JPH07216100A - Pellet for producing flame-resistant resin material, and method for producing flame-resistant resin material - Google Patents

Abstract

PURPOSE:To obtain the subject pellet comprising a polyphenylene ether resin, etc., and a specific phosphate ester, low in load deflection temperature, easy in extrusion molding processing, excellent in handleability, and capable of imparting flame retardancy to the resin materials. CONSTITUTION:This pellet comprises (A) a polyphenylene ether resin or a polycarbonate resin and (B) a phosphate ester of the formula (Q1 to Q4 each is a 1-6C alkyl; R1 to R4 each is H, methyl; (n) is >=1; n1, n2 are each 0-2; m1 to m4 each is 0-3) (e.g. the ester of bisphenol A bound two or more triphenyl phosphate molecules, etc.,) and has a load deflection temperature of 120 deg.C under a flextural stress of 18.5kgf/cm<2>. The pellets are blended with (C) a thermoplastic resin (preferably a styrenic resin) and subsequently melt-kneaded to obtain the flame-resistant resin material.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method of using a polyphenylene ether resin or a polycarbonate resin. Specifically, it can be used for the production of polyphenylene ether-based or polycarbonate-based flame-retardant resin materials, is easy to extrude and mold, and has excellent handleability. Pellets made of polyphenylene ether resin or polycarbonate resin and a specific phosphate ester. And a method for producing a flame-retardant resin material using the same.

[0002]

2. Description of the Related Art Polyphenylene ether resins and polycarbonate resins have excellent heat resistance, flame retardancy, mechanical properties, etc.
It is used for modifying various resins including styrene resins. Phosphate esters are widely used as flame retardants for polyphenylene ether resins and polycarbonate resins. For example, JP-A-55-118
No. 957 discloses a flame-retardant composition comprising a polyphenylene ether resin, a styrene resin and a polyfunctional phosphate ester,
JP-A-60-47054 discloses a flame-retardant composition comprising an ABS resin, a polyphenylene ether resin, an organic phosphoric acid ester and a brominated flame retardant, and JP-B-2-26656 discloses a polyamide resin, a polyphenylene ether resin and an aroma. Group consisting of phosphoric acid ester, JP-A-2-115
Japanese Patent No. 262 describes a flame-retardant resin composition comprising an aromatic polycarbonate, a styrene resin and a phosphoric acid ester.

Conventionally, as a method for industrially producing the above flame-retardant resin composition, that is, a resin composition comprising a polyphenylene ether resin or a polycarbonate resin, a second component resin and a phosphoric acid ester, The method relying on the mechanical kneading has been used. (1) A method of melting and kneading a mixture obtained by mixing two or more kinds of resin powders or pellets with a solid or liquid phosphoric acid ester using a twin-screw extruder or the like to form pellets.

(2) Two or more kinds of resin powders or pellets are mixed and melt-kneaded by using a twin-screw extruder or the like,
A method of pelletizing by adding a liquid phosphoric acid ester or a liquid phosphoric acid ester heated to a melting point or higher. However, since phosphoric acid ester is generally a liquid at room temperature and has a melting point lower than the processing temperature of polyphenylene ether resin or polycarbonate resin, when the amount added to the resin is large, the method of (1) makes it uniform with the resin. Difficult to mix. Even if it can be mixed, it will solidify into a dumpling, or as a stickiness, it will be weighed and put into an extruder,
It is very difficult to handle, such as not being able to perform quantitative feed. Further, if the phosphoric acid ester is liquefied by heating in the vicinity of the input port of the extruder or the viscosity is suddenly lowered, the entrapment of the resin becomes unstable, and continuous stable production cannot be performed. As described above, the method (1) has problems that it is difficult to set and control the processing conditions, and the manufacturing efficiency and workability are poor.

The method (2) also requires a special liquid addition device in addition to the kneading device such as an extruder. In the case of a highly viscous phosphoric acid ester or a phosphoric acid ester having a high melting point, further heating is required. Equipment is required. Further, since a liquid phosphoric acid ester is added to the high-viscosity resin, a high degree of skill is required to set and control the production conditions. Moreover, not only is it difficult to mix and add phosphate ester, but polyphenylene ether resin and polycarbonate resin have high heat resistance and the processing temperature is high, so a unique kneading technique is required when kneading with the second resin. However, the kneading efficiency also deteriorates. For example, in the case of a composition of polyphenylene ether resin and styrene resin, it is known that the two are completely compatible, but there is a large difference in melt viscosity at the same temperature, and in the methods (1) and (2), Not only the kneading efficiency is poor, but depending on the degree of kneading, unmelted polymer lumps of polyphenylene ether remain in the form of particles, which adversely affects the heat resistance, mechanical properties, appearance and the like of the product. If the kneading conditions are rigorous in order to eliminate the unmelted polymer, a gelled polymer is produced, which adversely affects the product.

In order to improve the method for producing polyphenylene ether resin and styrene resin, JP-A-4-11744 has been proposed.
No. 4 discloses a method in which a styrene resin and a polyphenylene ether resin are kneaded in advance to obtain a composition, and the composition is further mixed with the styrene resin. However, in this method, the difference in the processing temperature of the composition of the styrene resin and the polyphenylene ether resin and the styrene resin, the difference in the melt viscosity at the same temperature is smaller than the case of the polyphenylene ether resin and the styrene resin, It is not possible to obtain high kneading efficiency. Moreover, the handling situation of phosphate ester is not solved at all.

On the other hand, in the production of a composition of incompatible resins, for example, a resin composition of a polycarbonate resin and an acrylonitrile-butadiene-styrene resin (ABS resin), in order to obtain sufficient physical properties, the particle size of dispersed particles is required. Etc. need to be controlled. Since the two have different melt viscosities at the same temperature, in order to achieve a sufficient dispersion state, strict kneading conditions have to be adopted. Therefore, the physical properties and the like are deteriorated due to the deterioration of the resin, and a bad action such as modification and decomposition of the phosphoric acid ester occurs.

In this way, polyphenylene ether resin,
Alternatively, industrially producing a flame-retardant composition using a polycarbonate resin requires high technology and special production equipment, and its production efficiency is poor.

[0009]

INDUSTRIAL APPLICABILITY The present invention can be used for producing a polyphenylene ether-based or polycarbonate-based flame-retardant resin material, is easy to extrude and mold, has excellent handleability, and is difficult to use for resin materials. An object of the present invention is to provide a pellet for producing a flame-retardant resin material, which is capable of imparting flammability, and a method for producing a flame-retardant resin material using the pellet.

[0010]

The present inventor has accomplished the present invention as a result of extensive studies to solve the above-mentioned object. That is, the present invention comprises (A) a polyphenylene ether resin or a polycarbonate resin, (B) a general formula (I),

[0011]

[Chemical 2]

(Here, Q1, Q2, Q3, and Q4 each independently represent an alkyl group having 1 to 6 carbon atoms. R1, R2,
R3 and R4 independently represent hydrogen or a methyl group. n represents an integer of 1 or more. n1 and n2 each independently represent an integer of 0 to 2. m1, m2, m3 and m4 are independently 0 to 3
Indicates an integer. ) Consisting of a phosphate ester represented by
Bending stress: 18.5 kgf / cm ²
Provided is a pellet for producing a flame-retardant resin material having a temperature of 20 ° C. or less, and a method for producing a flame-retardant resin material, which comprises mixing the pellet (C) with a thermoplastic resin and melt-kneading the mixture.

The component (A) of the present invention is a polyphenylene ether resin or a polycarbonate resin. (A)
The polyphenylene ether resin used as a component is a homopolymer or a copolymer having a repeating unit represented by the general formula (II-1) and / or (II-2).

[0014]

[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, or hydrogen. However, R9 and R10 are not hydrogen at the same time. ) Representative examples of homopolymers of polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2-methyl-6-ethyl-ether).
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-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, and the like.

Among these, poly (2,6-dimethyl-1,
4-phenylene) ether is particularly preferred. Here, the polyphenylene ether 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.

The polyphenylene ether resin may be used as a mixture of styrene resins which are completely compatible with each other as long as the heat resistance of the pellet is not impaired. The preferable mixing ratio of the styrene resin is 10% by weight or less based on the total amount of the resin. Styrene is 1 to 10% by weight when the effect of addition is expressed
Is the range. The polycarbonate resin used as the component (A) is a polymer having a repeating unit represented by the general formula (III).

[0018]

[Chemical 4]

(Here, Z represents a mere bond, or is 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-1). X represents hydrogen or an alkyl group having 1 to 8 carbon atoms. a and b show the integer of 0-4 independently. )

[0020]

[Chemical 5]

Polycarbonate resin can be obtained, for example, by the 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. Next, the phosphate ester as the component (B) will be described. The phosphoric acid ester used as the component (B) of the present invention has the general formula (I):

[0023]

[Chemical 6]

(Here, Q1, Q2, Q3, and Q4 each independently represent an alkyl group having 1 to 6 carbon atoms. R1, R2,
R3 and R4 independently represent hydrogen or a methyl group. n represents an integer of 1 or more. n1 and n2 each independently represent an integer of 0 to 2. m1, m2, m3 and m4 are independently 0 to 3
Indicates an integer. ). The terminal phenyl group in the general formula (I) preferably has no substituent or is substituted with a methyl group.

In the general formula (I), R1 and R2 are preferably hydrogen, and R3 and R4 are preferably methyl groups. 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
~ 5. Further, the phosphoric acid ester may be a mixture of n-mers.

The phosphate ester as the component (B) is a combination of two or more phosphate esters with a specific bifunctional phenol. As the bifunctional phenol, 2,2-bis (4-hydroxyphenyl) propane [commonly called bisphenol A], 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl)
Examples include bisphenols such as methane, bis (4-hydroxy-3,5-dimethylphenyl) methane, and 1,1-bis (4-hydroxyphenyl) ethane. Bisphenol A is particularly preferable.

The phosphoric acid ester as the component (B) is greatly suppressed in volatility, and is excellent in stability and hydrolysis resistance. In addition, it does not cause a problem such as gelation by reacting with a thermoplastic resin, does not accelerate decomposition of the thermoplastic resin, and does not corrode metal parts such as a molding machine. . The phosphoric acid ester as the component (B) used in the present invention is a phosphoric acid ester generally used within a range that does not impair the effects of the present invention, such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl. It may contain phosphoric acid esters such as phosphates, 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 pellet of the present invention is JIS K7207.
It is preferable that the deflection temperature under load at a bending stress of 18.5 kgf / cm ² measured on the basis of 120 ° C. is 120 ° C. or lower. More preferably, the deflection temperature under load is 100 ° C. or lower. When the deflection temperature under load of the pellets is 120 ° C. or higher, the processing temperature required when manufacturing the flame-retardant resin material using the pellets is high, and it cannot be said that the extrusion and molding processes are sufficiently easy and easy to handle. The lower limit of the deflection temperature under load of pellets is not particularly limited as long as pellets can be produced,
The above is desirable. If it is less than 50 ° C, it is difficult to form pellets during the production.

The deflection temperature under load of the pellets is determined according to the heat resistance of the thermoplastic resin of the component (C),
The heat resistance can be adjusted to an arbitrary value depending on the mixing ratio of the component and the component (B), and the deflection temperature under load decreases as the amount of the component (B) increases. The deflection temperature under load also differs depending on the type of component (B). Deflection temperature under load 120
As a standard of the range of the component (B) corresponding to ℃ or less, 50 ℃ or less, for example, in the case of polyphenylene ether resin and bisphenol A.poly (diphenyl) phosphate, bisphenol A.poly (diphenyl) phosphate is added to the total weight of the pellet. It is in the range of 14% by weight or more and 45% by weight or less. Polycarbonate resin and bisphenol A
In the poly (diphenyl) phosphate, the amount of bisphenol A.poly (diphenyl) phosphate is 3% by weight or more and 40% by weight or less based on the total weight of the pellet.

The pellets of the present invention contain other additives such as plasticizers, other flame retardants, anti-dripping agents, stabilizers such as antioxidants and UV absorbers, and release agents within the range of not impairing the effects of the present invention. , Dyes and pigments may be contained. Pellets in the present invention, extruding a molten material using an extruder or the like into a thin rod (strand), then cold cut method,
A spherical, circular or prismatic shaped body having a diameter or a side of about 2 to 5 mm, which is cut by a hot cut method, an underwater cut method, or the like, or is extruded into a sheet and then cut into a small rectangular parallelepiped. Refers to. The method for producing the pellets of the present invention is not particularly limited, including a method of adding a liquid phosphoric ester while melt-kneading a polyphenylene ether resin or a polycarbonate resin in a twin-screw extruder or the like as described above. The kneading can be carried out using a kneading machine such as a known extruder, heating roll, kneader, Banbury mixer and the like.

Next, a method for producing a flame-retardant resin material by mixing the above-mentioned pellets for producing a flame-retardant resin material and the thermoplastic resin (C) and melting and kneading the mixture will be described. As the component (C), polystyrene, rubber-modified polystyrene, AS resin,
Sterene resin such as ABS resin, polyolefin resin such as polyethylene and polypropylene, 6-nylon,
Examples thereof include polyamide resins such as 6,6-nylon, 6,10-nylon and 12-nylon, thermoplastic elastomers, acrylic resins and the like, but are not limited thereto. (C)
The component may be a composition of two or more resins. Further, the component (C) may contain a polyphenylene ether resin or a polycarbonate resin. Among these thermoplastic resins, especially polystyrene, rubber-modified polystyrene,
Styrenic resins such as AS resin ABS resin are preferred.
The thermoplastic resin as the component (C) has a bending stress of 18.5.
Deflection temperature under load in kgf / cm ² is 120 ℃, 50 ℃
The above is preferable. Since the thermoplastic resin as the component (C) and the pellets for producing a flame-retardant resin material have approximately the same heat resistance, the flame-retardant resin material can be produced under milder conditions, and the production efficiency is improved. The pellets for producing the flame-retardant resin material and the thermoplastic resin as the component (C) in the present invention can be mixed and melt-kneaded at any mixing ratio depending on the required performance of the target flame-retardant resin material. Other additives such as a plasticizer within a range that does not impair the effects of the present invention at the time of mixing and melt-kneading the pellet for producing a flame-retardant resin material and the component (C),
Other flame retardants, anti-dripping agents, stabilizers such as antioxidants and ultraviolet absorbers, release agents, dyes and pigments may be mixed and melt-kneaded.

Production of flame-retardant resin material such as flame-retardant resin composition or molded article, that is, pellet for producing flame-retardant resin material and (C)
The mixing and melt-kneading of the thermoplastic resin can be easily performed by using a kneader such as a known extruder, heating roll, kneader, Banbury mixer and the like. The most widely used one for producing flame-retardant resin materials is a twin-screw extruder capable of performing melt-kneading under generally severe kneading conditions. In the pellets of the present invention, the flame retardant phosphate ester is completely compatible with the polyphenylene ether resin or the polycarbonate resin, and the heat resistance is adjusted according to the heat resistance of the component (C). The production can be performed under mild mixing and melt-kneading conditions as compared with the conventional production of a flame-retardant resin material. Therefore, in addition to the twin-screw extruder, the conventional polyphenylene ether-based, or polycarbonate-based flame-retardant resin material was not able to obtain a sufficient kneading effect in the single-screw extruder Can be extruded and produced, or a mixture of the pellet and the component (C) can be directly molded by an injection molding machine to produce a molded product.

[0033]

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.

[0034]

Production Example 1 Production of Partially Hydrogenated Conjugated Diene Rubber; The partially hydrogenated conjugated diene rubber used in the examples was produced by the method described below. Using a stirrer having an internal volume of 10 liters and an autoclave with a jacket as a reactor, a butadiene / n-hexane mixed solution (butadiene concentration 20%) was added at 20 l / hr, n
-Butyl lithium / n-hexane solution (concentration 5%) 7
It was introduced at 0 ml / hr and continuous polymerization of butadiene was carried out at a polymerization temperature of 110 ° C. 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 the temperature was adjusted to 6
At 0 ° C., di-p-tolyl-bis (1-
250 ml of a cyclopentadienyl) titanium / cyclohexane solution (concentration 1.2 mmol / l), n
-Butyllithium solution (concentration 6 mmol / l) 5
A mixture of 0 ml and 0 ° C. under a hydrogen pressure of 2.0 kg / cm ² was added, and a hydrogen partial pressure of 3.0 kg / cm ² was added to 60.
Let react for 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 were as shown in Table A.

[0035]

[Table 1]

[0036]

[Production Example 2] Production of impact-resistant polystyrene resin: The impact-resistant styrene-based resin used in the examples was produced by a bulk polymerization method. 10 parts of the partially hydrogenated conjugated diene rubber of Production Example 1 was converted into styrene 90
Parts and 8 parts of ethylbenzene, 0.05 parts of benzoyl peroxide and 0.10 parts of α-methylstyrene dimer are added to styrene, and the mixture is added at 80 ° C. for 4 hours and 110 ° C. for 4 hours. Polymerization was carried out at 150 ° C. for 4 hours with stirring. Further, heat treatment at around 230 ° C for 30 minutes,
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-based 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.

[0037]

[Production Example 3] Production of ABS resin: 750 parts by weight of a butadiene latex having an average particle size of 0.30 μm (40% by weight in terms of rubber) and 1 part by weight of an emulsifier (potassium disproportionated rosinate) were charged into a polymerization tank, While stirring, the temperature was raised to 70 ° C. in a nitrogen stream, and a mixture of 200 parts by weight of acrylonitrile, 500 parts by weight of styrene, 0.8 parts by weight of cumene hydroperoxide and 0.7 parts by weight of t-dodecyl mercaptan and distilled. To 500 parts by weight of water, 1.0 part by weight of sodium formaldehyde sulfoxylate, ferrous sulfate (FeSO ₄ ·.
7H ₂ O) 0.10 parts by weight, ethylenediamine tetraacetic acid.
Polymerization was carried out by adding an aqueous solution in which 0.2 part by weight of 2Na salt was dissolved for 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. Manufacture of AS resin; potassium persulfate 0.
4 parts by weight and 2.0 parts by weight of potassium rosinate were added and dissolved, 70 parts by weight of styrene, 30 parts by weight of acrylonitrile and 0.2 parts by weight of dodecyl mercaptan were added to this aqueous solution, and the mixture was reacted at 70 ° C. for 4 hours, An aromatic vinyl copolymer was obtained. 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.

[0039]

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.
made by ner Co.] into the main feeder of the twin-screw extruder,
Chemical formula (IV), which is heated to 70 ° C., while being quantitatively fed and melt-kneaded,

[0040]

[Chemical 7]

Phosphoric acid ester A (n = 1 to 3) represented by
Of the PPE and the phosphate ester A using a gear pump [TOKO SANGYO CO., LTD .: trade name Zenith high precision metering pump] is 65% by weight of PPE and phosphate ester A relative to the total weight. The side feed was performed by adjusting the content to 35% by weight. After water cooling the extruded strand,
It was cut with a pelletizer to obtain pellets (hereinafter referred to as pellets A1). This pellet is injection-molded to obtain a molded piece, which has a bending stress of 18.5 kg according to JIS K7207.
The deflection temperature under load of f / cm ² was measured (hereinafter referred to as deflection temperature under load). The results are shown in Table 2.

[0042]

Example 2 Instead of the phosphate ester A in Example 1, the chemical formula (V),

[0043]

[Chemical 8]

Phosphate ester B represented by (n = 1 to 3)
Pellets were obtained in the same manner as in Example 1 except that the mixture) was used, and the deflection temperature under load was measured (pellet A2). The results are shown in Table 2.

[0045]

[Examples 3 and 4] Pellets were obtained in the same manner as in Example 1 except that the types and proportions of PPE and phosphate ester in Example 1 were changed to those shown in Table 1, and the deflection temperature under load was measured (pellet A3, A4). The results are shown in Table 2.

[0046]

Comparative Example 1 The PPE powder used in Example 1 was melt-kneaded alone to obtain pellets in the same manner as in Example 1 except that the phosphate ester was not side-fed, and the deflection temperature under load was measured (pellet). B). The results are shown in Table 2.

[0047]

[Table 2]

[0048]

Example 5 Pellets of an aromatic polycarbonate resin (hereinafter abbreviated as PC) [Lexan 121 manufactured by Nippon GE Plastics Co., Ltd.] were used, and the barrel temperature was set to 280 ° C. Pellets were obtained in the same manner as in Example 1 except that the proportions were adjusted such that PC was 75% by weight and phosphoric acid ester A was 25% by weight based on the total weight, and the deflection temperature under load was measured (pellet C1). The results are shown in Table 3.

[0049]

[Examples 6 to 8] Example 5 except that the types and proportions of PC and phosphate in Example 5 were changed to those shown in Table 3.
Pellets were obtained in the same manner as above, and the deflection temperature under load was measured (pellets C2 to C4). The results are shown in Table 3.

[0050]

Comparative Example 2 Pellets were obtained in the same manner as in Example 5 except that the PC powder used in Example 5 was melt-kneaded alone and side-feeding of the phosphate ester was not performed, and the deflection temperature under load was measured (pellet). D). The results are shown in Table 3.

[0051]

[Table 3]

[0052]

Example 9 32.7 parts by weight of pellets A1, 10.3 parts by weight of pellets A3, 50 parts by weight of high impact polystyrene resin (hereinafter abbreviated as HIPS) prepared in Production Example 2, polystyrene resin (hereinafter Abbreviated as GPPS) [Asahi Kasei Kogyo KK: Asahi Kasei Polystyrene 685] 7 parts by weight, and octadecyl-3- (3-5-di-t-butyl-4-hydroxyphenyl) propionate 0.3 parts by weight as a stabilizer. The parts were mixed using a Henschel mixer. The shapes of HIPS and GPPS used were pellets, and their deflection temperatures under load were 82 ° C and 87 ° C, respectively. This mixture was subjected to Z with the barrel temperature set to 260 ° C.
With SK-25 twin-screw extruder, screw speed 250r
Pellets were obtained by melt kneading at a discharge rate of 11 kg / Hr. The pellets were injection-molded to obtain test pieces, and the appearance was observed and the tensile strength and elongation were measured according to ASTM D638. The results are shown in Table 4.

[0053]

[Example 10] Pellets A2 were used instead of the pellets A1 in Example 9, and pellets A were used instead of the pellets A3.
The pellets were mixed, melt-kneaded and obtained in the same manner as in Example 9 except that No. 4 was used to obtain pellets for evaluation. The results are shown in Table 4.

[0054]

Comparative Example 3 Mixing was performed in the same manner as in Example 9 except that 29 parts by weight of PPE powder and 14 parts by weight of phosphate ester A were used in place of the pellets A1 and A3 in Example 9. When the mixture was taken out, the phosphoric acid ester and PPE powder were remarkably attached inside the Henschel mixer.
When this mixture was melt-kneaded under the same conditions as in Example 9, a torque increase occurred, so the feed amount was reduced. The discharge rate was 7 Kg / Hr. Pellets were obtained and evaluated in the same manner as in Example 9. The appearance of the test piece had a rough surface, and when a thin plate was prepared from the pellets by compression molding, a large amount of particulate unmelted polymer lumps were observed.

[0055]

Comparative Example 4 Mixing was performed in the same manner as in Example 9 except that 29 parts by weight of pellet B and 14 parts by weight of phosphate ester A were used instead of pellets A1 and A3 in Example 9. When the mixture was taken out, the phosphate ester was remarkably attached inside the Henschel mixer. When this mixture was melt-kneaded under the same conditions as in Example 9, a torque increase occurred, so the feed amount was reduced. Discharge amount is 5
It was Kg / Hr. Also, clogging occurred due to blocking of the mixture at the bottom of the popper. Pellets were obtained and evaluated in the same manner as in Example 9. The appearance of the test piece had a rough surface, and many particles of unmelted polymer lumps remained.

[0056]

Comparative Example 5 Mixing was performed in the same manner as in Example 9 except that 29 parts by weight of PPE powder was used instead of the pellets A1 and A3 in Example 9. This mixture was used as Example 9.
While melt-kneading under the same conditions as in Example 1, the phosphoric acid ester A was used in the same manner as in Example 1, and the phosphoric acid ester A was added in an amount of 1 relative to the total weight.
When the side feed was carried out while adjusting the content to 4% by weight, a torque increase occurred, so the feed amount of the mixture and the phosphate ester was reduced. The discharge rate was 7 Kg / Hr. Pellets were obtained and evaluated in the same manner as in Example 9.
The appearance of the test piece had a rough surface, and many particles of unmelted polymer lumps remained.

[0057]

Comparative Example 6 Pellets were obtained by mixing, melting and kneading in the same manner as in Comparative Example 5 except that the barrel temperature in Comparative Example 5 was changed to 320 ° C., and evaluated. Although the appearance of the test piece was good, a few particulate molten polymer lumps were observed.

[0058]

[Table 4]

Since PPE, HIPS and GPPS have a large difference in melt viscosity at the same temperature, they can be extruded as in Comparative Examples 3 to 5, but the kneading is insufficient and the unmelted polymer mass of PPE remains in the form of particles. . Even when the extrusion temperature is high as in Comparative Example 6, it is difficult to give the kneading necessary for complete compatibility because the viscosity of HIPS and GPPS is further lowered. However, by using the pellets of PPE and phosphoric acid ester, the difference in melt viscosity becomes small, the unmelting of PPE does not occur, and a completely compatible flame-retardant resin material can be easily manufactured.

[0060]

Example 11 The mixture of Example 9 was heated to a barrel temperature of 260.
Single-screw extruder with a 40 mmφ vent set to ℃ [THER
MO-PLASTICS INDUSTRY Co., Ltd.] was melt-kneaded at a screw rotation speed of 110 rpm to obtain pellets. The pellets were evaluated as in Example 9.
The results are shown in Table 5.

[0061]

Comparative Example 7 Mixing was performed in the same manner as in Example 9 except that 29 parts by weight of PPE powder and 14 parts by weight of phosphoric acid ester A were used instead of the pellets A1 and A3 in Example 9. When the mixture was taken out, the phosphoric acid ester and PPE powder were remarkably attached inside the Henschel mixer.
An attempt was made to melt-knead this mixture under the same conditions as in Example 11, but the powder did not bite and extrusion was impossible.

[0062]

Comparative Example 8 Mixing was performed in the same manner as in Example 9 except that 29 parts by weight of pellet B and 14 parts by weight of phosphoric acid ester A were used instead of the pellets A1 and A3 in Example 11. When the mixture was taken out, the phosphate ester was remarkably attached inside the Henschel mixer. Further, this mixture was melt-kneaded under the same conditions as in Example 11, but liquid phosphate ester was accumulated under the popper, and extrusion was impossible.

[0063]

[Table 5]

Extrusion of powder or extrusion of a mixture containing a large amount of a liquid substance is difficult with a single-screw extruder, and it is impossible to produce a conventional composition of a system using PPE, HIPS or GPPS as a raw material. However, the use of PPE and phosphate ester pellets made it possible to manufacture a flame-retardant resin material with a single-screw extruder.

[0065]

Example 12 50 parts by weight of pellet A1 and HIPS5
Pellet blend 0 parts by weight, cylinder temperature 240
A test piece was obtained by molding with an injection molding machine set at ℃. The test piece had a uniform color tone and had good appearance such as surface gloss.

[0066]

Example 13 Using a Henschel mixer, 9.3 parts by weight of the pellet C1, 45.2 parts by weight of the pellet C3, 18.2 parts by weight of the ABS resin prepared in Production Example 3 and 27.3 parts by weight of the AS resin were used. Mixed. The deflection temperatures under load of ABS resin and AS resin were 85 ° C. and 94 ° C., respectively. This mixture was melt-kneaded in the same manner as in Example 9 except that the barrel temperature was set to 250 ° C., and pellets were obtained and evaluated. The results are shown in Table 6.

[0067]

Comparative Example 9 Mixing was performed in the same manner as in Example 13 except that 45.5 parts by weight of PC and 9 parts by weight of phosphate ester A were used in place of the pellets C1 and C3 in Example 13. When the mixture was taken out, the phosphoric acid ester, the ABS resin powder, and the AS resin powder were remarkably attached inside the Henschel mixer. Further, this mixture was melt-kneaded under the same conditions as in Example 13 to obtain pellets and evaluated. As a result, liquid phosphate ester was accumulated in the lower part of the hopper, and scorched dust was generated in the extruded strand, so that the test piece was black. Trash mixed in.

[0068]

[Table 6]

[0069]

Example 14 The mixture of Example 13 is heated to a barrel temperature of 25.
With a single screw extruder set at 0 ° C, the screw rotation speed is 11
Melt kneading was performed at 0 rpm to obtain pellets. The pellets were molded by an injection molding machine set to a cylinder temperature of 240 ° C. to obtain test pieces. The test piece had a uniform color tone and had a good appearance such as surface gloss.

[0070]

Comparative Example 10 When the mixture of Comparative Example 9 was melt-kneaded in the same manner as in Example 14, the melting of PC was not sufficient, the strand extruded from the die was not stable, and the amount of pellets required for evaluation was obtained. I couldn't.

[0071]

EFFECTS OF THE INVENTION It can be used for the production of polyphenylene ether-based or polycarbonate-based flame-retardant resin material, is easy to extrude and mold, and has excellent handleability, and can impart flame retardancy to the resin material. Provided are a pellet for producing a flame-retardant resin material, and a method for producing a flame-retardant resin material using the pellet.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C08L 71/12 LQM

Claims (7)

[Claims] 1. A polyphenylene ether resin or a polycarbonate resin (A), and (B) a general formula (I): (Here, Q1, Q2, Q3, and Q4 independently have 1 carbon atom.
Represents an alkyl group from 6 to 6. R1, R2, R3, and R4 each independently represent hydrogen or a methyl group. n represents an integer of 1 or more. n1 and n2 each independently represent an integer of 0 to 2. m
1, m2, m3 and m4 each independently represent an integer of 0 to 3. ) Is composed of a phosphoric acid ester and has a bending stress of 1
Pellets for producing a flame-retardant resin material having a deflection temperature under load of 8.5 kgf / cm ² of 120 ° C or lower. 2. A pellet for producing a flame-retardant resin material according to claim 1, which has a bending temperature under bending stress of 18.5 kgf / cm ² under 100 ° C. 3. A method for producing a flame-retardant resin material, which comprises mixing the pellet according to claim 1 with a thermoplastic resin (C) and melt-kneading the mixture. 4. The thermoplastic resin (C) has a bending stress of 18.5.
The method for producing a flame-retardant resin material according to claim 3, wherein the deflection temperature under load of kgf / cm ² is 120 ° C or lower. 5. The method for producing a flame-retardant resin material according to claim 3, wherein the thermoplastic resin (C) is a styrene resin. 6. The method for producing a flame-retardant resin material according to claim 3, wherein the pellets and the thermoplastic resin (C) are melt-kneaded by a single-screw extruder. 7. The method for producing a flame-retardant resin material according to claim 3, wherein the pellets and the thermoplastic resin (C) are melt-kneaded by an injection molding machine.