JPH10298438A - Thermoplastic resin composition containing liquid additive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition containing a liquid additive and giving a molding having excellent appearance and mechanical properties by adding the liquid additive to a thermoplastic resin in a special manner. SOLUTION: This composition is obtained by dissolving a thermoplastic resin having a number-average particle diameter of 0.01-1,000 μm in a liquid additive having a viscosity of 100,000 cSt or below at 25 deg.C at a temperature of 25-250 deg.C. It is particularly desirable that the thermoplastic resin is a polyphenylene ether and/or that the liquid additive is an aromatic phosphoric acid ester. The composition may further contain a silicon-containing compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a liquid additive-containing thermoplastic resin composition having excellent appearance and mechanical properties by adding a liquid additive to a thermoplastic resin by a special method.

[0002]

2. Description of the Related Art Thermoplastic resins such as polyphenylene ether resins are used in various fields such as automobile parts, home electric appliance parts, and OA equipment parts because of their excellent heat resistance and impact resistance.

In recent years, various polymer additives have been used in such fields for higher functions. For example, it is common practice to add liquid paraffin (mineral oil) to improve processability, and to mix an organic phosphorus compound to impart flame retardancy. However,
When a thermoplastic resin such as polyphenylene ether is melt-extruded, not only a special feed facility is required for adding a liquid additive, but also handling is complicated. Furthermore, when melt mixing a low viscosity liquid additive and a high viscosity thermoplastic resin such as polyphenylene ether,
Due to the formation of unmelted thermoplastic resin with high viscosity,
There are problems that the appearance is impaired and the mechanical properties are reduced.

In order to solve these problems, there is a conventional technique in which a resin and a liquid additive are absorbed at a relatively low temperature without melting and mixing the resin and the liquid additive, and a resin comprising an oil absorbing resin and a liquid additive is used. A composition or method for improving properties is disclosed. For example, a resin composition comprising an oil-containing resin and a thermosetting resin in which a liquid oil is adsorbed on a porous styrene-divinylbenzene copolymer (Japanese Patent Publication No. 7-122024), an additive is contained in an oil-absorbent crosslinked polymer. A method for preventing bleeding of an additive using a resin modifying additive and a resin composition comprising a resin (Japanese Patent Application Laid-Open No. 5-214114), and matting by kneading a specific cross-linked polymer into the resin. (JP-A-6-57007), a method of improving impact resistance by kneading a specific cross-linked polymer into a resin (JP-A-6-73190), A powdery flame retardant impregnated with a phosphorus-based flame retardant (JP-A-7-331244) is known. The above publication discloses the appearance by dissolving the liquid additive of the present invention,
It has not even been suggested that a thermoplastic resin composition having excellent mechanical properties can be obtained.

[0005]

SUMMARY OF THE INVENTION In view of the above situation, the present invention is free from the above-mentioned problems, that is, it not only facilitates the handling of liquid additives but also has excellent appearance and mechanical properties. It is an object of the present invention to provide a thermoplastic resin composition containing a liquid additive.

[0006]

Means for Solving the Problems As a result of diligent studies of a thermoplastic resin composition containing a liquid additive having excellent appearance and mechanical properties, the present inventors have found that a thermoplastic resin having a specific particle diameter has a specific temperature. The present inventors have found that the dissolution in a liquid additive by (1) surprisingly significantly improves the appearance such as color tone and mechanical properties as compared with melt extrusion, and has reached the present invention.

That is, the present invention relates to (A) a thermoplastic resin having a number average particle diameter of 0.01 to 1000 μm;
Resin composition obtained by dissolving in a liquid additive having a viscosity of 100,000 centistokes or less at a temperature of 25 ° C. to 250 ° C., in particular, the thermoplastic resin is polyphenylene ether and / or the liquid additive is aromatic. An object of the present invention is to provide a thermoplastic resin composition which is an aromatic phosphate ester and, if necessary, a thermoplastic resin composition further containing (C) a silicon-containing compound.

Hereinafter, the present invention will be described in detail.

The present invention is a resin composition containing (A) a thermoplastic resin composition having a specific particle diameter, (B) a specific liquid additive, and, if necessary, (C) a silicon-containing compound.

[0010] The above (A) is a main component of the molding resin composition and plays a role in maintaining the strength of the molded article, and (B) imparts functionality such as flame retardancy and fluidity to the thermoplastic resin. (C) is a component for preventing the pellets of the obtained thermoplastic resin composition from fusing together.

Here, it is important that the number average particle diameter of the thermoplastic resin (A) is 0.01 to 1000 μm, preferably 0.1 to 100 μm, more preferably 1 to 50 μm. If the number average particle diameter is less than 0.01, the strength of the compound is reduced due to reduced stability, and if the number average particle diameter exceeds 1000 μm, the dissolution rate of (B) is significantly reduced, and It forms and impairs appearance and mechanical properties.

Next, (A) is added to (B) a liquid additive having a viscosity at 25 ° C. of 100,000 centistokes or less, preferably from 25 ° C. to 250 ° C., more preferably from 100 ° C. to 20 ° C.
It is important to dissolve or partially dissolve at a temperature of 0 ° C, most preferably 130 ° C to 180 ° C. The dissolution is
Without performing melt extrusion with an extruder, using (B) as a solvent,
Dissolving (A) batchwise or continuously at a temperature of 250 ° C. or less. It has been found that, when melting at a temperature exceeding 250 ° C., (A) is thermally deteriorated and the mechanical strength and color tone are reduced, and the present invention has been completed.

In the present invention, (A) the thermoplastic resin comprises:
There is no particular limitation as long as it is compatible with or homogeneously dispersed with (B). For example, polystyrene-based, polyphenylene ether-based, polyolefin-based, polyvinyl chloride-based, polyamide-based, polyester-based, polyphenylene sulfide-based, polycarbonate-based, polymethacrylate-based, or a mixture of two or more of them can be used. . Here, a polyphenylene ether-based or polystyrene-based thermoplastic resin is particularly preferred as the thermoplastic resin. The polystyrene resin is a rubber-modified styrene resin and / or a non-rubber-modified styrene resin.

In the present invention, one of the thermoplastic resins (A), polyphenylene ether (hereinafter abbreviated as PPE), is a homopolymer and / or a copolymer comprising a bonding unit represented by the following formula.

[0015]

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(However, R ¹ , R ² , R ³ , and R ⁴ are each selected from the group consisting of hydrogen, hydrocarbon, and substituted hydrocarbon groups, and may be the same or different. Specific examples of the PPE include poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol. Among them, poly (2,6-dimethyl-1,4-phenylene ether) is preferable. Such P
The method for producing PE is not particularly limited. For example, a complex of a cuprous salt and an amine according to the method described in U.S. Pat. No. 3,306,874 is used as a catalyst to oxidize 2,6 xylenol, for example. It can be easily produced by polymerization, and in addition, US Pat.
No. 61,075, U.S. Pat. No. 3,257,357, U.S. Pat. No. 3,257,358, JP-B-52-17880, and JP-A-50-51197.
Can be easily manufactured by the method described in Japanese Patent Application Publication No. The reduced viscosity ηsp / C of the above PPE used in the present invention (0.5 g /
dl, chloroform solution, measured at 30 ° C.)
It is preferably in the range of 0.70 dl / g, and 0.3
More preferably, it is in the range of 0 to 0.60 dl / g. The above requirement for the reduced viscosity of PPE is 9ηsp / C
As a means for satisfying the condition, adjustment of the amount of the catalyst in the production of the PPE can be exemplified.

The liquid additive used as (B) in the present invention has a viscosity at 25 ° C. of 100,000 centistokes or less, and is a component for imparting a special function to the polyphenylene ether resin.

Here, the liquid additive includes a plasticizer, a stabilizer,
UV absorbers, antistatic agents, organic phosphorus compounds, coloring agents,
Foaming agents, lubricants, perfumes, antioxidants and the like.

The amount of (B) in the thermoplastic resin composition comprising (A) and (B) is preferably 1 to 99 parts by weight, more preferably 10 to 90 parts by weight, and most preferably 20 to 90 parts by weight.
80 parts by weight.

Examples of the plasticizer include phthalic acid esters such as dimethyl phthalate, diethyl phthalate and diisobutyl phthalate; phthalic acid mixed esters such as butyl benzyl phthalate; diisodecyl succinate and dioctyl adipate. Aliphatic dibasic acid esters, glycol esters such as diethylene glycol dibenzoate, aliphatic acid esters such as butyl oleate and methyl acetyl ricinoleate, epoxy plasticizers such as epoxidized soybean oil and epoxidized linseed oil; Trioctyl melitate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, tributyl acetyl citrate, chlorinated paraffin, polypropylene adipate, polyethylene sebacate, triacetin, tributyrin, toluene sulfone N'amido, may be mentioned alkyl benzene, biphenyl, partially hydrogenated terphenyl, camphor and the like.

Examples of the stabilizer as (B) include:
Metal soap, a lead stabilizer, an organic tin stabilizer, a composite stabilizer, an epoxy compound and the like can be mentioned.

Examples of the foaming agent include azo foaming agents such as azobisformamide, azobisisobutyronitrile and diazoaminobenzene, and N, N'dimethyl N, N '.
Examples thereof include N-nitroso-based blowing agents such as dinitrosoterephthalamide and N, N 'dinitrosopentamethylenetetramine, and sulfonyl hydrazides such as benzenesulfonyl hydrazide, toluene 4-sulfonyl hydrazide, and benzene 1,3 disulfonyl hydrazide.

Examples of the lubricant as (B) include hydrocarbon lubricants such as liquid paraffin, fatty acid lubricants, fatty acid amide lubricants, alcohol lubricants, metal soaps and the like.

Examples of the organic phosphorus compound (B) include phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinate, phosphate, phosphite and the like. More specifically, triphenyl phosphate, methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphonate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphate, Dineopentyl hypophosphite, phenylpyrocatechol phosphite, ethyl pyrocatechol phosphate, and dipyrocatechol hypopositive phosphate.

Here, as the organic phosphorus compound, an aromatic phosphate ester monomer represented by the following formula (1) and an aromatic phosphate ester condensate represented by the following formula (2) are particularly preferred.

[0026]

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[0027]

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(However, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , A
r ₅ and Ar ₆ represent a phenyl group, a xyenyl group, an ethylphenyl group, an isopropylphenyl group, a butylphenyl group,
An aromatic group selected from 4,4'-dioxydiarylalkane groups. N represents an integer of 0 to 3;
Represents an integer of 1 or more. Among the above-mentioned aromatic phosphate ester monomers, particularly, hydroxyl group-containing aromatic phosphate ester monomers such as tricresyl phosphate and triphenyl phosphate shown in the formula (1) are particularly preferred. A phosphate ester monomer containing one or more phenolic hydroxyl groups or an aromatic phosphate ester monomer represented by the following formula (3) is preferred.

[0029]

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(Where a, b, and c are 1 to 3, R ¹ ,
R ² and R ³ are hydrogen or an alkyl group having 1 to 30 carbon atoms, and the total number of carbon atoms of the substituents R ¹ , R ² and R ³ is 12 to 30 on average as the whole compound. Here, when it comprises a plurality of aromatic phosphates having different substituents, the total number of carbon atoms of the substituents R ¹ , R ² , R ³ of the flame retardant is represented by a number average, It is the sum of the product of the weight fraction of each aromatic phosphate component in the flame retardant and the total number of carbon atoms of the substituent of each component. In the present invention, among the aromatic phosphate ester monomers, the number average of the total number of carbon atoms of the substituents R ¹ , R ² and R ³ is 1
5-30 are preferable, and 20-30 are more preferable,
25 to 30 are most preferred.

Specific substituents include butyl such as nonyl, t-butyl, t-amyl, hexyl, cyclohexyl, heptyl, octyl, decyl, undecyl, dodecyl, tridecyl. , A tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an otadecyl group, a nonadecyl group, an octadodecyl group, and the like. One or a plurality of substituents are in any position of ortho, meta, and para on one aromatic ring. Can be substituted, but a para-substituted product is preferable. The total number of carbon atoms of the alkyl group substituted by one phosphate ester monomer is 12 to
Most preferably, the number of aromatic rings substituted by only one alkyl group is more than that of the phosphate ester monomer having only one aromatic ring substituted by only one long-chain alkyl group. The phosphoric acid ester monomer has better heat resistance and water resistance. For example, even if the total number of carbon atoms of the alkyl group to be substituted is 18, bis (nonylphenyl) phenyl phosphate is preferable because of its higher heat resistance than octadecylphenyl diphenyl phosphate.

In the present invention, among the organic phosphorus compounds, a phosphate ester monomer in which at least one of R ¹ , R ² , and R ³ is a nonyl group is preferable, and R ¹ , R ² , and R ³ are preferred.
Is the most preferred from the viewpoint of fluidity and volatility of an aromatic phosphate monomer [tris (nonylphenyl) phosphate] having a nonyl group. When the phosphoric acid ester monomer is contained in the flame retardant at 50% by weight or more, a particularly large flame retardant effect is exhibited. The phosphoric acid ester monomer is excellent in fire dropping properties, and is extremely excellent as a flame retardant of rank V-2 according to UL-94 flame retardancy standards. This fact was not previously known.

Further, from the viewpoint of volatility resistance, the total number of carbon atoms of the substituents must satisfy the requirements of the present invention, but the ratio of those having a total number of carbon atoms of the substituent of less than 12 is 1% by weight or less. In some cases, even better volatility is developed.

From the viewpoint of the thermal stability of the flame retardant, particularly from the viewpoint of heat discoloration resistance, JIS-K6
751 or less, more preferably 0.5 mgKOH / g, and / or the alkylphenol is preferably 1% by weight or less, more preferably 0.5% by weight or less. Is more preferably 1000 ppm or less. When the hindered phenolic antioxidant is contained in the flame retardant in an amount of 1 to 1000 ppm by weight, the thermal stability is remarkably improved.

Next, from the viewpoint of light resistance, the substituents R ¹ , R ² , and R ³ are not aryl groups, and even when they are alkyl groups, it is preferable that the alkyl groups have few branches. One alkyl group is particularly preferred.

Further, the number of substituents to be substituted on one aromatic ring of the aromatic phosphate ester is preferably one. The viscosity of an aromatic phosphate ester monomer in which one aromatic ring is substituted with a plurality of substituents is high, and the viscosity increases with the number of substituents. When the viscosity of the aromatic phosphate ester monomer becomes high, not only the handling problem but also the high viscosity makes purification difficult, and the above-mentioned impurities remain, thereby deteriorating the light resistance and heat discoloration resistance.

The most preferred combination of the aromatic phosphate ester monomers in the present invention contains mainly tris (nonylphenyl) phosphate (TNPP) and a small amount of bis (nonylphenyl) phenylphosphate (BNPP). The total number of carbon atoms of the substituents R ¹ , R ² and R ³ is 20 to 27, preferably 25 to 27,
It is more preferably 26 to 27, and most preferably 26.5 to 27. In order to satisfy the above number average of the total number of carbon atoms, for example, BNPP is contained in an amount of 78 to 0% by weight, preferably 22 to 0% by weight, more preferably 11 to 0% by weight, and most preferably 5 to 0% by weight. Yes, TNPP is 22-1
00% by weight, preferably 78-100% by weight, more preferably 89-100% by weight, most preferably 95-1% by weight.
It is in the range of 00% by weight. The flame retardant of such a combination is particularly excellent in balance characteristics of flame retardancy, fluidity, heat resistance, impact strength, water gloss retention, and surface hardness of the obtained molded article. TNPP not only has a high volatility resistance and a high effect of imparting heat resistance, but also has excellent water gloss retention because it is structurally symmetric. As described above, TNPP exerts a specific effect and cannot be predicted by conventional knowledge.

The aromatic phosphate ester monomers used in the present invention are described in JP-A-1-95149 and JP-A-3-95149.
It can be produced by a known method disclosed in, for example, JP-A-294284. For example, there is a method of reacting an alkylphenol, phosphorus oxychloride, and anhydrous aluminum chloride as a catalyst under heating, or a method of oxidizing a phosphite triester with oxygen to convert it to a corresponding aromatic phosphate.

Among the above aromatic phosphate ester condensates, bisphenol A bis (diphenyl phosphate), bisphenol A bis (dicresyl phosphate), and aromatic phosphate ester condensates represented by the following formula (4) Is preferred.

[0040]

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(Where a, b, c, d, and e are 0 to 3 (however, a, b, c, d, and e are not simultaneously 0), and R ¹ to R ^{5 each} have a carbon number of A hydrocarbon of 1 to 10 and n represents an integer of 1 to 3.) The aromatic phosphate ester condensate represented by the formula (4) is a known aromatic phosphate ester condensate disclosed in JP-A-5-1079. It can be manufactured by a method. For example, a monofunctional phenol substituted at the 2,6-position is reacted with phosphorus oxyhalide in the presence of a Lewis acid catalyst to obtain a diaryl phosphorohalide, which is then reacted with a bifunctional phenol in the presence of a Lewis acid catalyst. There is a way to react.

In the present invention, a silicon-containing compound (C) can be blended as required from the viewpoint of handling properties such as prevention of fusion of the resin composition comprising (A) and (B). For example, silica, silicone, and silicone resin are preferred.

The amount of (C) is preferably from 0.001 to 50 parts by weight, more preferably from 0.01 to 50 parts by weight, per 100 parts by weight of the thermoplastic resin composition comprising (A) and (B).
10 parts by weight, most preferably 0.1-5 parts by weight.

In the present invention, in order to further increase the solubility of (A) and (B), if necessary, the solubility parameter (SP value) may be changed from the SP value of (A) to the value of (B). SP
A compatibilizing agent (D) having a value within the range can be added at the time of dissolution. For example, when the thermoplastic resin (A) is polyphenylene ether and the liquid additive (B) is an aromatic phosphate, the above-mentioned SP value also satisfies the requirements. Phosphin is preferred.

The amount of (D) is preferably 0.001 to 50 parts by weight, more preferably 0.01 to 50 parts by weight, per 100 parts by weight of the thermoplastic resin composition comprising (A) and (B).
10 parts by weight, most preferably 0.1 to 5 parts by weight.

The resin composition of the present invention is prepared by charging (B) in a melting tank, adding (A) little by little at a temperature of 25 ° C. to 250 ° C. with stirring, and then stirring the belt with a cooling system. Pelletize in cooler. Such a process was developed by Sandvik and an example is shown in FIG.

In the present invention, a resin composition containing (A) and (B) as essential components and, if necessary, (C) and (D) is used as a masterbatch, and (E) a styrene resin, (B)
Flame retardants other than those described above, styrene-based thermoplastic elastomers, antioxidants, ultraviolet absorbers, tin-based heat stabilizers, lubricants such as stearic acid and zinc stearate, fillers, reinforcing agents such as glass fibers, dyes and the like A coloring agent such as a pigment can be blended by a melt extrusion method.

The (E) styrene-based resin is a rubber-modified styrene-based resin and / or a non-rubber-modified styrene-based resin. preferable.

The amount of the above (E) depends on the amount of the master batch 1
1 to 1000 parts by weight with respect to 00 parts by weight,
More preferably, 1 to 500 parts by weight, most preferably,
5 to 100 parts by weight.

Such a rubber-modified styrenic resin refers to a polymer in which a rubbery polymer is dispersed in a matrix of a vinyl aromatic polymer in the form of particles. It can be obtained by adding a group IV vinyl monomer and, if necessary, a vinyl monomer copolymerizable therewith, and subjecting the monomer mixture to a known bulk polymerization, bulk suspension polymerization, solution polymerization, or emulsion polymerization.

Examples of such resins include impact-resistant polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acryl rubber-styrene copolymer), and AES resin (acrylonitrile-ethylene copolymer). Propylene rubber-styrene copolymer).

Here, the rubbery polymer needs to have a glass transition temperature (Tg) of -30 ° C. or less,
If the temperature exceeds -30 ° C, the impact resistance decreases.

Examples of such rubbery polymers include diene rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), and saturated rubbers obtained by hydrogenating the diene rubbers, isoprene rubbers, chloroprene rubbers. , An acrylic rubber such as polybutyl acrylate, and an ethylene-propylene-diene monomer terpolymer (EPDM). A diene rubber is particularly preferred.

The aromatic vinyl monomer as an essential component in the graft-polymerizable monomer mixture to be polymerized in the presence of the rubbery polymer is, for example, styrene, α-methylstyrene, paramethylstyrene, p-methylstyrene, -Chlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene and the like, and styrene is most preferred, but the above aromatic vinyl monomer may be copolymerized mainly with styrene.

If necessary, one or more monomer components copolymerizable with the aromatic vinyl monomer can be introduced as components of the rubber-modified styrenic resin. When it is necessary to increase oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used.

When it is necessary to lower the melt viscosity during blending, an acrylate comprising an alkyl group having 1 to 8 carbon atoms can be used. Further, when it is necessary to further increase the heat resistance of the resin composition, α-methylstyrene, acrylic acid, methacrylic acid,
Monomers such as maleic anhydride and N-substituted maleimide may be copolymerized. The content of the vinyl monomer copolymerizable with the vinyl aromatic monomer in the monomer mixture is from 0 to 40.
% By weight.

The rubbery polymer in the rubber-modified styrenic resin of the present invention is preferably from 5 to 80% by weight, particularly preferably from 10 to 50% by weight, and the monomer mixture capable of graft polymerization is preferably from 95 to 20% by weight. %, More preferably in the range of 90 to 50% by weight. Outside this range, the balance between the impact resistance and the rigidity of the target resin composition cannot be achieved. Furthermore, the rubber particle diameter of the styrene polymer is
0.1 to 5.0 μm is preferable, and 0.2 to 3.0 μm is particularly preferable.
m is preferred. Within the above range, impact resistance is particularly improved.

The reduced viscosity ηsp / c which is a measure of the molecular weight of the rubber-modified styrenic resin used in the present invention.
(0.5 g / dl, 30 ° C. measurement: toluene solution when the matrix resin is polystyrene, methyl ethyl ketone when the matrix resin is an unsaturated nitrile-aromatic vinyl copolymer), 0.30 to 0.80 dl / g And more preferably in the range of 0.40 to 0.60 dl / g. Means for satisfying the above requirements regarding the reduced viscosity ηsp / c of the rubber-modified styrenic resin include adjustment of the polymerization initiator amount, polymerization temperature, and chain transfer agent amount.

The thermoplastic resin composition of the present invention preferably comprises (A) 20 to 80% by weight of a polyphenylene ether having a number average particle diameter of 20 μm, and (C) 0.01 to 1% of silica.
(B) 80 to 20% by weight of aromatic phosphate ester
Is a thermoplastic resin composition obtained by melting at a temperature of 130 ° C. to 180 ° C., and by mixing the composition with a styrene resin by a melt extrusion method, functions such as flame retardancy, molding processing, etc. A resin composition having excellent balance properties of fluidity (fluidity), impact resistance and heat resistance can be obtained.

[0060]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention.

The measurements in the examples and comparative examples were performed using the following methods or measuring instruments.

(1) Analysis of Flame Retardant 5 g of the resin composition was dissolved in 100 ml of methyl ethyl ketone and separated using an ultracentrifuge (20,000 rpm).
m, 1 hour). Then, the supernatant obtained by separation was added with 2
A double amount of methanol was added to precipitate a resin component, and the solution portion and the resin portion were separated using an ultracentrifuge. For the solution part, use GPC (gel permeation chromatography) [manufactured by Tosoh Corporation, Japan;
HLC-8020; column, manufactured by Tosoh Corporation, two G1000HXL; mobile phase, tetrahydrofuran; flow rate, 0.8 ml / min; pressure, 60 kg
f / cm ² ; temperature INLET 35 ° C, OVEN 4
0 ° C., RI 35 ° C .; sample loop 100 ml; injected sample amount 0.08 g / 20 ml], and the area ratio of each component on the chromatogram is assumed to be the weight fraction of each component, and the phosphate ratio is determined from the area ratio. Was determined in terms of composition and amount. On the other hand, for the above resin portion, the ratio of integral values of aromatic protons or aliphatic protons was determined by using a Fourier transform nuclear magnetic resonance apparatus (proton-FT-NMR), and a rubber-modified styrene resin and polyphenylene ether, etc. The amount of the thermoplastic resin was determined.

(2) SP value (δ) [Solubility Parameter] and average SP value The SP value was obtained from Polymer Engineering a.
nd Science, 14, (2), 147 (197)
It was calculated from the Fedors equation described in 4) and the data of Δe1 and Δv1 summarized in the literature.

Δ = √ [Σ (Δe1) / Σ (Δv1)] [where, Δe1 is the aggregation energy per unit functional group, Δv1 is the molecular volume per unit functional group, and the unit of δ is ( cal / cm ³ ) １ ／. The SP value of the copolymer and the blend of the copolymer is assumed to satisfy the addition rule. In the case of a copolymer, a monomer unit is used, or in the case of a blend, each component copolymer is used. Was calculated by proportional distribution of the weight ratio of the SP values, and this was defined as the average SP value.

For example, the average SP value of the acrylonitrile-styrene copolymer was calculated by the proportional distribution of the weight ratio of the polyacrylonitrile SP value of 14.39 and the polystyrene SP value of 10.52.

(3) Number average particle diameter of component (A) The number average particle diameter of each particle was determined by an electron microscope. That is, each particle is assumed to be a sphere, and the arithmetic average of the major axis and the minor axis is defined as the average diameter of each particle. Then, the number average particle diameter was determined by arithmetic mean of the average diameter of 100 particles.

(4) Yellowness ΔYI SM Measured according to JIS-Z-8722 using SM Color Computer Model SM-3 (manufactured by Suga Test Instruments Co., Ltd.) and used as an index of appearance (color tone). .

(5) Izod impact strength Measured at 23 ° C. by a method according to ASTM-D256. (1/8 inch test piece, no notch) The following components were used in Examples and Comparative Examples.

(A) Polyphenylene ether (PPE)
After the inside of a stainless steel reactor having an oxygen inlet at the bottom of the reactor and having a cooling coil and stirring blades inside was sufficiently replaced with nitrogen, 54.8 g of cupric bromide, di-n-
1110 g of butylamine and 20 liters of toluene,
8.75 kg of 2,6-xylenol was dissolved in a mixed solvent of 16 liters of n-butanol and 4 liters of methanol and charged into the reactor. Oxygen was continuously blown into the reactor while stirring, and polymerization was performed for 90 minutes while controlling the internal temperature to 30 ° C. After completion of the polymerization, the precipitated polymer was separated by filtration. A mixed solution of methanol / hydrochloric acid was added thereto to decompose the remaining catalyst in the polymer, further sufficiently washed with methanol, and dried to obtain a powdered polyphenylene ether (referred to as PPE). The reduced viscosity ηsp / C is 0.4
It was 1 dl / g. The number average particle size was 20 μm.

(B) Styrene-based resin: Non-rubber-modified styrene-based resin (GPPS) Polystyrene having a weight average molecular weight of 200,000 (produced by Asahi Kasei Kogyo Co., Ltd.) (referred to as GPPS) is pulverized, and the number average particle diameter is 20 μm. GPPS was used.

By controlling the milling time, GPPS with different number average particle diameter was produced.

(C) Liquid additive: phosphorus-based flame retardant alkyl group-substituted aromatic phosphate ester monomer (FR-
Production of 1) Nonylphenol 287.3 parts by weight (molar ratio 2.0)
0.87 parts by weight of aluminum chloride (molar ratio 0.01) was placed in a flask, and 100 parts by weight of phosphorus oxychloride (molar ratio 1.0) was added dropwise at 90 ° C. over 1 hour. 61.4 parts by weight of phenol (molar ratio 1.0) was added to the resulting intermediate, and further reacted. In order to complete the reaction, the temperature was gradually raised and finally raised to 180 ° C. to complete the esterification. Next, the reaction product is cooled, washed with water to remove the catalyst and chlorine, and mixed with a phosphate mixture (hereinafter referred to as F).
R-1). This mixture was subjected to GPC (gel permeation chromatography, manufactured by Tosoh Corporation).
When analyzed by HLC-8020 mobile phase tetrahydrofuran, bis (nonylphenyl) phenyl phosphate (hereinafter referred to as BNPP), trisnonylphenyl phosphate (hereinafter referred to as TNPP),
Nonylphenyl diphenyl phosphate (hereinafter N
PDP) and nonylphenol, and the weight ratio was 77.8 / 11.3 / 8.4 / 2.5, respectively.

The average of the total number of carbon atoms of the substituent is 1
7.9, (18 × 0.778 + 27 × 0.113
+ 9 × 0.084 = 17.9) The phosphorus content is 5.5% by weight.

On the other hand, BNPP or TNPP was obtained by distillation of the above aromatic phosphate ester monomer mixture (FR-1) and further fractionation by liquid chromatography.

(D) Silicon compound Commercially available silica (Nibucil VN3LP, trade name, manufactured by Nippon Silica Industry Co., Ltd.) was used.

Examples 1 to 7 and Comparative Examples 1 to 6 The compositions shown in Table 1 were produced by the following two addition methods. The pellet obtained in this manner is injected into an injection molding machine (Model JSW J100EP manufactured by Japan Steel Works, Ltd.).
Then, a test piece was prepared under the conditions of a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C., and the color tone ΔYI of the molded body was measured. The results are shown in Table 1.

Method of adding each component: I: In a batch type mixing tank equipped with a stirrer, using (C) as a solvent,
(A) was melted with stirring at the temperature at the time of addition shown in Table 1, and introduced into a belt conveyor type cooling dryer (belt cooler) to pelletize.

II: PPE was fed from the main feeder and TNPP was fed from the side feeder using a twin-screw extruder capable of side feeding, and was melt-extruded at the temperature at the time of addition shown in Table 1 to pelletize.

[0079]

[Table 1]

According to Table 1, PPE or GPPS is 2
It can be seen that the molded product obtained by melting at a temperature of 50 ° C. or less has an excellent appearance (color tone) as compared with the molded product obtained by melt extrusion. On the other hand, when PPE is melt-extruded at a temperature of 250 ° C. or lower, although the color tone is excellent, a large number of unmelted PPE are formed, which impairs the appearance of the molded product.

[0081]

According to the present invention, a liquid additive-containing thermoplastic resin composition having excellent appearance and mechanical properties can be obtained by adding a liquid additive to a thermoplastic resin by a special method. it can.

This resin composition can be used in household electrical appliance housings such as VTRs, distribution boards, televisions, audio players, capacitors, household outlets, radio cassettes, video cassettes, video disc players, air conditioners, humidifiers, electric warm air machines, etc. Chassis or parts, CD-RO
OA of M mainframe (mechanical chassis), printer, fax, PPC, CRT, word processor copier, electronic cash register, office computer system, floppy disk drive, keyboard, type, ECR, calculator, toner cartridge, telephone, etc. Equipment housing, chassis or parts, connector, coil bobbin, switch, relay, relay socket, LED, variable condenser,
AC adapter, FBT high pressure bobbin, FBT case,
IFT coil bobbin, jack, volume shaft,
Suitable for electronic and electrical materials such as motor parts, and automotive materials such as instrument panels, radiator grills, clusters, speaker grills, louvers, console boxes, defroster garnishes, ornaments, fuse boxes, relay cases, connector shift tapes, etc. And play a large role in these industries.

[Brief description of the drawings]

FIG. 1 shows a process for producing a resin composition of the present invention.

Claims (3)

[Claims] (A) a number average particle diameter of 0.01 to 10
(B) a viscosity of 10 μm at 25 ° C.
A liquid additive-containing thermoplastic resin composition obtained by dissolving a liquid additive having a density of 10,000 centistokes or less at a temperature of 25 ° C to 250 ° C. 2. The liquid additive-containing thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is polyphenylene ether and / or the liquid additive is an aromatic phosphate. 3. The liquid additive-containing thermoplastic resin composition according to claim 1, further comprising (C) a silicon-containing compound.