplastic resin composition which is excellent in flame retardancy and impact resistance, in particular, while containing an antimony compound, with less variation in flame retardancy and impact resistance. Provide a safe way of manufacturing without problems of health damage to workers.

Hereinafter, the contents of the present invention will be described in detail. The description of each constituent element described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is not The present invention is not construed as being limited to the specific embodiments and specific examples, and can be implemented with arbitrary modifications without departing from the scope of the present invention.
In addition, in this specification, "-" is used in the meaning included as a lower limit and an upper limit with the numerical value described before and behind that.

[Summary of the Invention]
The method for producing a thermoplastic resin composition of the present invention is a method for producing a thermoplastic resin composition containing an antimony compound in a thermoplastic resin, and 20 to 90 mass of the antimony compound in thermoplastic resin (I) It is characterized in that a masterbatch containing a% of the thermoplastic resin (II), which is the same as or different from the thermoplastic resin (I), is blended and melt-kneaded.

[Antimony compound]
Antimony trioxide (Sb ₂ O ₃ ), antimony pentoxide (Sb ₂ O ₅ ), sodium antimonate and the like are preferably mentioned as the antimony compound used in the method for producing a thermoplastic resin composition of the present invention, but in particular, Antimony trioxide is preferred.

[Masterbatch of antimony compounds]
In the present invention, the antimony compound is used as a masterbatch mixed with a thermoplastic resin (II) of the same type or a different type as the thermoplastic resin (I) which is a component of the thermoplastic resin composition. . Under the present circumstances, content of the antimony compound in a masterbatch shall be 20-90 mass% on the basis of a total of 100 mass% of thermoplastic resin (II) and an antimony compound.
The thermoplastic resin (I) used as the main component of the thermoplastic resin composition and the thermoplastic resin (II) used to masterbatch the antimony compound are not limited as long as they are thermoplastic resins. The type and the like will be described later.

The method for forming a master batch is not particularly limited, but a method of melt-kneading thermoplastic resin (II) and an antimony compound may be mentioned.
Examples of the method of melt-kneading include methods using a single-screw or twin-screw extruder type kneader, a continuous kneader such as a kneader roll or a calender roll, or a known kneader such as a pressure kneader or a Banbury mixer. Be Above all, it is preferable to use a twin-screw extruder.
In addition, it is also preferable to dry the thermoplastic resin (II) in advance at the time of melt-kneading. The drying is preferably hot air drying, the temperature is preferably 100 to 140 ° C., more preferably 110 to 130 ° C., and the drying time is preferably 1 to 5 hours, more preferably 2 to 4 hours.

When an extruder is used, the thermoplastic resin (II) and the antimony compound are supplied to the extruder, the mixture is melt-kneaded, the resin composition is extruded from the die nozzle into strands, and then cooled and cut to obtain a masterbatch Pellets are produced.
At this time, it is preferable to use a twin-screw extruder as the melt kneader. Among them, L / D which is a ratio of screw length L (mm) and screw diameter D (mm) preferably satisfies the relationship of 10 <(L / D) <100, and 15 <(L) It is more preferable to satisfy / D) <70. When the ratio is 10 or less, the thermoplastic resin (II) and the antimony compound are hardly finely dispersed, and conversely, even if it exceeds 100, the thermoplastic resin tends to be decomposed, which is not preferable.

  As conditions for melt-kneading, the temperature is preferably 140 to 320 ° C., more preferably 160 to 310 ° C. at barrel temperature. If the melting temperature is less than 140 ° C., the melting is insufficient and aggregation of the unmelted gel and the antimony compound tends to occur frequently, and conversely, if it exceeds 320 ° C., the resin composition is thermally deteriorated and easily colored.

  It is preferable that it is 100-1,000 rpm, and, as for screw rotation speed at the time of melt-kneading, 120-800 rpm is more preferable. If the screw rotation speed is less than 100 rpm, the antimony compound tends to be hardly dispersed finely, and conversely, even if it exceeds 1,000 rpm, the thermoplastic resin tends to be easily decomposed, which is not preferable. Further, the discharge amount is preferably 5 to 2,000 kg / hr, and more preferably 10 to 1,500 kg / hr. If the discharge amount is less than 5 kg / hr, the strands are not stable and the yield tends to decrease, and even if it exceeds 2,000 kg / hr, the antimony compound tends to aggregate and the dispersibility tends to decrease, which is preferable. Absent.

The proportions of the thermoplastic resin (II) and the antimony compound as raw materials to be subjected to the melt-kneading are, as described above, 20 to 90 mass% of the antimony compound based on 100 mass% in total of the thermoplastic resin (II) and the antimony compound. Do. When the content of the antimony compound is less than 20% by mass, the proportion of the antimony compound in the flame retardant masterbatch is small, and the effect of improving the flame retardancy to the thermoplastic resin (I) to which it is blended is small. On the other hand, when the content of the antimony compound exceeds 90% by mass, the dispersibility of the antimony compound tends to decrease, and when this is blended into the thermoplastic resin (I), the flame retardancy of the thermoplastic resin composition becomes unstable, and The workability at the time of flame retardant masterbatch production is also significantly reduced. For example, in the case of production using an extruder, it is not preferable because the strand is not stable and problems such as easy breakage occur easily.
The content of the antimony compound in the masterbatch is preferably 30 to 85% by mass, more preferably 40 to 80% by mass, based on 100% by mass in total of the thermoplastic resin (II) and the antimony compound.

  When the thermoplastic resin (II) and the antimony compound are melt-kneaded into a master batch, various additives such as a stabilizer may be blended, if necessary.

[Production of Thermoplastic Resin Composition]
The masterbatch of the thermoplastic resin (II) and the antimony compound is blended with the thermoplastic resin (I) which is a component of the thermoplastic resin composition, and is melt-kneaded to be a flame retardant thermoplastic resin composition Ru.

  The compounding of the antimony compound masterbatch may be carried out so that the content of the antimony compound in the thermoplastic resin composition obtained is 0.5 to 10% by mass in 100% by mass of the entire thermoplastic resin composition. Preferably, it is more preferably 0.7 to 9% by mass, still more preferably 1 to 8% by mass, particularly 1.5 to 7% by mass, and most preferably 2 to 6% by mass.

The thermoplastic resin (I) and the antimony compound masterbatch, and optionally other flame retardants and additives, are each fed to the extruder in the desired proportions. As an extruder, a single- or twin-screw extruder provided with a die nozzle is used.
At this time, the antimony compound masterbatch is preferably supplied to the extruder from a dedicated feeder provided separately from other raw materials. Antimony compound masterbatch is not mixed with other flame retardants and additives and supplied from the same feeder, but supplied from an independent dedicated feeder, classification is suppressed, and flame resistance and impact resistance are reduced. It is preferable from the point which becomes favorable and the variation is also small.
When the antimony batter batch is supplied from a dedicated feeder, the hopper of the extruder may be fed simultaneously with other raw materials from the dedicated feeder or may be fed to the middle of the extruder. When feeding in the middle of the extruder, it is preferable to feed to the hopper side rather than the kneading zone.

After being supplied to the extruder, the mixture is melt-kneaded, and the resin composition is extruded from the die nozzle into a strand, which is then cooled and cut to produce a molded article (pellet) of the thermoplastic resin composition.
At this time, it is preferable to use a twin-screw extruder as the melt kneader. Among them, L / D which is a ratio of screw length L (mm) and screw diameter D (mm) preferably satisfies the relationship of 10 <(L / D) <150, 15 <(L) It is more preferable to satisfy / D) <100. When this ratio is 10 or less, the thermoplastic resin (I) and the antimony compound and other flame retardants are difficult to finely disperse, and conversely, even if it exceeds 150, the thermal deterioration of the other flame retardants becomes remarkable, and the gas of the free compound It is not preferable because the mechanical strength of the resin composition tends to decrease due to problems or thermal deterioration.

  Moreover, it is preferable that it is 180-350 degreeC, and, as for the melting temperature of the resin composition at the time of melt-kneading, it is more preferable that it is 190-320 degreeC. If the melting temperature is less than 180 ° C., the melting is insufficient and the unmelted gel tends to occur frequently. If the temperature exceeds 350 ° C., the resin composition is thermally deteriorated and easily colored.

  It is preferable that it is 100-1,500 rpm, and, as for screw rotation speed at the time of melt-kneading, 120-1,000 rpm is more preferable. If the screw rotation speed is less than 100 rpm, the antimony compound tends to be hardly dispersed finely, and conversely, even if it exceeds 1,500 rpm, the antimony compound tends to aggregate and not finely dispersed, which is not preferable. Further, the discharge amount is preferably 5 to 5,000 kg / hr, and more preferably 10 to 3,000 kg / hr. If the discharge amount is less than 5 kg / hr, the dispersibility of the antimony compound tends to decrease, and even if it exceeds 5,000 kg / hr, the reaggregation of the antimony compound tends to decrease the dispersibility, which is not preferable.

[Thermoplastic resin (I)]
The thermoplastic resin (I) used as a component of the thermoplastic resin composition in the above production method of the present invention is not particularly limited as long as it is a thermoplastic resin, but polyethylene terephthalate resin, polytrimethylene terephthalate Resin, thermoplastic polyester resin such as polybutylene terephthalate resin; polyamide resin; polycarbonate resin; styrene resin; polyolefin resin such as polyethylene resin, polypropylene resin, cyclic cycloolefin resin; polyacetal resin; polyimide resin; polyetherimide resin; polyurethane Resins; polyphenylene ether resins; polyphenylene sulfide resins; polysulfone resins; polymethacrylate resins;
In addition, thermoplastic resin (I) may be used individually by 1 type, and may be used 2 or more types by arbitrary combinations and a ratio.
Among the above, thermoplastic polyester resins, polycarbonate resins, styrene resins and polyamide resins are preferred as the thermoplastic resin (I), and among these, thermoplastic polyesters are preferred as the thermoplastic resin (I). It is resin, polycarbonate resin, styrene resin.

  The thermoplastic polyester resin is a polyester obtained by polycondensation of a dicarboxylic acid compound and a dihydroxy compound, polycondensation of an oxycarboxylic acid compound, or polycondensation of these compounds, and may be either homopolyester or copolyester. .

As a dicarboxylic acid compound which comprises a thermoplastic polyester resin, aromatic dicarboxylic acid or its ester-forming derivative is preferably used.
As aromatic dicarboxylic acids, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, Biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid Diphenyl isopropylidene-4,4'-dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, anthracene-2,5-dicarboxylic acid, anthracene-2,6-dicarboxylic acid, p -Terphenylene-4,4'-dicarboxylic acid, pyridine-2,5-dicarboxylic acid and the like can be mentioned. Refutaru acid can be preferably used.

These aromatic dicarboxylic acids may be used as a mixture of two or more. As well known, these can be used in the polycondensation reaction as ester-forming derivatives such as dimethyl ester other than the free acid.
In addition, if it is a small amount, together with these aromatic dicarboxylic acids, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecanedioic acid, sebacic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and One or more kinds of alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid can be mixed and used.

Examples of dihydroxy compounds constituting the thermoplastic polyester resin include ethylene glycol, propylene glycol, butanediol, hexylene glycol, neopentyl glycol, 2-methylpropane-1,3-diol, aliphatic glycol such as diethylene glycol and triethylene glycol And cycloaliphatic diols such as cyclohexane-1,4-dimethanol and the like, and mixtures thereof. If the amount is small, one or more long chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like may be copolymerized.
In addition, aromatic diols such as hydroquinone, resorcine, naphthalenediol, dihydroxydiphenyl ether and 2,2-bis (4-hydroxyphenyl) propane can also be used.

  In addition to the above difunctional monomers, trifunctional monomers such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, and trimethylolpropane for introducing a branched structure, fatty acids for controlling molecular weight, etc. Small amounts of monofunctional compounds can also be used in combination.

  As the thermoplastic polyester resin, one usually composed mainly of a polycondensation of a dicarboxylic acid and a diol, that is, one in which 50% by mass, preferably 70% by mass or more of the entire resin consists of this polycondensate is used. The dicarboxylic acid is preferably an aromatic carboxylic acid, and the diol is preferably an aliphatic diol.

Among them, preferred is polyalkylene terephthalate in which 95% by mole or more of the acid component is terephthalic acid and 95% by mass or more of the alcohol component is an aliphatic diol. Typical ones are polybutylene terephthalate and polyethylene terephthalate. It is preferable that these be close to homopolyesters, that is, those in which 95% by mass or more of the whole resin consists of a terephthalic acid component and a 1,4-butanediol or ethylene glycol component.
In the present invention, the main component of the thermoplastic polyester resin is preferably polybutylene terephthalate.
Further, those obtained by copolymerizing polyalkylene glycols such as isophthalic acid, dimer acid and polytetramethylene glycol (PTMG) are also preferable. In addition, these copolymers say that whose copolymerization amount is 1 mol% or more and less than 50 mol% in all segments of polybutylene terephthalate. Among them, the copolymerization amount is preferably 2 to 50 mol%, more preferably 3 to 40 mol%, and particularly preferably 5 to 30 mol%.

  The intrinsic viscosity of the thermoplastic polyester resin is preferably 0.5 to 2 dl / g. From the viewpoint of formability and mechanical properties, those having an intrinsic viscosity in the range of 0.6 to 1.5 dl / g are preferred. When the intrinsic viscosity is lower than 0.5 dl / g, the resulting resin composition molded article tends to have low mechanical strength. Moreover, when it is higher than 2 dl / g, the fluidity of the resin composition may be deteriorated and the moldability may be deteriorated. The intrinsic viscosity of the thermoplastic polyester resin is to be measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

  The polycarbonate resin is an optionally branched thermoplastic polymer or copolymer obtained by reacting a dihydroxy compound or this with a small amount of a polyhydroxy compound with phosgene or a carbonic diester. The method for producing the polycarbonate resin is not particularly limited, and those produced by a conventionally known phosgene method (interfacial polymerization method) or a melting method (transesterification method) can be used.

  As a raw material dihydroxy compound, an aromatic dihydroxy compound is preferable, and 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, Hydroquinone, resorcinol, 4, 4- dihydroxy diphenyl etc. are mentioned, Preferably bisphenol A is mentioned. In addition, compounds in which one or more of tetraalkylphosphonium sulfonates are bonded to the above-mentioned aromatic dihydroxy compounds can also be used.

  Among polycarbonate resins mentioned above, aromatic polycarbonate resins derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxys, among others. Aromatic polycarbonate copolymers derived from compounds are preferred. Moreover, the copolymer which has an aromatic polycarbonate resin as a main, such as a copolymer with the polymer or oligomer which has a siloxane structure, may be sufficient. Furthermore, you may mix and use 2 or more types of polycarbonate resin mentioned above.

  In order to adjust the molecular weight of the polycarbonate resin, monovalent aromatic hydroxy compounds may be used, for example, m- and p-methylphenol, m- and p-propylphenol, p-tert-butylphenol, p-long chain Alkyl substituted phenol etc. are mentioned.

  The viscosity average molecular weight (Mv) of the polycarbonate resin is preferably 20,000 or more, more preferably 23,000 or more and 25,000 or more. When the viscosity average molecular weight is lower than 20,000, the resulting resin composition tends to have low mechanical strength such as impact resistance. It is preferably 60,000 or less, more preferably 40,000 or less, and still more preferably 35,000 or less. If it is higher than 60,000, the flowability of the resin composition may be deteriorated and the moldability may be deteriorated.

In the present invention, the viscosity average molecular weight (Mv) of the polycarbonate resin is obtained by measuring the viscosity of a methylene chloride solution of the polycarbonate resin at 20 ° C. using an Ubbelohde viscometer to determine the limiting viscosity ([η]). The value calculated from the following Schnell's viscosity equation is shown.
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83

  The method for producing the polycarbonate resin is not particularly limited, and polycarbonate resins produced by any of the phosgene method (interfacial polymerization method) and the melting method (ester exchange method) can also be used. Moreover, the polycarbonate resin which gave the post-process which adjusts the amount of OH groups of the terminal to the polycarbonate resin manufactured by the melting method is also preferable.

Examples of the styrene-based resin include homopolymers of styrene-based monomers, copolymers of styrene-based monomers and other copolymerizable monomers, and the like.
More specifically, as the styrene resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), high impact polystyrene resin (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile- Acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylene propylene-based rubber-styrene copolymer (AES resin), styrene-IPN type rubber copolymer And the like. Among these, high impact polystyrene resin (HIPS) and acrylonitrile-butadiene-styrene copolymer (ABS resin) are preferable, and high impact polystyrene (HIPS) is more preferable.

  When a styrene resin contains a rubber component, 3-70 mass% is preferable, as for content of the rubber component in styrene resin, 5-50 mass% is more preferable, and 7-30 mass% is more preferable. When the content of the rubber component is less than 3% by mass, impact resistance may be lowered, and when it exceeds 50% by mass, the flame retardancy tends to be lowered, which is not preferable. The average particle diameter of the rubber component is preferably 0.05 to 10 μm, more preferably 0.1 to 6 μm, and still more preferably 0.2 to 3 μm. If the average particle size is less than 0.05 μm, the impact resistance tends to decrease, and if it exceeds 10 μm, the gloss may be lost and a good appearance may not be obtained.

  The mass average molecular weight of the styrene resin is usually 50,000 or more, preferably 100,000 or more, more preferably 150,000 or more, and usually 500,000 or less, preferably It is 400,000 or less, more preferably 300,000 or less. The number average molecular weight is usually 10,000 or more, preferably 30,000 or more, more preferably 50,000 or more, and usually 300,000 or less, preferably 200, It is 000 or less, more preferably 150,000 or less. Use of such a styrene-based resin is preferable because impact resistance can be easily improved.

  The melt flow rate (MFR) of the styrene resin measured according to JIS K 7210 (temperature 200 ° C., load 5 kgf) is preferably 0.1 to 30 g / 10 min, and 0.5 to 25 g / More preferably, it is 10 minutes. If the MFR is less than 0.1 g / 10 min, the flowability may be lowered, and if it exceeds 30 g / 10 min, the impact resistance tends to be lowered, which is not preferable.

  Examples of methods for producing such styrenic resins include known methods such as emulsion polymerization, solution polymerization, suspension polymerization and bulk polymerization.

  Moreover, there is no restriction | limiting in particular as a polyamide resin used preferably as thermoplastic resin (I), As long as it has an amide bond in a polymer principal chain, any thing can be used. Generally, polyamide resins are obtained by ring-opening polymerization of lactams, polycondensation of diamines and dicarboxylic acids, polycondensation of aminocarboxylic acids, etc., but are not limited thereto.

  The diamine is not limited to the following, but broadly classified, aliphatic diamines, alicyclic diamines and aromatic diamines may be mentioned. Specifically, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodeca Methylenediamine, tridecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4, 4-trimethylhexamethylenediamine, 5-methyl nanomethylenediamine, 1,3-bisaminomethylcyclohexane, 1,4- Bisaminomethylcyclohexane, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine and the like can be mentioned.

  Examples of the dicarboxylic acids include, but are not limited to, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids and aromatic dicarboxylic acids, which are roughly classified into, for example, adipic acid, suberic acid, azelaic acid and sebacine. Acids, dodecanedioic acid, 1,1,3-tridecanedioic acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, dimer acid and the like.

  Specific examples of lactams include ε-caprolactam, enanthate lactam, ω-laurolactam and the like.

  Moreover, as an aminocarboxylic acid, although it is not limited to the following, specifically, ε-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12 -Aminododecanoic acid, 13-aminotridecanoic acid and the like.

  A copolymerized polyamide resin may be obtained by polycondensing a mixture of two or more of the above diamines, dicarboxylic acids, lactams and aminocarboxylic acids. Further, those obtained by polymerizing the above diamines, dicarboxylic acids, lactams and aminocarboxylic acids up to the stage of low molecular weight oligomers in a polymerization reactor and polymerizing them with an extruder or the like can also be suitably used.

  Examples of polyamide resins that can be suitably used as the thermoplastic resin (I) in the present invention include, for example, polyamide 6, polyamide 66, polyamide 46, polyamide 6/66, polyamide 10, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 6/612, polyamide MXD6 consisting of metaxylylenediamine and adipic acid, polyamide 6 / MXD6, polyamide 66 / MXD6, metaxylylenediamine and paraxylylenediamine, and polyamide MP6 consisting of adipic acid, hexamethylenediamine and Polyamide 6T consisting of terephthalic acid, polyamide 6I consisting of hexamethylenediamine and isophthalic acid, polyamide 6 / 6T, polyamide 6 / 6I, polyamide 66 / 6T, polyamide 66 / I, polyamide 6 / 6T / 6I, polyamide 66 / 6T / 6I, polyamide 6/12 / 6T, polyamide 66/12 / 6T, polyamide 6/12 / 6I, polyamide 66/12 / 6I, etc. A polyamide resin obtained by copolymerizing a polyamide resin by an extruder or the like can also be used. Of course, two or more of these may be used in combination.

The preferred relative viscosity of the polyamide resin is preferably 1.6 to 5, more preferably 1.7 to 4, and most preferably 1.8 to 3. When the relative viscosity is too low, the mechanical strength is insufficient, and when it is too high, the formability is reduced and the surface appearance is likely to be reduced.
Here, the relative viscosity is a value measured under the conditions of a concentration of 1 g / 100 ml and a temperature of 25 ° C. in 98% sulfuric acid.

[Thermoplastic resin (II)]
In the present invention, the thermoplastic resin (II) used for the masterbatching of the antimony compound is not limited as long as it is a thermoplastic resin, and the same type of thermoplastic resin as the thermoplastic resin (I) may be used. Also, different types of thermoplastic resins may be used.
Examples of thermoplastic resin (II) include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin; polyamide resin; polycarbonate resin; polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile -Styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES) Styrene resin such as resin); Polyolefin resin such as polyethylene resin, polypropylene resin, cyclic cycloolefin resin; Polyacetal resin; Polyimide resin; Polyether imide resin Polyurethane resins; polyphenylene ether resin; polyphenylene sulfide resins; polysulfone resins; polymethacrylate resins; and the like.

  Among the thermoplastic resins (II), thermoplastic polyester resins, polyamide resins, polystyrene resins, high impact polystyrene resins (HIPS), acrylonitrile-styrene copolymers and polyolefin resins are preferable, and thermoplastic polyester resins are more preferable.

When a thermoplastic polyester resin is used as the thermoplastic resin (II), the intrinsic viscosity is preferably 0.6 to 1.3 dl / g, and more preferably 0.7 to 1.2 dl / g, It is more preferably 0.71 to 1.1 dl / g, and particularly preferably 0.72 to 1 dl / g. If the intrinsic viscosity is lower than 0.6 dl / g, the strands tend to be difficult to draw during melt-kneading, and the productivity tends to decrease. Moreover, if it is higher than 1.3 dl / g, it is easy to vent up at the time of melt-kneading, and the productivity may be lowered. The intrinsic viscosity of the thermoplastic polyester resin is to be measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.
As a thermoplastic polyester resin, polybutylene terephthalate resin is preferable.

As a preferable combination of thermoplastic resin (I) and thermoplastic resin (II) in the manufacturing method of the thermoplastic resin of this invention, the following i)-iv) can be mentioned, for example.
i) The thermoplastic resin (I) is a polybutylene terephthalate resin, and the thermoplastic resin (II) is a polybutylene terephthalate resin having an intrinsic viscosity of 0.7 to 1.2 dl / g.
ii) The thermoplastic resin (I) is a mixture of a polybutylene terephthalate resin and a polycarbonate resin, and the thermoplastic resin (II) is a polybutylene terephthalate resin having an intrinsic viscosity of 0.7 to 1.2 dl / g.
iii) The thermoplastic resin (I) is a mixture of a polybutylene terephthalate resin, a polycarbonate resin and a styrenic resin, and the thermoplastic resin (II) is an intrinsic viscosity of 0.7 to 1.2 dl / g polybutylene terephthalate resin .
iv) Both thermoplastic resins (I) and (II) are polyamide resins.
In the case of the above i) and iv), the compatibility of the thermoplastic resins (I) and (II) is good, so the mechanical properties are good and it is easy to be stabilized. Further, in the case of the above ii) and iii), since the antimony compound is easily present in the polybutylene terephthalate resin phase, the damage to the polycarbonate resin is small, and the impact resistance tends to be good. Moreover, the ester effect reaction of polybutylene-terephthalate resin and polycarbonate resin is suppressed, and a mechanical physical property is easy to be maintained favorably, and is preferable.
Among the above i) to iv), the combination of i) to iii) is more preferable.

  In the present invention, the content of the antimony compound in the thermoplastic resin composition is 0.5 to 20 parts by mass with respect to a total of 100 parts by mass of the thermoplastic resins (I) and (II), and more preferably The amount is 0.7 to 18 parts by mass, more preferably 1 to 15 parts by mass, particularly 1.5 to 10 parts by mass, and most preferably 2 to 8 parts by mass. If the content is less than 0.5 parts by mass, the flame retardancy tends to decrease, and if it exceeds 20 parts by mass, the crystallization temperature decreases, the releasability deteriorates, and the mechanical properties such as impact resistance decrease. To

[Flame retardants]
In the method of the present invention, it is preferable to blend a flame retardant.
As the flame retardant, for example, a halogen-based flame retardant, a phosphorus-based flame retardant, or a silicone-based flame retardant can be contained, and it is preferable to contain a halogen-based flame retardant or a phosphorus-based flame retardant. preferable.

  Examples of phosphorus-based flame retardants include metal salts of (di) phosphinates such as aluminum ethylphosphinate, aluminum diethylphosphinate, aluminum ethylmethylphosphinate, zinc diethylphosphinate, and melamine and phosphorus represented by melamine polyphosphate. Reaction products with acids, phosphoric esters, cyclic phenoxy phosphazenes, linear phenoxy phosphazenes, phosphazenes such as cross-linked phenoxy phosphazenes, etc. are mentioned, among which (di) phosphinate metal salts, melamine polyphosphate, phosphazenes are thermally stable It is preferable from the point which is excellent.

As the halogen-based flame retardant, brominated flame retardants are preferable. Preferred examples thereof include brominated polycarbonate resin, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated Bisphenol A, glycidyl brominated bisphenol A, pentabromobenzyl polyacrylate, brominated imide (brominated phthalimide etc.), etc. are mentioned. Among them, brominated flame retardants are preferable, brominated polycarbonate resin, brominated epoxy resin, brominated Polystyrene resins, glycidyl brominated bisphenol A and pentabromobenzyl polyacrylate tend to be easy to suppress the decrease in impact resistance, and are more preferable.
In particular, when a brominated epoxy resin is used as a flame retardant, it tends to be easily thickened when the resin composition is retained, and the retention heat stability may be unstable. However, the production of the thermoplastic resin of the present invention According to the method, such thickening can be suppressed, and the retention heat stability is improved, which is preferable because the productivity is improved.

  It is preferable that content of a flame retardant is 1-40 mass parts with respect to a total of 100 mass parts of thermoplastic resin (I) and (II). When the amount of the flame retardant is less than 1 part by mass, sufficient flame retardancy is hardly obtained. When the amount exceeds 40 parts by mass, mechanical properties such as impact resistance may be deteriorated. The more preferable content of the flame retardant is 3 to 35 parts by mass, more preferably 5 to 30 parts by mass, particularly preferably 7 to 25 parts by mass with respect to 100 parts by mass in total of the thermoplastic resins (I) and (II). It is a mass part.

[Other ingredients]
The thermoplastic resin composition may further contain various additives as long as the effects of the present invention are not impaired. As such additives, stabilizers such as phosphorus stabilizers and phenol stabilizers, reinforcing agents (fillers), anti-drip agents, release agents, UV absorbers, dyes and pigments, fluorescent whitening agents, charging Examples thereof include antifogging agents, antifogging agents, lubricants, antiblocking agents, flowability improvers, plasticizers, dispersing agents, antibacterial agents and the like.

For the purpose of further improving the flame retardancy, it is preferable to incorporate an anti-dripping agent and a pigment, preferably titanium oxide, for the purpose of enhancing the impact resistance and the flame retardancy.
It is preferable that it is 0.01-3 mass parts with respect to a total of 100 mass parts of thermoplastic resin (I) and (II), and content of a dripping preventing agent is 0.05-2 mass parts. More preferably, it is further preferably 0.1 to 1.4 parts by mass. When the content of the anti-drip agent is less than 0.01 parts by mass, it is difficult to obtain sufficient anti-drip performance at the time of combustion. There is a case.
In addition, the content of the pigment is preferably 0.1 to 10 parts by mass, and 0.5 to 8 parts by mass with respect to 100 parts by mass in total of the thermoplastic resins (I) and (II). More preferably, it is more preferably 1 to 6 parts by mass. When the content of the pigment is less than 0.1 parts by mass, sufficient flame retardancy and impact resistance are difficult to be obtained, and even when it exceeds 10 parts by mass, improvement in flame retardancy and impact resistance may not be recognized in some cases. .

  Hereinafter, the present invention will be more specifically described with reference to examples. However, the present invention is not construed as being limited to the following examples.

(Production Example 1 of Antimony Compound Masterbatch: Production of “MB1”)
Polybutylene terephthalate resin (Mitsubishi Engineering Plastics Co., Ltd., trade name "Novaduran (registered trademark) 5020", intrinsic viscosity 1.20 dl / g, and "Novaduran 5008", intrinsic viscosity, dried in hot air at 120 ° C for 3 hours in advance 30 parts by mass of a 1: 1 mixture of 0.85 dl / g) and 70 parts by mass of an antimony compound (trade name “GMA” manufactured by Yamanaka Sangyo Co., Ltd.) in an interlocking type same direction twin screw extruder (Japan Steel Works, Ltd.) It supplied at 300 kg / hr to "TEX44 (alpha) II" by a company, and 47 mm of screw diameters and L / D = 55.2. Barrel temperature setting C1~C15 a 260 ° C. The extruder, the die 250 ° C., a screw speed of a 230 rpm, the number nozzles 10 holes (round (.phi.4 mm), length 1.5 cm), shear rate (γ) 1012sec ^- It melt-kneaded on condition of ¹ . The strand temperature immediately after extrusion was 290.degree.
After melt-kneading, the resin composition is extruded from a die nozzle into a strand and then cooled, cut, and a masterbatch containing 70 mass% of an antimony compound in which a polybutylene terephthalate resin and an antimony compound are kneaded I got "MB1."

(Production Example 2 of Antimony Compound Masterbatch: Production of “MB2”)
The same procedure as in Production Example 1 was carried out except using only "Novaduran 5007", trade name "Novaduran 5007", manufactured by Mitsubishi Engineering Plastics Co., Ltd., as polybutylene terephthalate resin, polybutylene terephthalate resin and antimony. A masterbatch (hereinafter referred to as "MB2") containing 70% by mass of an antimony compound was obtained, in which the compound and the compound were kneaded.

(Production Example 3 of Antimony Compound Masterbatch: Production of “MB3”)
It is carried out under the same conditions as in Production Example 1 except that only Polyvinyl terephthalate resin manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name "Novaduran 5006" and intrinsic viscosity 0.60 dl / g is used, and polybutylene terephthalate resin and antimony are used. A masterbatch (hereinafter, referred to as "MB3") containing 70% by mass of the antimony compound was obtained, in which the compound and the compound were kneaded. Strand breakage may occur during production of the masterbatch because the strands were difficult to pull.

(Production Example 4 of Antimony Compound Masterbatch: Production of “MB4”)
As polybutylene terephthalate resin, it carried out on the same conditions as manufacture example 1 except using Mitsubishi Engineering Plastics company make, brand name "Novaduran 5026", and intrinsic viscosity 1.26 dl / g only. When the barrel set temperature C1 to C15 of the extruder is performed at 260 ° C, the resin may overflow from the vent part, and it is difficult to draw the strand stably and the stable production is difficult. Therefore, the set temperature of C1 to C15 is increased to 280 ° C. Production was carried out to obtain a masterbatch (hereinafter referred to as "MB4") containing 70% by mass of an antimony compound, in which a polybutylene terephthalate resin and an antimony compound were kneaded.

(Production Example 5 of Antimony Compound Masterbatch: Production of “MB5”)
The procedure of Production Example 1 is repeated except that the amount of the polybutylene terephthalate resin mixture is 20 parts by mass and the amount of the antimony compound is 80 parts by mass in Production Example 1, and the polybutylene terephthalate resin and the antimony compound are kneaded. Further, a master batch (hereinafter referred to as "MB5") containing 80% by mass of the antimony compound was obtained.

Examples 1 to 11 and Comparative Examples 1 to 6 (Production of Thermoplastic Resin Composition)
Raw material components used in Examples and Comparative Examples are as shown in Table 1 below.

Among the components listed in Table 1, the antimony compound master batch (MB1 to 5) is from an independent dedicated feeder, and the other components are blended to give a ratio shown in Table 2 to Table 4 (all mass Supply the hopper to a hopper, and use the 30 mm vent type twin screw extruder (double screw extruder “TEX30α” made by Japan Steel Works Co., Ltd.), hopper when using reinforcing material (glass fiber) The mixture is supplied from the 7th side feeder, melt-kneaded at a barrel temperature of 270 ° C, discharge 80 kg / hr, screw rotation speed 280 rpm, extruded into strands, then pelletized by a strand cutter, and pellets of thermoplastic resin composition Obtained.
In Example 1 and Comparative Example 1, 0.05 parts by mass of calcium stearate was dry-blended with 100 parts by mass of the obtained thermoplastic resin composition pellets to externally add the pellets.
In Example 9, the antimony compound master batch (MB1) is combined with other components without using a dedicated dedicated feeder and blended, and is collectively supplied from the root feeder to obtain thermoplastic resin composition pellets. The

  The obtained thermoplastic resin composition pellets are dried by heating at 120 ° C. for 7 hours, and the conditions of a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. using an injection molding machine (“J85AD” manufactured by Japan Steel Works, Ltd.) Flame retardant and impact resistant were injection molded.

The evaluations of productivity, flame retardancy, impact resistance, crystallization temperature and retention heat stability were conducted as follows.
・ Productivity (strand stability)
The degree of strand breakage per hour during the long run production for 10 hours at the time of thermoplastic resin composition pellet melt-kneading was evaluated based on the following criteria, and was used as an index of production stability.
"Stable": No strand breakage "Slightly unstable": 1 to 2 times

・ Flame retardancy (UL94):
The flame retardancy was tested using five test pieces (thickness: 0.75 mmt or 1.50 mmt) according to the method of Subject 94 (UL 94) of Underwriters Laboratories. The flame retardancy was classified into V-0, V-1 and V-2 according to the evaluation method described in UL94. V-0 is the highest in flame retardancy.
Further, the total combustion time (the total of the combustion time after the first flame contact and the combustion time after the second flame contact) in each of the combustion test pieces was measured, and the dispersion of the combustion time was evaluated by the standard deviation value. Moreover, the total burning time of five test pieces was totaled and it described in the table | surface as total burning time.

・ Notched Charpy impact strength:
An ISO test piece (thickness 4.0 mm) is injection molded, and a 4.0 mm thick notched test piece is prepared from the test piece, and notched Charpy according to ISO 179 standard for 10 test pieces. Impact strength (unit: kJ / m ² ) was measured.
Moreover, the dispersion | variation in Charpy impact strength was evaluated by the standard deviation value.

-Surface impact strength:
A box-shaped molded product (wall thickness 1.5 mmt) of 150 × 80 × 40 mm in size is formed, 2.75 kg of steel balls are dropped from a predetermined height, and the height when the molded product is totally destroyed (unit: : Cm) was determined. The higher the height of total destruction, the better the impact resistance. The test was conducted to a height of 205 cm, and those not broken at 205 cm were described as ">200" in the table.

Crystallization temperature:
Using a differential scanning calorimetry (DSC) machine ("Pyris Diamond" manufactured by PerkinElmer Co., Ltd.), the temperature is raised at a heating rate of 20 ° C / min to 30 ° C and held at 300 ° C for 3 minutes, then the temperature drop rate 20 The peak top temperature of the exothermic peak observed when the temperature was lowered at ° C./min was measured as the crystallization temperature (unit: ° C.).
An exothermic peak due to crystallization is observed, and as the crystallization temperature is higher, transesterification between the thermoplastic polyester resin and the polycarbonate resin is suppressed, which means that it is preferable.

Melt viscosity stability (thickening evaluation):
Melt when retained for 3 minutes after charging the pellet of the thermoplastic resin composition obtained above using a capillary with a measuring temperature of 270 ° C. and a 1φ × 30 flat according to Capirograph (Capirograph 1C manufactured by Toyo Seiki Co., Ltd.) Based on the viscosity (melt viscosity at a shear rate of 91.2 sec ^-1 ), the melt viscosity (melt viscosity at a shear rate of 91.2 sec ^-1 ) when measured for 60 minutes is measured, and the melt viscosity ratio ( 60 min / 3 min) was obtained. As the ratio of the melt viscosity for 3 minutes retention and the melt viscosity for 60 minutes does not change, it means that the thickening is less and the retention stability is excellent.
The above evaluation results are shown in Tables 2 to 4.

It can be seen that the thermoplastic resin composition produced by the production method of the present invention is excellent in flame retardancy and impact resistance, and has little variation in flame retardancy and impact resistance. On the other hand, the resin composition obtained by the comparative example not based on the manufacturing method of the present invention has large variations in flame retardancy and impact resistance, and is inferior in flame retardancy and impact resistance, and satisfies the effects of the present invention. It is not a thing.
Further, from the comparison of Example 3 and Comparative Example 3, Example 11 and Comparative Example 6 in which a brominated epoxy resin is used as a flame retardant, thickening of the resin composition by retention is realized by adopting the production method of the present invention. Is suppressed, and it is understood that a resin composition excellent in staying heat stability can be obtained.
Furthermore, from the comparison of Examples 4 to 9 (the crystallization temperature by DSC is 150 to 151 ° C.) and Comparative Example 4 (the crystallization exothermic peak is not observed by DSC), by adopting the production method of the present invention, It can be seen that the transesterification reaction that occurs when using a mixture of polybutylene terephthalate resin and polycarbonate resin as the thermoplastic resin (I) can be effectively suppressed.

  The method for producing a thermoplastic resin composition according to the present invention safely produces a flame retardant thermoplastic resin composition having little variation in flame retardancy and impact resistance and excellent impact resistance without causing any problem of health damage. , Industrial availability is very high.

Claims (7)

A method for producing a thermoplastic resin composition comprising an antimony compound in a thermoplastic resin,
Thermoplastic resin (I), master batch comprising 70 to 90% by mass of an antimony compound and composed of thermoplastic resin (II) of the same or different type as thermoplastic resin (I) , brominated flame retardant and glass fiber Mix,
The method for producing a thermoplastic resin composition, wherein the masterbatch is supplied to an extruder from a dedicated feeder provided separately from other raw materials, and glass fibers are supplied from a side feeder and melt-kneaded. The method for producing a thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (I) is a thermoplastic polyester resin, a polycarbonate resin, a polyamide resin, a styrene resin, and a mixture thereof . The thermoplastic resin composition according to claim 1 or 2 , wherein the thermoplastic resin (I) is a mixture of a thermoplastic polyester resin, a thermoplastic polyester resin and a polycarbonate resin, or a mixture of a thermoplastic polyester resin, a polycarbonate resin and a styrenic resin. Method of manufacturing objects. The thermoplastic resin (II) is selected from thermoplastic polyester resin, polyamide resin, polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer and polyolefin resin according to any one of claims 1 to 3. The manufacturing method of the thermoplastic resin composition as described. The thermoplastic resin (I) contains polybutylene terephthalate resin, and the thermoplastic resin (II) is polybutylene terephthalate resin having an intrinsic viscosity of 0.7 to 1.2 dl / g. The manufacturing method of the thermoplastic resin composition of any one of-. The content of the antimony compound in the thermoplastic resin composition obtained is, any claim 1-5 total 100 parts by weight of the thermoplastic resin (I)及Beauty (II) to from 0.5 to 20 parts by weight The manufacturing method of the thermoplastic resin composition of any one of-. Brominated flame retardants, the total relative to 100 parts by weight, the thermoplastic resin composition according to any one of claims 1 to 6 containing 1 to 30 parts by weight of the thermoplastic resin (I)及Beauty (II) Manufacturing method.