JPH0892264A - Method for producing flame-retardant resin composition - Google Patents

Abstract

(57) [Summary] [Structure] In a method for producing a flame-retardant resin composition using an extruder, the extruder is a first raw material supply port provided on the upstream side with respect to the flow direction of the raw material, and a downstream side. Has a second raw material supply port, the thermoplastic resin of the component (A) is supplied from the first raw material supply port, and the specific phosphoric acid ester of the component (B) is supplied from the second raw material supply port. A method for producing a flame-retardant resin composition, which comprises heating the compound to 50 ° C. to 120 ° C. and supplying it by liquid addition. [Effect] A flame-retardant resin composition comprising a thermoplastic resin and a specific phosphoric acid ester compound in which a flame-retardant agent does not evaporate during molding can be industrially stably produced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a flame-retardant resin composition comprising a thermoplastic resin and a specific phosphoric acid ester compound in which a flame-retardant agent does not evaporate during molding.

[0002]

2. Description of the Related Art Phosphate ester compounds include polyphenylene ether resins and polycarbonate resins,
Widely used as a flame retardant for many resins. However, relatively low molecular weight phosphoric acid ester compounds such as triphenyl phosphate volatilize from the resin phase during molding and adhere to the mold surface and degassing part, causing molding problems and poor appearance of molded products. Therefore, a phosphoric acid ester compound having a large molecular weight is being developed. For example, JP-A-55-118957 discloses a flame-resistant composition comprising a polyphenylene ether resin, a styrene resin and a polyfunctional phosphate ester, and JP-A-60-47054 discloses an ABS resin, a polyphenylene ether resin, Flame-retardant blend consisting of organic phosphate such as functional phosphate and brominated flame retardant, JP-B-2-26656
JP-A No. 2-115262 discloses a modified blend of a polyamide resin, a polyphenylene ether resin and an aromatic phosphate ester containing a polyfunctional phosphate ester, and JP-A-2-115262 discloses an aromatic polycarbonate, a styrene resin and an oligomeric phosphate. Polymer mixtures consisting of esters are described.

Conventionally, as a method for industrially producing a resin composition comprising a thermoplastic resin and a phosphoric acid ester compound as described above, a resin and a phosphoric acid ester compound are mainly mixed and the resulting mixture is mixed. A mechanical kneading method of melt-kneading using a shaft extruder or the like and pelletizing has been used. However, since phosphoric acid esters are generally liquid at room temperature or have a melting point lower than the processing temperature of the resin, it becomes difficult to uniformly mix the resin with the resin when the amount added to the resin increases in the above method. Become. Even if it can be mixed, the mixture is hard to handle because it hardens in a dumpling form, becomes sticky, and cannot be weighed, put into an extruder or the like, and cannot be fed in a fixed amount. In addition, the phosphoric acid ester liquefies by heating near the extruder input port, and the viscosity drops sharply, so that the phosphoric acid ester does not stay and the resin does not get caught. Is difficult. Even if it can be fed, the resin is sent through the cylinder at the same time as the low-viscosity material, so the plasticization of the resin in the extruder is insufficient, and the phosphate ester blows out from the die or the vent port, or the resin is not added to the composition. Melt may be generated or resin may be surging. Further, in these methods, the heat resistance and heat stability of the phosphoric acid ester compound are not sufficient as compared with the processing temperature of the resin, and the phosphoric acid ester compound is exposed to a high temperature during processing and volatilizes, decomposes, or decomposes. There is a problem that the generated decomposition product reacts with the resin to generate a gelled product or a carbide, or deteriorates the resin.

As described above, the conventional methods for industrially producing a flame-retardant resin composition using a phosphoric acid ester compound have problems that workability is poor, stable production is difficult, and production efficiency is poor. there were.

[0005]

DISCLOSURE OF THE INVENTION The present invention industrially and stably produces a flame-retardant resin composition comprising a thermoplastic resin and a specific phosphoric acid ester compound without volatilization of a flame retardant during molding. The task is to do.

[0006]

The present inventor has accomplished the present invention as a result of extensive studies to solve the above problems. That is, the present invention is a method for producing a flame-retardant resin composition using an extruder, wherein the extruder is provided at a first raw material supply port provided on the upstream side with respect to the flow direction of the raw material and provided on the downstream side. A second raw material supply port, the thermoplastic resin of the component (A) is supplied from the first raw material supply port, and the general formula (I) of the component (B) is supplied from the second raw material supply port.

[0007]

[Chemical 2]

(Here, Q1, Q2, Q3 and Q4 each independently represent an alkyl group having 1 to 6 carbon atoms. R1 and R2 each independently represent a methyl group, and R3 and R4 each independently represent a methyl group or hydrogen. n represents an integer greater than or equal to 1. n1 and n2 are 0 independently.
Represents an integer from 2 to 2. m1, m2, m3, and m4 each independently represent an integer of 0 to 3. ) A phosphoric ester compound represented by the formula (4) is heated from 50 ° C. to 120 ° C., and is supplied by liquid addition, which is a method for producing a flame retardant resin composition.

As the thermoplastic resin as the component (A) of the present invention, polyphenylene ether resin, polycarbonate resin, polystyrene, rubber-modified polystyrene, AS resin,
Polystyrene resin such as ABS resin, polyethylene,
Polyolefin resin such as polypropylene, polyamide resin such as 6-nylon, 6,6-nylon, 6,10-nylon and 12-nylon, thermoplastic elastomer,
Polyethylene terephthalate, polybutylene terephthalate, acrylic resin, polyvinyl alcohol, polyvinyl acetate, polyacetal and the like can be used alone or in combination of two or more, but are not limited thereto. Among these, polyphenylene ether resin, polyphenylene ether resin and polystyrene resin, polycarbonate resin, polycarbonate resin and polystyrene resin are particularly preferable.

The polyphenylene ether resin which can be used as the component (A) is represented by the following general formula (II-
1) and / or a homopolymer having a repeating unit represented by (II-2), or a copolymer.

[0011]

[Chemical 3]

(Where R5, R6, R7, R8, R
9 and R10 independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen, or hydrogen. However, R9 and R10 are not hydrogen at the same time. ) A typical example of a homopolymer of polyphenylene ether resin is poly (2,6-dimethyl-1,4-phenylene).
Ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4)
-Phenylene) ether, poly (2-ethyl-6-n-)
Propyl-1,4-phenylene) ether, poly (2,
6-di-n-propyl-1,4-phenylene) ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-) Examples thereof include phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, and poly (2-methyl-6-chloroethyl-1,4-phenylene) ether.

Among these, poly (2,6-dimethyl-1,
4-phenylene) ether is particularly preferred. The polyphenylene ether resin copolymer is a copolymer having a phenylene ether structure as a main monomer unit. Examples thereof include copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol, copolymers of 2,6-dimethylphenol and o-cresol, or 2,6-dimethylphenol and 2 , 3,6-trimethylphenol and a copolymer with o-cresol.

Further, in the polyphenylene ether resin of the present invention, various other phenylene ether units which have been proposed to be present in the polyphenylene ether resin may be used, as long as they do not violate the gist of the present invention. It may be included as a partial structure. As an example of what is proposed to coexist in a small amount, JP-A-1-29 is known.
2- (dialkylaminomethyl) -6 described in JP 7428 and JP-A 63-301222.
-Methylphenylene ether unit, 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit, and the like.

Further, a polyphenylene ether resin in which a small amount of diphenoquinone or the like is bound in the main chain is also included.
Furthermore, for example, polyphenylene ether modified with a compound having a carbon-carbon double bond, as described in JP-A-2-276823, JP-A-63-108059, JP-A-59-59724 and the like. Also includes.

The method for producing the polyphenylene ether resin used in the present invention is not particularly limited, but, for example, in the presence of dibutylamine in the presence of dibutylamine according to the method described in JP-B-5-13966. It can be produced by oxidative coupling polymerization of xylenol. Moreover, the molecular weight and the molecular weight distribution are not particularly limited.

The polystyrene resin that can be used as the component (A) is a vinyl aromatic polymer or a rubber-modified vinyl aromatic polymer. As the vinyl aromatic polymer, in addition to styrene, nuclear alkyl-substituted styrenes such as o-methylstyrene, p-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene and p-tert-butylstyrene, α-methylstyrene,
Polymers of α-alkyl-substituted styrenes such as α-methyl-p-methylstyrene, and copolymers of one or more of these with at least one of other vinyl compounds, and these 2
One or more copolymers may be mentioned. As the compound copolymerizable with the vinyl aromatic compound, methyl methacrylate,
Methacrylic acid esters such as ethyl methacrylate,
Examples thereof include unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile, and acid anhydrides such as maleic anhydride. Among these polymers, particularly preferred polymers are polystyrene and styrene-acrylonitrile copolymer (AS resin).

Examples of the rubber used for the rubber-modified vinyl aromatic polymer include polybutadiene, styrene-butadiene copolymer, polyisoprene, butadiene-isoprene copolymer, natural rubber and ethylene-propylene copolymer. You can In particular, polybutadiene and a styrene-butadiene copolymer are preferable, and as the rubber-modified aromatic polymer, rubber-modified polystyrene (HIPS),
Rubber-modified styrene-acrylonitrile copolymer (ABS
Resin) is preferred.

The polycarbonate resin which can be used as the component (A) is a polymer having a repeating unit represented by the general formula (III-1).

[0020]

[Chemical 4]

(Here, Z represents a mere bond, or alkylene having 1 to 8 carbon atoms, alkylidene having 2 to 8 carbon atoms, cycloalkylene having 5 to 15 carbon atoms, SO ₂ , S
It represents O, O, CO, or a group represented by formula (III-2). X represents hydrogen or an alkyl group having 1 to 8 carbon atoms. a and b show the integer of 0-4 independently. )

[0022]

[Chemical 5]

Polycarbonate resin can be obtained by, for example, a solvent method,
That is, in the presence of a known acid acceptor and a molecular weight modifier in a solvent such as methylene chloride, the reaction between a dihydric phenol and a carbonate precursor such as phosgene, or a dihydric phenol and a carbonate precursor such as diphenyl carbonate. It can be produced by a transesterification reaction. The dihydric phenol that can be used here is 2,
2-bis (4-hydroxyphenyl) propane [commonly called bisphenol A], hydroquinone, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) alkane, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxy) Phenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether and the like. These can be used alone or in combination. Among these, bisphenol A and a mixture of bisphenol A and another dihydric phenol are preferable, and bisphenol A is most preferable. Further, instead of these dihydric phenols, a homopolymer of dihydric phenol or a copolymer of two or more kinds or a mixture of a homopolymer and a copolymer may be used.

The polycarbonate resin used in the present invention may be a thermoplastic random branched polycarbonate obtained by reacting a polyfunctional aromatic compound with a dihydric phenol and / or a carbonate precursor. The phosphoric acid ester compound used as the component (B) of the present invention has the general formula (I):

[0025]

[Chemical 6]

(Here, Q1, Q2, Q3, and Q4 independently represent an alkyl group having 1 to 6 carbon atoms. R1 and R2 each independently represent a methyl group, and R3 and R4 independently represent a methyl group or hydrogen. n represents an integer greater than or equal to 1. n1 and n2 are 0 independently.
Represents an integer from 2 to 2. m1, m2, m3, and m4 each independently represent an integer of 0 to 3. ). General formula (I)
It is preferable that n1 and n2 are 0 and R3 and R4 are methyl groups.

In the general formula (I), m1, m2,
m3 and m4 are 0, that is, there is no substitution of an alkyl group on the terminal phenyl group, or Q1, Q2, Q3,
Most preferably, Q4 is a methyl group, that is, a terminal phenyl group is substituted with a methyl group. N in the general formula (I) is an integer of 1 or more, and heat resistance and workability vary depending on the number. The preferred range of n is 1
It is -10. The component (B) may be a mixture of n-mers.

The phosphoric acid ester compound of the component (B) of the present invention has a binding structure with a specific bifunctional phenol and a terminal structure with a specific monofunctional phenol. Examples of the bifunctional phenol include 2,2-bis (4-hydroxyphenyl) propane [commonly called bisphenol A], 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) methane, Bis (4-hydroxy-3,5-dimethylphenyl) methane, 1,1-
Examples include, but are not limited to, bisphenols such as bis (4-hydroxyphenyl) ethane. Bisphenol A is particularly preferable.

As the monofunctional phenol, unsubstituted phenol, monoalkylphenol, dialkylphenol and trialkylphenol can be used alone or as a mixture of two or more kinds. Phenol, cresol, dimethylphenol (mixed xylenol) and trimethylphenol are particularly preferable. The phosphoric acid ester compound as the component (B) is significantly less volatile than conventional phosphoric acid esters such as triphenyl phosphate, and is excellent in heat resistance, heat stability, hydrolysis resistance and the like. ing. Heat resistance, because it is excellent in thermal stability, it is possible to heat for liquid addition that could not withstand with conventional phosphoric acid ester compounds, at the heating temperature of the present invention, even for long-term retention, volatilization, Does not decompose or deteriorate.

Further, it does not cause a problem such as gelation by causing a reaction with the resin, does not accelerate the decomposition of the resin, and does not corrode a metal part such as a molding machine. The phosphoric acid ester compound as the component (B) can be obtained by reacting the above-mentioned bifunctional phenol and monofunctional phenol with phosphorus oxychloride, but the production method is not limited at all.

The phosphoric acid ester as the component (B) used in the present invention is a phosphoric acid ester generally used within a range not impairing the effects of the invention, such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, It may contain phosphoric acid esters such as cresyl diphenyl phosphate, dicresyl phenyl phosphate, hydroxyphenyl diphenyl phosphate, compounds obtained by modifying these with various substituents, various condensation type phosphoric acid ester compounds, and the like.

The extruder used in the present invention has a first raw material supply port provided on the upstream side with respect to the flow direction of the raw material and a second raw material supply port provided on the downstream side. A thermoplastic resin, a stabilizer, a colorant, etc. are introduced from the first raw material supply port, and a liquid phosphoric acid ester compound is supplied by liquid addition from the second raw material supply port. At this time, the temperature from the first raw material supply port to the second raw material supply port is preferably as low as possible as long as the thermoplastic resin is sufficiently melted and kneaded.
The same applies to the temperature from the second raw material supply port to the die. Further, the second raw material supply port can be provided at any position in the downstream direction of the first raw material supply port, as long as sufficient kneading can be provided to obtain a uniform resin composition. The extruder may be any known single-screw extruder, non-meshing counter-rotating twin-screw extruder, interlocking counter-rotating twin-screw extruder, interlocking co-rotating twin screw extruder as long as sufficient melt-kneading is obtained. A shaft screw extruder or the like can be used.

The addition of the phosphoric acid ester compound at the second raw material supply port is carried out from a feed port provided in a barrel of a usual extruder at a discharge pressure higher than the resin pressure in the extruder by a known pump for liquid transportation. . At this time, the phosphoric acid ester compound to be supplied is heated in a temperature range of 50 ° C. to 120 ° C. to reduce the viscosity of the phosphoric acid ester compound to a viscosity suitable for liquid addition and then supplied. At this time, if the heating temperature is 50 ° C. or lower, the viscosity of the phosphoric acid ester compound cannot be lowered sufficiently, and if it exceeds 120 ° C., the phosphoric acid ester compound volatilizes, decomposes, modifies, deteriorates due to long-term heating. It is not preferable.

By adding the phosphoric acid ester compound from the second raw material supply port, it is possible to measure and supply the resin component separately from the resin component, and to improve the difficulty of mixing the liquid phosphoric acid ester compound and the solid resin component. can do. Also,
Avoids the phenomenon that when resin and liquid components with remarkably different melting and softening temperatures are top-fed at the same time, the resin component does not melt sufficiently and is extruded to float in the liquid component, or the unmelted portion remains in the resin component. By adding the liquid component to the sufficiently melted and kneaded resin component, the kneading of both can be stably performed.

By supplying the phosphoric acid ester compound from the second raw material supply port, the thermal history of the phosphoric acid ester compound can be reduced, and the volatilization, decomposition, modification and deterioration of the phosphoric acid ester compound can be suppressed. be able to. At the same time, by supplying a liquid phosphoric acid ester compound after the resin is melted, shear heat of kneading can be reduced and the resin temperature can be lowered.

The extruder of the present invention has other raw material supply ports in addition to the first and second raw material supply ports, and divides the resin component within a range not impairing the effects of the present invention, or glass filler, glass flakes. Reinforcing fillers and fillers such as, and other additives can also be supplied. In the resin composition of the present invention, other additives within a range that does not impair the effects of the present invention, for example, plasticizers, other flame retardants, antioxidants, stabilizers such as ultraviolet absorbers, release agents, dyes and pigments. , Or fiberglass,
Fibrous reinforcing agents such as carbon fibers, and further fillers such as glass beads, calcium carbonate and talc can be added.

[0037]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. The impact-resistant polystyrene resin, ABS resin, and AS resin used in the examples and comparative examples were prepared by the manufacturing method described below.

[0038]

[Production Example 1] (Production of partially hydrogenated conjugated diene rubber for impact-resistant polystyrene resin) Using a stirrer with an internal volume of 10 liters and an autoclave with a jacket as a reactor, butadiene / n
-Hexane mixed solution (butadiene concentration 20%) at 20 liters / hour and n-butyllithium / n-hexane solution (concentration 5%) at 70 ml / hour were introduced to continuously polymerize butadiene at a polymerization temperature of 110 ° C. Carried out. The obtained active polymer was deactivated with methanol, and 8 liters of the polymer solution was transferred to another reactor with a stirrer and a jacket having an internal volume of 10 liters, and at a temperature of 60 ° C., di-p-as a hydrogenation catalyst. 250 ml of trilyl-bis (1-cyclopentadienyl) titanium / cyclohexane solution (concentration 1.2 mmol / liter) and 50 ml of n-butyllithium solution (concentration 6 mmol / liter) were added at 0 ° C. and 2.0 kg. The mixture mixed under a hydrogen pressure of / cm ² was added, and the mixture was reacted at a hydrogen partial pressure of 3.0 kg / cm ^{2 for} 60 minutes. The resulting partially hydrogenated polymer solution was added with 0.5 part of 2,6-di-t-butylhydroxytoluene per polymer as an antioxidant to remove the solvent. The analytical values of the partially hydrogenated conjugated diene rubber obtained by sampling after deactivation of methanol are shown in Table 1.

[0039]

[Table 1]

(Production of Impact-Resistant Polystyrene Resin) The impact-resistant styrene resin used in the examples was produced by the bulk polymerization method. 10 parts of the partially hydrogenated conjugated diene rubber produced by the above method was dissolved in 90 parts of styrene and 8 parts of ethylbenzene, and further 0.05 parts of benzoyl peroxide and 0.10 parts of α-methylstyrene 2 was added to styrene. Add body, 80 ° C for 4 hours, 110 ° C for 4 hours, 150 ° C
Polymerization was carried out for 4 hours with stirring. Further around 230 ℃ 30
Heat treatment was carried out for a minute, and then unreacted styrene and ethylbenzene were removed in vacuum to obtain a high impact polystyrene resin. The content of partially hydrogenated polybutadiene in the obtained impact-resistant polystyrene resin was 11%, and the average particle diameter of partially hydrogenated polybutadiene in the state of containing dispersed polystyrene particles was 1.3 μm. The reduced viscosity measured in toluene at 30 ° C. was 0.65.

(Production of ABS resin) The average particle size is 0.3.
A polymerization tank was charged with 750 parts by weight of 0 μm butadiene latex (40% by weight in terms of rubber) and 1 part by weight of an emulsifier (potassium disproportionated rosin acid) and heated to 70 ° C. in a nitrogen stream while stirring. Acrylonitrile 200 parts by weight, styrene 500 parts by weight, cumene hydroperoxide 0.8 parts by weight, t-dodecyl mercaptan 0.7.
1.0 part by weight of sodium formaldehyde sulfoxylate, 0.10 part by weight of ferrous sulfate (FeSO ₄ .7H ₂ O), ethylenediamine tetraacetic acid / 2Na salt of 0.2 part by weight of a mixed solution of 500 parts by weight and distilled water of 500 parts by weight. Polymerization was carried out by adding an aqueous solution in which 2 parts by weight was dissolved over 6 hours.

After the addition was completed, the mixture was stirred for 2 hours to complete the polymerization. The polymerization rate was 94%. The produced graft copolymer latex was coagulated with a dilute sulfuric acid aqueous solution, washed, dehydrated and dried to obtain a white powder of ABS resin.

[0043]

Production Example 2 (Production of AS resin) To 180 parts by weight of water, 0.4 parts by weight of potassium persulfate and 2.0 parts by weight of potassium rosinate were added and dissolved, and 70 parts by weight of styrene and 30 parts by weight of acrylonitrile were added to this aqueous solution. And 0.2 part by weight of dodecyl mercaptan were added and reacted at 70 ° C. for 4 hours to obtain an aromatic vinyl copolymer. The polymerization rate was 94%. The produced copolymer was coagulated with a dilute sulfuric acid aqueous solution, washed, dehydrated and dried to obtain a white powder AS resin.

[0044]

Example 1 Poly 2,6-dimethyl-1,4 having an intrinsic viscosity [η] of 0.53 measured at 30 ° C. in chloroform.
Powder of phenylene ether (hereinafter abbreviated as PPE) was used as ZSK-25 [Wer with the barrel temperature set at 320 ° C.
manufactured by Ner Co.] is charged into the hopper of the first raw material supply port of the twin-screw extruder, quantitatively fed by a screw feeder and melt-kneaded, while the chemical formula (IV),

[0045]

[Chemical 7]

Phosphate ester A represented by (n = 1 to 3)
Mixture) is heated to 70 ° C., and P is applied using a gear pump (Toko Sangyo Co., Ltd .: trade name Zenith high precision metering pump).
The ratio of PE and phosphate ester A is PPE with respect to the total weight.
Was adjusted to 65% by weight and the phosphoric acid ester A was adjusted to 35% by weight, and side feed was performed from the second raw material supply port.
The extruded strand was cooled with water and then cut with a pelletizer to obtain pellets. The production conditions were good, and pellets could be obtained stably. Injection molding was performed using the pellets, and flame retardancy was evaluated. The flame retardancy was evaluated by using a 1/8 inch test piece based on the UL standard 94 vertical combustion test method and ranked. The results are shown in Table 2.

[0047]

Example 2 The phosphoric acid ester A in Example 1 was replaced by the chemical formula (V),

[0048]

Embedded image

Phosphate ester B represented by (n = 1 to 3)
The same evaluation as in Example 1 was carried out except that the mixture was replaced with the mixture), and the results are shown in Table 2.

[0050]

Comparative Example 1 The powder of PPE used in Example 1 and the phosphoric acid ester A heated to 70 ° C. were mixed with a Henschel mixer, and then charged into a hopper of a first raw material supply port of the extruder to obtain Example 1. When an attempt was made to perform melt-kneading in the same manner as in, blocking of the mixture occurred in the hopper and stable quantitative feed could not be performed. The mixture was constantly fed by hand while breaking the blocking to obtain pellets for evaluation.

[0051]

[Table 2]

[0052]

Example 3 The powder of PPE in Example 1 was used as an aromatic polycarbonate resin (hereinafter abbreviated as PC) [Japan GE
Plastics Co., Ltd .: Lexane 121] was used in place of the pellets, the barrel temperature was set to 280 ° C., and the ratio of PC to phosphate ester A was 75% by weight of PC relative to the total weight.
Evaluation was performed in the same manner as in Example 1 except that the phosphoric acid ester A was adjusted to 25% by weight, and the results are shown in Table 3.

[0053]

Example 4 The same evaluation as in Example 3 was carried out except that the phosphoric acid ester A in Example 3 was replaced with the phosphoric acid ester B, and the results are shown in Table 3.

[0054]

[Comparative Example 2] PC pellets used in Example 3 and 70 ° C
The heated phosphoric acid ester A was dry-blended, the mixture was put into the hopper of the first raw material supply port of the extruder, and melt kneading was carried out in the same manner as in Example 3. The mixture in the hopper was The blocking was so bad that the mixture could not be fed by the screw feeder. When the mixture was manually fed to the supply port, the phosphate ester was reduced in viscosity and accumulated, and the pellets slipped and could not be extruded without being caught in the screw.

[0055]

[Table 3]

[0056]

Example 5 PPE powder used in Example 1 and Production Example 1
Impact-resistant polystyrene resin (hereinafter abbreviated as HIPS) and polystyrene resin (hereinafter abbreviated as GPPS) prepared in [Asahi Kasei Kogyo Co., Ltd .: Asahi Kasei Polystyrene 68
5] are dry blended in a weight ratio of 29, 7, and 7, respectively,
Preliminary kneading was carried out with an extruder having a barrel temperature set to 320 ° C. to obtain pellets. 43 parts by weight of the pre-kneading pellets and H
43 parts by weight of IPS and octadecyl-3 as a stabilizer
0.3 parts by weight of-(3-5-di-t-butyl-4-hydroxyphenyl) propionate were mixed, charged into the first raw material supply port of the extruder whose barrel temperature was set to 280 ° C, and fed quantitatively. While melting and kneading the phosphoric acid ester A in the same manner as in Example 1,
It was adjusted to 4 parts by weight and side-fed from the second raw material supply port. The production conditions were good, and pellets could be obtained stably. Evaluation was performed in the same manner as in Example 1,
The results are shown in Table 4.

[0057]

Example 6 Evaluations were made in the same manner as in Example 5 except that the phosphate ester A in Example 5 was replaced with the phosphate ester B, and the results are shown in Table 4.

[0058]

Comparative Example 3 Pre-kneaded pellets 43 prepared in Example 5
Parts by weight, 43 parts by weight of HIPS, phosphate ester A heated to 70 ° C., and octadecyl-3-as a stabilizer.
(3-5-di-t-butyl-4-hydroxyphenyl)
When 0.3 part by weight of propionate was dry-blended and charged into the hopper of the first raw material supply port of the extruder to perform melt kneading in the same manner as in Example 5, blocking of the mixture in the hopper was severe, The mixture could not be quantitatively fed by the screw feeder. When the mixture was manually fed to the supply port, the phosphate ester was reduced in viscosity and accumulated, and the pellets slipped and could not be extruded without being caught in the screw.

[0059]

[Table 4]

[0060]

Example 7 45.5 parts by weight of the PC used in Example 3,
18.2 parts by weight of the ABS resin prepared in Production Example 2 and 27.3 parts by weight of the AS resin were dry blended, and the barrel temperature was adjusted to 2
Into the first raw material supply port of the extruder set to 50 ° C., quantitatively feeding and melting and kneading, the phosphoric acid ester A was 9 parts by weight in the same manner as in Example 1. Thus, the side feed was performed from the second raw material supply port. The production conditions were good and stable pellets could be obtained. Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 5.

[0061]

Example 8 Evaluations were made in the same manner as in Example 7 except that the phosphate ester A in Example 7 was replaced with the phosphate ester B, and the results are shown in Table 5.

[0062]

Comparative Example 4 45.5 parts by weight of the PC used in Example 7,
AS resin 18.2 parts by weight, AS resin 27.3 parts by weight, 7
When 9 parts by weight of phosphoric acid ester A heated to 0 ° C. was dry blended and charged into the hopper of the first raw material supply port of the extruder, an attempt was made to perform melt kneading in the same manner as in Example 7,
Blocking of the mixture in the hopper was so bad that the mixture could not be quantitatively fed by the screw feeder. When the mixture was manually sent to the supply port, the phosphate ester became less viscous and accumulated, the pellets slipped, the screw was not well bitten, and burnt dust was generated in the extruded strand, so black dust was generated on the test piece. Mixed.

[0063]

[Table 5]

[0064]

INDUSTRIAL APPLICABILITY A flame-retardant resin composition comprising a thermoplastic resin and a specific phosphoric acid ester compound in which a flame-retardant agent does not evaporate during molding can be produced industrially and stably.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C08L 69/00 LPQ 71/12 LQP 85/04 LSB

Claims (5)

[Claims] 1. A method for producing a flame-retardant resin composition using an extruder, wherein the extruder is provided at a first raw material supply port provided on the upstream side and a downstream side with respect to the flow direction of the raw material. It has a second raw material supply port and supplies the thermoplastic resin of the component (A) from the first raw material supply port, and the general formula (I) of the component (B) from the second raw material supply port: ] (Here, Q1, Q2, Q3, and Q4 independently have 1 carbon atom.
Represents an alkyl group from 6 to 6. R1 and R2 are methyl groups,
R3 and R4 independently represent a methyl group or hydrogen. n is 1
Represents the above integers. n1 and n2 each independently represent an integer of 0 to 2. m1, m2, m3, and m4 each independently represent an integer of 0 to 3. ) The phosphoric acid ester compound represented by 50
A method for producing a flame-retardant resin composition, which comprises heating from 0 ° C to 120 ° C and supplying it by adding a liquid. 2. The method for producing a flame-retardant resin composition according to claim 1, wherein the thermoplastic resin as the component (A) is a polyphenylene ether resin. 3. The thermoplastic resin as the component (A) is a polyphenylene ether resin and a polystyrene resin.
A method for producing the flame-retardant resin composition described. 4. The method for producing a flame-retardant resin composition according to claim 1, wherein the thermoplastic resin as the component (A) is a polycarbonate resin. 5. The method for producing a flame retardant resin composition according to claim 1, wherein the thermoplastic resin as the component (A) is a polycarbonate resin and a polystyrene resin.