JP2010126578A - Polyphenylene ether based resin composition and molded product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyphenylene ether based resin composition which gives moldability without damaging the excellent flame retardance possessed by the polyphenylene ether based resin and further can inhibit the deterioration of the strength and the oil resistance of a molded product obtained and a molded product obtained by molding the resin composition. <P>SOLUTION: The polyphenylene ether based resin composition contains a polyphenylene ether based resin (A) and a polystyrenic resin (B) and the polystyrenic resin (B) contains a resin obtained by copolymerizing a multibranched macromonomer (b1) having a plurality of branches and a plurality of polymerizable double bonds at the end of the branches and a styrenic monomer (b2). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polyphenylene ether-based resin composition containing a specific polystyrene-based resin and a molded body formed by molding the resin composition.

  Conventionally, polyphenylene ether resins have been widely used in the field of electrical equipment due to their high heat resistance, flame retardancy, and excellent electrical properties. Since polyphenylene ether resins are generally slightly inferior in moldability, they are commercially available as “modified polyphenylene ether resins” mixed with polystyrene resins, and are being developed for various uses (see, for example, Patent Document 1).

  Polystyrene resins are known to lack flame retardancy, and there is a trade-off between improving the processability of polyphenylene ether resins and maintaining flame retardancy. In this regard, a solution by a method of selecting and using a high molecular weight polyphenylene ether resin (for example, see Patent Document 2) or a method of using a specific flame retardant in combination (for example, Patent Documents 3 and 4). Means are provided. However, since it is generally known that the moldability is deteriorated as the molecular weight increases, the means of the above-mentioned Patent Document 2 has a poor improvement effect in terms of the moldability, and when a flame retardant is used in combination. In order to ensure the uniform dispersibility, better moldability (fluidity during heating) is necessary, and it is still difficult to balance the two. Furthermore, the processing and melting temperature of polyphenylene ether resins is as high as about 280 ° C. When a polystyrene resin is melted and kneaded at this temperature, the polystyrene resin is likely to deteriorate (breakage of molecular chains), resulting in a decrease in molecular weight. This leads to a decrease in strength and oil resistance of the molded body.

  Further, with the recent high integration in the electric and electronic field, the miniaturization of molded parts is also progressing. In particular, in order to obtain a compact molded body by injection molding, further moldability is required.

JP 2002-097362 A JP-A-2005-154584 JP 2003-87929 A JP 2008-0379970 A

  In view of the above circumstances, the problem to be solved by the present invention is to impart molding processability without impairing the excellent flame retardancy of the polyphenylene ether-based resin, and to further deteriorate the strength and oil resistance of the obtained molded body. An object of the present invention is to provide a polyphenylene ether-based resin composition that can be suppressed, and a molded body obtained by molding the resin composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have blended a specific polystyrene resin having a branched structure with a conventional polyphenylene ether resin, thereby achieving good molding even in injection molding and the like. It has been found that the flame retardancy, mechanical strength, and oil resistance of the polyphenylene ether resin are not impaired while having the properties, and the present invention has been completed.

  That is, the present invention is a resin composition containing a polyphenylene ether resin (A) and a polystyrene resin (B), wherein the polystyrene resin (B) has a plurality of branches, and a tip portion thereof. Containing a resin obtained by copolymerizing a multi-branched macromonomer (a1) having a plurality of polymerizable double bonds and a styrene monomer (a2), and using the same The molded body obtained by the above is provided.

  The polyphenylene ether resin composition of the present invention is excellent in processability, and the resulting molded article has good flame retardancy, mechanical strength, and oil resistance. Therefore, even when a molded body is obtained by injection molding or the like, the mold reproducibility is good, and it can be suitably used particularly for electrical and electronic parts that are downsized with higher integration. In addition, even when flame retardants and other additives are used in combination, the ratio of use can be reduced because of its excellent uniform dispersibility, and it is an environment-friendly molded product that can be recovered and recycled. Is also suitable.

The present invention is described in detail below.
[Polyphenylene ether resin (A)]
The polyphenylene ether resin (hereinafter abbreviated as PPE resin) (A) used in the present invention is a homopolymer or copolymer composed of a repeating unit represented by the following general formula (1). Or a mixture of two or more resins having different substituents.

［式（１）中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４はそれぞれ独立して、水素原子、ハロゲン原子、置換基を有していても良いアルキル基、アルコキシ基又は置換基を有していても良いアリール基であり、ｎは繰り返し数である。］

[In Formula (1), R ₁ , R ₂ , R ₃ and R ₄ each independently have a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a substituent which may have a substituent. And n is the number of repetitions. ]

  Examples of the homopolymer represented by the general formula (1) include poly (2,6-dimethyl-1,4-phenylene) ether and 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-phenylene) ether, poly (2- Methyl-6-chloroethyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly (2,6-dichloro-1,4-phenylene) ether Etc. The.

  Examples of the copolymer include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, -A copolymer of dimethylphenol and 2,3,6-trimethylphenol and the like.

  Among these, particularly preferred PPE resins (A) include poly (2,6-dimethyl-1,4-phenylene) ether, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, Or a mixture of these.

  The production method of the PPE resin (A) used in the present invention is not particularly limited, and can be obtained by various methods, for example, U.S. Pat. Nos. 3,306,874 and 3,306,875, Examples thereof include the production methods described in JP-A-3257357, JP-A-3257358, JP-A-50-51197, JP-B-52-17880, JP-A-63-152628, and the like.

The PPE resin (A) used in the present invention may contain other various phenylene ether units as partial structures as long as the effects of the present invention are not impaired. Examples of the phenylene ether unit include a 2- (dialkylaminomethyl) -6-methylphenylene ether unit and a 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit. Further, a small amount of diphenoquinone or the like may be bonded to the main chain of the PPE resin. Furthermore, one of two carboxyl groups of maleic acid, fumaric acid, chloromaleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid and acid anhydrides thereof, and these unsaturated dicarboxylic acids or General ones such as those in which two are esters, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, epoxidized natural oil, allyl alcohol, 4-penten-1-ol, 1,4-pentadien-3-ol, etc. Unsaturated alcohols of the formula C _n H _2n-3 OH (n is a positive integer), unsaturated alcohols such as the general formulas C _n H _2n-5 OH, C _n H _2n-7 OH (n is a positive integer), etc. PPE resin modified by the above may be used. These modified PPE resins may be used alone or in combination of two or more.

  The molecular weight (number average molecular weight determined by gel permeation chromatography) of the PPE resin (A) used in the present invention is usually 1,000 to 100,000, preferably 6,000 to 60,000. The reduced viscosity (measured with 0.5 g / dl chloroform solution, 30 ° C., Ubbelohde type viscosity tube) of the PPE resin (A) is usually in the range of 0.35 dl / g to 0.55 dl / g, preferably Is in the range of 0.40 dl / g to 0.50 dl / g. In the present invention, even a blend of two or more PPE resins (A) having different reduced viscosities can be used.

[Polystyrene resin (B)]
The polystyrene resin (B) used in the present invention comprises a multi-branched macromonomer (b1) having a plurality of branches and a plurality of polymerizable double bonds at the tip thereof, and a styrene monomer (b2). A multi-branched resin obtained by copolymerization is essential. The polystyrene resin (B) used in the present invention is produced simultaneously with the copolymer having a multi-branched structure obtained by copolymerizing the multi-branched macromonomer (b1) and the styrene monomer (b2). It may contain a homopolymer (linear resin) of the styrenic monomer. Further, a linear resin produced in advance may be mixed with a resin obtained by copolymerizing the hyperbranched macromonomer (b1) and the styrene monomer (b2).

  About the fluidity of the polystyrene resin (B), it is in balance with mold reproducibility and mold release property, shortening of molding cycle, appearance, heat resistance, etc. when mixed with the PPE resin (A) described above. From the standpoint of superiority, a resin having an MFR of 0.5 or more and 7.5 or less is preferable.

[GPC-MALS]
When the molecular weight of the polystyrene resin (B) used in the present invention is measured by GPC-MALS (MALS: multi-angle light scattering detector), for example, the chromatograph shown in FIG. 2 is obtained. In FIG. 2, the peak on the low molecular weight side is P1, and the peak on the high molecular weight side is P2. The peak P1 is presumed to contain a linear resin and a resin with a low degree of branching. The peak P2 is presumed to contain mainly a multi-branched resin having a high degree of branching. The region of peak P2 includes a perpendicular line drawn from the highest point of peak P2 to the baseline (a dotted line drawn substantially parallel to the volume axis in FIG. 2), a baseline, and a molecular weight curve on the left side from the highest point. And a molecular weight curve formed when the region (1) is folded to the right side with the perpendicular as the axis of symmetry (in FIG. 2, a virtual line indicated by a dotted line on the right side of the perpendicular). This is a region formed by a region (2) surrounded by a molecular weight curve), a perpendicular, and a base line. The region of peak P1 is a portion obtained by subtracting the region of peak P1 composed of the region (1) and region (2) from the region surrounded by the molecular weight curve and the baseline.

[Molecular weight of polystyrene resin (B)]
The polystyrene-based resin (B) used in the present invention is GPC in terms of the balance of molding processability when mixed with the PPE resin (A) to form a composition, and the heat resistance, mechanical strength, oil resistance, etc. of the resulting molded product. The weight average molecular weight determined from -MALS is preferably 150,000 to 550,000, more preferably 250,000 to 500,000. When the weight average molecular weight is 150,000 or less, the strength tends to decrease, and when it exceeds 550,000, the workability tends to decrease.

[Slope of double logarithm graph of polystyrene resin (B)]
For the polystyrene resin (B), the slope in the region of molecular weight of 250,000 to 10 million in the logarithmic graph with the horizontal axis representing the molecular weight of the resin determined from GPC-MALS and the vertical axis representing the inertial radius represents the strength and It is most preferable that it is 0.30-0.45 from the point which expresses moldability with the outstanding balance. When the slope is larger than 0.45, the physical properties are closer to those of the linear resin. Conversely, when the slope is smaller than 0.30, the fluidity is lowered due to the increase in the molecular weight accompanying the increase in the degree of branching, which affects the moldability. There is.

[Blend ratio of resin in peak P1 region and resin in peak P2 region]
The mass ratio of the resin in the region of peak P1 and the resin in the region of peak P2 in the polystyrene-based resin (B) is excellent in the balance between strength and moldability (resin in the region of peak P2) / (Resin in the region of peak P1) = 30/70 to 70/30 is preferable, and 40/60 to 60/40 is more preferable. This ratio can be easily controlled by adjusting the use ratio of the hyperbranched macromonomer (b1) and the styrenic monomer (b2), the type of chain transfer agent, and the amount used.

[Multi-branched macromonomer (b1)]
As the multi-branched macromonomer (b1) having a plurality of branches used in the present invention and having a plurality of polymerizable double bonds at the tip thereof, a polystyrene resin (B) excellent in the above properties is used. From the viewpoint of easily obtaining the point, particularly the weight average molecular weight of the multi-branched resin to 10 million or less, the weight average molecular weight having a plurality of branches and having a plurality of polymerizable double bonds at the tip thereof (Mw) is preferably a macromonomer having a molecular weight of 1,000 to 15,000, more preferably 3,000 to 8,000.

  Although there is no restriction | limiting in particular as said branched structure, All three bonds except an electron withdrawing group and the bond couple | bonded with this electron withdrawing group are branched by the quaternary carbon atom couple | bonded with the carbon atom. And those in which a branched structure is formed by repeating structural units having an ether bond, an ester bond or an amide bond are preferred.

When the multi-branched resin forms a branched structure with the quaternary carbon, the electron withdrawing group content is 2.5 × 10 ⁻⁴ mmol to 5.0 × per 1 g of the multi-branched resin. It is preferably in the range of 10 ⁻¹ mmol, more preferably in the range of 5.0 × 10 ⁻⁴ mmol to 5.0 × 10 ⁻² mmol.

  It is essential that the tip of the multi-branched macromonomer (b1) has two or more polymerizable double bonds per molecule. The content of the polymerizable double bond is preferably in the range of 0.1 to 5.5 mmol, and more preferably in the range of 0.5 to 3.5 mmol, per 1 g of the macromonomer. When the amount is less than 0.1 mmol, it is difficult to obtain a high-molecular-weight multi-branched resin. When the amount exceeds 5.5 mmol, the molecular weight of the multi-branched resin tends to increase excessively.

  The multi-branched macromonomer (b1) that can be used in the present invention includes a branched structure formed by repeating a structural unit having an ester bond, an ether bond or an amide bond, and two or more polymerizable groups in one molecule at the branch end. A multi-branched macromonomer (b1-i) having a double bond can be mentioned.

  In the multibranched macromonomer (b1-i-1) in which a structural unit having an ester bond is repeatedly formed to form a branched structure, the carbon atom adjacent to the carbonyl group of the ester bond forming the molecular chain is a quaternary carbon atom. A preferred embodiment is one in which a polymerizable double bond such as a vinyl group or an isopropenyl group is introduced into a multi-branched polyester polyol. Introducing a polymerizable double bond into a multi-branched polyester polyol can be carried out by an esterification reaction or an addition reaction.

  In the multi-branched polyester polyol, a substituent may be introduced into a part of the hydroxy group in advance by an ether bond or other bond, and a part of the hydroxy group may be oxidized or other reaction. It may be denatured. Further, in the hyperbranched polyester polyol, a part of the hydroxy group may be esterified in advance.

  Examples of the hyperbranched macromonomer (b1-i-1) include a compound having one or more hydroxy groups, a carbon atom adjacent to the carboxy group being a quaternary carbon atom, and two or more hydroxy groups. It is obtained by reacting a monocarboxylic acid having a multi-branched polymer, and then reacting the hydroxyl group, which is a terminal group of the polymer, with an unsaturated acid such as acrylic acid or methacrylic acid or an acrylic compound containing an isocyanate group. Things. In addition, about the multibranched polymer which formed the branched structure by repeating the structural unit which has an ester bond, "Angew.Chem.Int.Ed.Engl.29" p138-177 (1990) by Mr. Tamalia etc. Are listed.

  Examples of the compound having at least one hydroxy group include a) aliphatic diol, alicyclic diol, or aromatic diol, b) triol, c) tetraol, d) sugar alcohols such as sorbitol and mannitol, e) anne Hydroenenea-heptitol or dipentaerythritol, f) α-alkyl glucoside such as α-methyl glycoside, g) monofunctional alcohol such as ethanol, hexanol, h) alkylene oxide having a weight average molecular weight of at most 8,000, or The hydroxy group containing polymer etc. which were produced | generated by making the derivative and the hydroxyl group in 1 or more types of compounds selected from any of said a) -g) react can be mentioned.

  Examples of the a) aliphatic diol, alicyclic diol and aromatic diol include, for example, 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1, 6-hexanediol, polytetrahydrofuran, dimethylolpropane, neopentylpropane, 2-propyl-2-ethyl-1,3-propanediol, 1,2-propanediol, 1,3-butanediol, diethylene glycol, triethylene glycol , Polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol; cyclohexanedimethanol, 1,3-dioxane-5,5-dimethanol; 1,4-xylylenediethanol, 1-phenyl-1,2-ethanediol Etc. . Examples of the b) triol include trimethylolpropane, trimethylolethane, trimethylolbutane, glycerol, 1,2,5-hexanetriol, 1,3,5-trihydroxybenzene, and the like. Examples of c) tetraol include pentaerythritol, ditrimethylolpropane, diglycerol, and ditrimethylolethane.

  Examples of the monocarboxylic acid in which the carbon atom adjacent to the carboxyl group is a quaternary carbon atom and having two or more hydroxy groups include, for example, dimethylolpropionic acid, α, α-bis (hydroxymethyl) butyric acid, α , Α, α-tris (hydroxymethyl) acetic acid, α, α-bis (hydroxymethyl) valeric acid, α, α-bis (hydroxymethyl) propionic acid, and the like. By using the monocarboxylic acid, the ester decomposition reaction is suppressed and a multibranched polyester polyol can be formed.

  Further, it is preferable to use a catalyst when producing the multi-branched polyester polyol. Examples of the catalyst include organic tins such as dialkyltin oxide, halogenated dialkyltin, dialkyltin biscarboxylate, and stannoxane. Examples thereof include compounds, titanates such as tetrabutyl titanate, organic sulfonic acids such as Lewis acid and p-toluenesulfonic acid.

Examples of the multibranched macromonomer (b1-i-2) in which a structural unit having an ether bond is repeatedly formed to form a branched structure include, for example, a cyclic ether having one or more hydroxy groups in a compound having one or more hydroxy groups The compound is reacted to form a hyperbranched polymer, and then the terminal hydroxyl group of the polymer is unsaturated acid such as acrylic acid or methacrylic acid, isocyanate group-containing acrylic compound, halogen such as 4-chloromethylstyrene And those obtained by reacting methyl styrene. Further, as a method for producing the multi-branched polymer, a compound having one or more hydroxy groups, two or more hydroxy groups and a halogen atom, -OSO ₂ OCH ₃ or -OSO ₂ is based on Williamson's ether synthesis method. A method of reacting with a compound containing CH ₃ is also useful.

As the compound having one or more hydroxy groups, any of those mentioned above can be used, and as the cyclic ether compound having one or more hydroxy groups, for example, 3-ethyl-3- (hydroxymethyl) Examples include oxetane, 2,3-epoxy-1-propanol, 2,3-epoxy-1-butanol, and 3,4-epoxy-1-butanol. The compounds having one or more hydroxy groups used in the Williamson ether synthesis method may be those described above, but aromatic compounds having two or more hydroxy groups bonded to an aromatic ring are preferred. Examples of the compound include 1,3,5-trihydroxybenzene, 1,4-xylylenediethanol, 1-phenyl-1,2-ethanediol and the like. Examples of the compound containing two or more hydroxy groups and a halogen atom, —OSO ₂ OCH ₃ or —OSO ₂ CH ₃ include, for example, 5- (bromomethyl) -1,3-dihydroxybenzene, 2-ethyl-2. -(Bromomethyl) -1,3-propanediol, 2-methyl-2- (bromomethyl) -1,3-propanediol, 2- (bromomethyl) -2- (hydroxymethyl) -1,3-propanediol, etc. Can be mentioned. In addition, when manufacturing the said hyperbranched polymer, it is preferable to use a normal catalyst, and examples of the catalyst include BF ₃ diethyl ether, FSO ₃ H, ClSO ₃ H, HClO _{4 and the} like. Can do.

  In addition, examples of the multibranched macromonomer (b1-i-3) in which a structural unit having an amide bond is repeatedly formed to form a branched structure include those having an amide bond in a repeating structure via a nitrogen atom in the molecule. A typical example is the generation 2.0 (PAMAM dentrimer) manufactured by Dentorite.

  Examples of the styrene monomer (b2) that can be used in the present invention include the following. Styrene and derivatives thereof; for example, styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, alkyl styrene such as octyl styrene, fluorostyrene, chlorostyrene , Halogenated styrene such as bromostyrene, dibromostyrene and iodostyrene, nitrostyrene, acetylstyrene, methoxystyrene and the like.

  Moreover, in the range which does not impair the effect of this invention, you may use together the other monomer copolymerizable with the said multibranched macromonomer (b1) and a styrene-type monomer (b2) as needed. Examples of monomers that can be used in combination include acrylic acid acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, and the like. Methacrylic acid acrylic ester, methacrylic acid, maleic acid, fumaric acid, itaconic acid and other polymerizable unsaturated fatty acids, vinylcyan compounds, unsaturated carboxylic acid anhydrides, amino group-containing unsaturated compounds, etc. Two or more of these may be used simultaneously. Among these, it is preferable to use an alkyl acrylate because it is easy to control the polymerization reaction with the styrene monomer (b2) and is easily available industrially, and the molding processability of the resulting PPE resin composition It is more preferable to use butyl acrylate from the viewpoint of the transparency and heat resistance of the molded body.

[Polymerization method of hyperbranched macromonomer (b1) and styrene monomer (b2)]
Lines generated simultaneously by the multibranched resin and the polymerization conditions by copolymerizing the multibranched macromonomer (a1), the styrene monomer (a2), and other monomers used in combination as necessary. A resin mixture which is a mixture of a resin in the form of a resin and a low-branched resin is obtained. At this time, the above-mentioned multibranched macromonomer (b1) is preferably 50 ppm to 1%, more preferably 100 ppm to 3000 ppm (mass basis) with respect to the total amount of the styrene monomer (b2) and other monomers. By using it, it is easy to produce a multi-branched resin, it is easy to suppress gelation, and the polystyrene resin (B) used in the present invention can be obtained efficiently.

  Various commonly used polymerization methods of styrene monomers can be applied to the polymerization reaction. The polymerization method is not particularly limited, but bulk polymerization, suspension polymerization, or solution polymerization is preferable. Among them, continuous bulk polymerization is particularly preferable from the viewpoint of production efficiency.For example, by performing continuous bulk polymerization incorporating one or more stirred reactors and a tubular reactor in which a plurality of mixing elements having no moving parts are fixed. An excellent resin can be obtained. Although thermal polymerization can be performed without using a polymerization initiator, it is preferable to use various radical polymerization initiators. Moreover, what is used for manufacture of a normal polystyrene can be used for polymerization adjuvants, such as a suspending agent and an emulsifier required for superposition | polymerization.

  In order to reduce the viscosity of the reaction product in the polymerization reaction, an organic solvent may be added to the reaction system. Examples of the organic solvent include toluene, ethylbenzene, xylene, acetonitrile, benzene, chlorobenzene, dichlorobenzene, and anisole. , Cyanobenzene, dimethylformamide, N, N-dimethylacetamide, methyl ethyl ketone and the like. In particular, when it is desired to increase the amount of the hyperbranched macromonomer, it is preferable to use an organic solvent from the viewpoint of suppressing gelation. Thereby, the addition amount of the multibranched macromonomer (b1) shown above can be dramatically increased, a large amount of branched structures can be introduced, and gelation hardly occurs.

  The radical polymerization initiator is not particularly limited. For example, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, 2,2-bis (4 , 4-di-butylperoxycyclohexyl) propane and other peroxyketals, cumene hydroperoxide, hydroperoxides such as t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, di Dialkyl peroxides such as -t-hexyl peroxide, diacyl peroxides such as benzoyl peroxide and disinamoyl peroxide, t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, t-butyl peroxide Pao such as oxyisylpropyl monocarbonate Siesters, N, N′-azobisisobutylnitrile, N, N′-azobis (cyclohexane-1-carbonitrile), N, N′-azobis (2-methylbutyronitrile), N, N′-azobis ( 2,4-dimethylvaleronitrile), N, N′-azobis [2- (hydroxymethyl) propionitrile] and the like, and these can be used alone or in combination.

  Furthermore, you may add a chain transfer agent so that the molecular weight of the resin mixture obtained may not become too large. As the chain transfer agent, either a monofunctional chain transfer agent having one chain transfer group or a polyfunctional chain transfer agent having a plurality of chain transfer groups can be used. Examples of the monofunctional chain transfer agent include alkyl mercaptans and thioglycolic acid esters. Polyfunctional chain transfer agents include ethylene glycol, neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol and the like, hydroxy groups in polyhydric alcohols such as thioglycolic acid or 3-mercaptopropionic acid. And the like esterified with.

  The PPE resin composition of this invention should just be what mixed the above-mentioned PPE resin (A) and polystyrene-type resin (B), and the mixing ratio is the application field of the molded object obtained and desired molding processability. Depending on the physical properties according to Since the polystyrene resin (B) used in the present application has high fluidity when melted when compared with a general polystyrene resin of the same molecular weight, the polystyrene resin is used as an improvement in the molding processability of the PPE resin. In the scene where it is used, it is possible to lower the blending ratio from the conventional use ratio. For this reason, the high heat resistance and flame retardancy inherently possessed by the PPE resin (A) are not greatly impaired, and molding processability can be imparted while suppressing deterioration of mechanical strength and oil resistance. It is.

  In general applications, the proportions of PPE resin (A) and polystyrene resin (B) used are usually 10 to 80 parts by mass of PPE resin (A) and 20 to 90 parts by mass of polystyrene resin (B), preferably Are 20-70 parts by mass of PPE resin (A) and 30-80 parts by mass of polystyrene-based resin (B).

  The PPE resin composition of the present invention does not significantly impair the flame retardancy of the PPE resin (A) as described above. However, in order to impart a higher level of flame retardancy to the molded body, C) is preferably blended.

  The type of the flame retardant (C) is not particularly limited, and a specific flame retardant conventionally used for a resin composition of a PPE resin and a polystyrene resin or provided in Patent Document 4 or the like is used. Can be used.

  Examples of the flame retardant (C) include red phosphorus such as red phosphorus; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, and norosinol-bis- (diphenyl). Phosphate), phosphoric acid esters such as 2-ethylerhexyl diphenyl phosphate, dimethylmethyl phosphate, triallyl phosphate; halogen-containing phosphate esters such as trichloroethyl phosphate, trisdichloropropyl phosphate, tris-β-chloropropyl phosphate; Condensed phosphoric acid esters such as group condensed phosphoric acid esters and halogen-containing condensed phosphoric acid esters; and polyphosphates such as ammonium polyphosphate and polychlorophosphite.

  Of these, from the viewpoint of avoiding the generation of harmful gases during combustion, those not containing halogen are preferable, and in this respect, red phosphorus-based ones are preferably used. In addition, red phosphorus can be used even if it is coated with a phenolic resin or contains magnesium hydroxide or titanium oxide.

  In addition, as the flame retardant (C), inorganic flame retardants such as aluminum hydroxide, antimony trioxide, antimony pentoxide, and magnesium hydroxide can be used.

  The proportion of the flame retardant (C) used can be appropriately selected according to the required level of flame retardancy of the molded article to be obtained. As described above, the polystyrene resin (B) used in the present invention is the same. Compared with general-purpose polystyrene having a degree of fluidity, it has a high molecular weight, so that the flame retardancy of the PPE resin (A) is not significantly impaired, and the use ratio can be lowered. Therefore, it is also possible to reduce the contamination of the mold and the like due to the bleedout of the flame retardant (C).

  Generally, the amount of the flame retardant (C) used is usually in the range of 0.5 to 30 parts by weight, preferably 1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the resin components.

[Other additives]
In the PPE resin composition of the present invention, auxiliary agents such as stearic acid, sodium stearate, barium stearate, magnesium stearate, liquid paraffin, olefin wax, stearyl amide compound and the like are provided so long as the object of the present invention is not impaired. It can also be used together. Moreover, you may mix | blend various additives as needed. Examples of such additives include antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, lubricants, antiblocking agents, pigments, dyes, crosslinking agents, crosslinking aids, foaming agents, and foaming agents. Auxiliaries, plasticizers, phosphate ester compounds, inorganic substances such as silica, talc, wollastonite, calcium silicate, kaolin, mica, clay, zinc oxide, calcium carbonate and the like can be mentioned.

  Furthermore, other resin compositions can be appropriately blended with the PPE resin composition of the present invention as long as the effects of the present invention are not impaired. Examples of the other resin composition include rubber-containing polystyrene (HIPS), styrene-butadiene copolymer, styrene-acrylic resin, and styrene-methacrylic resin. Moreover, flexibility is imparted to the resulting molded body by blending the styrene elastomer. Styrenic elastomers are highly compatible with polyphenylene ether resins and have been selected as low dielectric constant and low dielectric loss tangent elastomers. The styrene elastomer is a styrene-polyolefin copolymer, and has a styrene ratio of 50% or more, more preferably 50 to 80% by mass ratio. As the polyolefin phase, one or more styrenic elastomers such as poly (polyethylene-propylene), polyethylene-polybutylene random copolymer, polybutadiene, and polyisoprene can be used.

[Method for producing molded article]
The PPE resin composition of the present invention contains a PPE resin (A), a polystyrene-based resin (B), a flame retardant (C) blended as necessary, and the above-mentioned various additives, which are optional components. For example, it can be obtained by melt-kneading at a temperature of about 180 to 300 ° C. using a screw extruder, a pressure kneader, a Banbury mixer or the like. In the present invention, the resin composition may have a shape that is generally widely used as a feedstock supplied to a molding apparatus for obtaining a molded product according to a specific application. Specifically, for example, a so-called primary molded product such as a plate shape, a rod shape, a cylindrical shape, a conical shape, and a fibrous shape can be used.

  In addition, the PPE resin composition of the present invention can be processed by cast extrusion, extrusion molding, injection molding, or the like to produce a molded body having a desired shape. However, the processing method has a good yield. An injection molding method is preferred.

[Injection molding method]
The injection molding method is not limited at all, but it is preferable to use a mold having a multi-point pin gate, a side gate, etc. in that the molten resin composition can be uniformly flowed and molded in a balanced manner. . Further, in order to obtain a molded article having good dimensional accuracy and free from gas haze, a mold provided with a vacuum drawing hole is preferable so that the mold cavity can be decompressed when the molten resin composition is injected. Furthermore, a die having a hot runner is preferable because no scrap is generated and the loss during production is small. When a hot runner is used, a needle valve that closes the gate after completion of the flow of the molten resin composition into the mold cavity is also preferably used so as not to generate a gate mark.

[Use of molded body]
The use of the molded body of the present invention is not limited at all, and is useful as a material for molding various molded products such as home appliance parts, electrical / electronic parts, automobile parts, machine / mechanical parts, cosmetic containers and the like. is there. For example, pipe materials such as hoses and tubes; civil engineering materials such as artificial turf, mats, tunnel sheets, waterproof sheets and roofing; building materials such as furniture, flooring and foam sheets; carpet lining materials, door panel tarpaulins, mud Automotive interior and exterior parts such as gaskets and moldings; Household appliances such as packing and damping sheets; Breaker parts, switch parts, motor parts, ignition coil cases, power plugs, power outlets, coil bobbins, connectors, relay cases, fuse cases, fly It can be suitably used for back transformer parts, focus block parts, distributor caps, harness connectors and the like. Furthermore, thinning housings, casings or chassis, such as electronic and electrical products (such as telephones, personal computers, printers, fax machines, copiers, televisions, VCRs, audio equipment and other home appliances / OA equipment, or parts thereof) Useful for housings, casings or chassis. In particular, it is also useful as a printer casing, fixing unit parts, and other machine / mechanical parts of home appliances and OA products such as fax machines that require particularly excellent heat resistance and flame retardancy.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention should not be limited to the scope of these examples. Hereinafter, “part” and “%” are based on mass unless otherwise specified.

The measurement method used will be described.
[GPC measurement conditions for hyperbranched macromonomer]
GPC measurement of a multi-branched macromonomer was performed using high performance liquid chromatography (HLC-8220GPC manufactured by Tosoh Corporation), RI detector, TSK gel G6000H × 1 + G5000H × 1 + G4000H × 1 + G3000H × 1 + TSK guard column H × 1, solvent THF, flow rate 1 The test was carried out under the conditions of 0.0 ml / min and a temperature of 40 ° C.

[GPC-MALS measurement]
GPC-MALS measurement of the styrene resin was performed under the conditions of Shodex HPLC, detector Wyatt Technology DAWN EOS, Shodex RI-101, column Shodex KF-806L × 2, solvent THF, and flow rate of 1.0 ml / min. In addition, the analysis of GPC-MALS measurement was performed with Wyatt's analysis software AST RA, and the weight average molecular weight was determined for the polystyrene resin (B), and the molecular weight of the resin mixture determined from GPC-MALS was plotted on the horizontal axis. In the logarithmic graph with the inertial radius as the vertical axis, the slope in the region of molecular weight 250,000-10 million (automatically calculated by the software based on the measured value of only the linear portion obtained in the molecular weight range) Slope of the approximate straight line).

[NMR measurement method]
The amount of the polymerizable double bond of the hyperbranched macromonomer was determined by nuclear magnetic resonance spectroscopy ( ¹ H-NMR, JNM-LA300 type manufactured by JEOL), and indicated by the number of moles per sample mass.

[Melt Mass Flow Rate Measurement Method]
The measurement was performed according to JIS K7210. The measurement conditions are a temperature of 200 ° C. and a load of 49N.

  As the PPE resin (A), poly (2,6-dimethyl-1,4-phenyl ether) (A-1) having a reduced viscosity of 0.53 dl / g at 30 ° C. in 0.5 g / 100 ml chloroform is used. did.

  As a flame retardant, product name CR741 (aromatic condensed phosphate ester compound) (C-1) manufactured by Daihachi Chemical Industry Co., Ltd. was used.

[Molding method]
PPE resin (A), polystyrene resin (B), and flame retardant (C) are dry blended in advance and melt mixed (residence time 3 minutes, 280) using a twin screw extruder (PCM-30 manufactured by Ikegai Seisakusho). C.), water-cooled, strand-cut and re-pelletized. Using the repelleted sample, a molded article for evaluation was obtained with an injection molding machine (melting temperature: 280 ° C.). The appearance of the obtained molded article for evaluation (dumbbell piece) was judged visually. (Good appearance ○, slightly bad Δ, bad x)

  As for the mechanical strength of molded products (dumbbells), a Charpy impact test is conducted. If there is no problem in practice, ○, if there is a problem in practical use, △ indicates that it can be used depending on the application, and if there is a problem in practical use. X. Moreover, as evaluation of the oil resistance of the obtained molded product, the molded product was placed on a ¼ ellipsoid, machine oil was applied to the surface, and the surface condition after 12 hours was visually confirmed. The crack-free one was 5, the microcrack was 4, the small crack was 3, the medium crack was 2, and the large crack was 1.

  About flame retardancy, according to UL-94 standard, the thing suitable for V-0 standard was set as (circle).

Reference Example 1 Synthesis of Multibranched Macromonomer (Mm-1) <Synthesis of Multibranched Polyether Polyol 1>
To a 2 liter flask equipped with a stirrer, a thermometer, a dropping funnel and a condenser, 50.5 g of ethoxylated pentaerythritol (5 mol-ethylene oxide-added pentaerythritol) and 1 g of BF ₃ diethyl ether solution (50%) were added at room temperature. Heated to 110 ° C. To this, 450 g of 3-ethyl-3- (hydroxymethyl) oxetane was slowly added over 25 minutes while controlling the exotherm due to the reaction. When the exotherm had subsided, the reaction mixture was further stirred at 120 ° C. for 3 hours and then cooled to room temperature. The resulting multi-branched polyether polyol had a weight average molecular weight of 3,000 and a hydroxyl value of 530.

<Synthesis of Multibranched Polyether 1 Having Methacryloyl Group and Acetyl Group>
In a reactor equipped with a Dean-Stark decanter equipped with a stirrer, a thermometer, a condenser, and a gas introduction tube, 50 g of the multi-branched polyether polyol obtained in the above-mentioned <Synthesis of multi-branched polyether polyol 1>, methacrylic acid 13 .8 g, 150 g of toluene, 0.06 g of hydroquinone and 1 g of paratoluenesulfonic acid, and stirring under normal pressure while blowing 7% oxygen-containing nitrogen (v / v) into the mixed solution at a rate of 3 ml / min. Heated. The amount of heating was adjusted so that the amount of distillate in the decanter was 30 g per hour, and heating was continued until the amount of dehydration reached 2.9 g. After completion of the reaction, the mixture was cooled once, 36 g of acetic anhydride and 5.7 g of sulfamic acid were added, and the mixture was stirred at 60 ° C. for 10 hours. Thereafter, in order to remove the remaining acetic acid and hydroquinone, it was washed with 50 g of 5% aqueous sodium hydroxide solution four times, and further washed once with 50 g of 1% aqueous sulfuric acid solution and twice with 50 g of water. To the obtained organic layer, 0.02 g of methoquinone was added, the solvent was distilled off while introducing 7% oxygen-containing nitrogen (v / v) under reduced pressure, and 60 g of a multibranched polyether having an isopropenyl group and an acetyl group was obtained. Obtained. The obtained multi-branched polyether had a mass average molecular weight of 3,900, and the introduction rate of isopropenyl group and acetyl group into the multi-branched polyether polyol was 30 mol% and 62 mol%, respectively.

Reference Example 2 Synthesis of Multibranched Macromonomer (Mm-2) <Synthesis of Multibranched Polyether 1 Having Styryl Group and Acetyl Group>
In a reactor equipped with a stirrer, a condenser equipped with a drying tube, a dropping funnel and a thermometer, 50 g of the multibranched polyether polyol obtained in the above-mentioned <Synthesis of multibranched polyether polyol 1>, 100 g of tetrahydrofuran and sodium hydride 4.3 g was added and stirred at room temperature. To this was added dropwise 26.7 g of 4-chloromethylstyrene over 1 hour, and the resulting reaction mixture was further stirred at 50 ° C. for 4 hours. After completion of the reaction, the reaction mixture was once cooled, 34 g of acetic anhydride and 5.4 g of sulfamic acid were added, and the mixture was stirred at 60 ° C. for 10 hours. Thereafter, the tetrahydrofuran was distilled off under reduced pressure, the resulting mixture was dissolved in 150 g of toluene, washed with 50 g of 5% aqueous sodium hydroxide solution to remove the remaining acetic acid, and further 50 g of 1% aqueous sulfuric acid solution. And once with 50 g of water. The solvent was distilled off from the obtained organic layer under reduced pressure to obtain 70 g of a multi-branched polyether having a styryl group and an acetyl group. The obtained multi-branched polyether had a mass average molecular weight of 4,800, and the styryl group and acetyl group introduction rates into the multi-branched polyether polyol were 38 mol% and 57 mol%, respectively.

(Reference Example 3) Synthesis of hyperbranched macromonomer (Mm-3) <Synthesis of hyperbranched macromonomer having a methacryloyl group and an acetyl group>
A four-necked flask was equipped with a stirrer, pressure gauge, condenser and saucer, to which 308.9 g of ethoxylated pentaerythritol and 0.46 g of sulfuric acid were added. Then, it heated to 140 degreeC and 460.5g of 2, 2- di (hydroxymethyl) propionic acid was added over 10 minutes. After 2,2-di (hydroxymethyl) propionic acid is completely dissolved and becomes a transparent solution, the pressure is reduced to 30 to 40 mmHg and the reaction is continued for 4 hours while stirring and the acid value becomes 7.0 mgKOH / g. I let you. Thereafter, 921 g of 2,2-di (hydroxymethyl) propionic acid and 0.92 g of sulfuric acid were added to the reaction solution over 15 minutes to obtain a transparent solution, and then the pressure was reduced to 30 to 40 mmHg, while stirring. The polyester polyol was obtained by reacting for a period of time. In a reaction vessel equipped with a 7% oxygen introduction tube, a thermometer, a Dean-Stark decanter equipped with a condenser, and a stirrer, 10 g of the polyester polyol produced above, 1.25 g of dibutyltin oxide, and 100 g of methyl methacrylate having an isopropenyl group And 0.05 g of hydroquinone were added, and the mixture was heated with stirring while blowing 7% oxygen at a rate of 3 ml / min. The amount of heating is adjusted so that the amount of distillate in the decanter is 15 to 20 g per hour, the distillate in the decanter is taken out every hour, and the corresponding amount of methyl methacrylate is added for 4 hours. Reacted. After completion of the reaction, methyl methacrylate was distilled off under reduced pressure, and 10 g of acetic anhydride and 2 g of sulfamic acid were added to cap the remaining hydroxy groups, followed by stirring at room temperature for 10 hours. After removing sulfamic acid by filtration and distilling off acetic anhydride and acetic acid under reduced pressure, the residue was dissolved in 70 g of ethyl acetate and washed 4 times with 20 g of 5% aqueous sodium hydroxide to remove hydroquinone. Further, it was washed twice with 20 g of a 7% aqueous sulfuric acid solution and twice with 20 g of water. To the obtained organic layer, 0.0045 g of methoquinone was added, and the solvent was distilled off while introducing 7% oxygen under reduced pressure to obtain 11 g of a hyperbranched macromonomer (Mm-3) having an isopropenyl group and an acetyl group. It was. The resulting multi-branched macromonomer (Mm-3) has a weight average molecular weight of 3,000, a number average molecular weight of 2,100, and a double bond introduction amount of 2.00 mmol / g, an isopropenyl group and an acetyl group. The introduction rates were 55 mol% and 36 mol%, respectively.

(Reference Example 4) Synthesis of hyperbranched macromonomer (Mm-4) <Synthesis of PAMAM dendrimer having a styryl group>
To a reactor equipped with a stirrer, a condenser equipped with a drying tube, a dropping funnel and a thermometer, 50 g of a methanol solution (20%) of PAMAM dendrimer (Generation 2.0: manufactured by Dentritech) was added and stirred under reduced pressure. Methanol was distilled off. Subsequently, 50 g of tetrahydrofuran and 3.0 g of finely divided potassium hydroxide were added, and the mixture was stirred at room temperature. 4-chloromethylstyrene 7.0g was dripped at this over 10 minutes, and the obtained reaction mixture was further stirred at 50 degreeC for 3 hours. After completion of the reaction, the mixture was cooled and the solid was filtered, and then tetrahydrofuran was distilled off under reduced pressure to obtain 13 g of a PAMAM dendrimer having a styryl group. The resulting styryl group content of the dendrimer was 2.7 mmol / gram.

Reference Example 5 Synthesis of Multibranched Macromonomer (Mm-5) <Multibranched Polyether Polyol 2 Having Styryl Group and Acetyl Group>
A light-shielding reaction vessel equipped with a stirrer, a condenser, a light-shielding dropping funnel and a thermometer, and capable of nitrogen sealing. Under nitrogen flow, anhydrous 1,3,5-trihydroxybenzene 0.5 g, potassium carbonate 29 g, 18-crown -6 2.7 g and acetone 180 g were added, and a solution composed of 21.7 g of 5- (bromomethyl) -1,3-dihydroxybenzene and 180 g of acetone was added dropwise over 2 hours while stirring. Thereafter, the mixture was heated and refluxed with stirring until 5- (bromomethyl) -1,3-dihydroxybenzene disappeared. Thereafter, 9.0 g of 4-chloromethylstyrene was added, and the mixture was further heated and refluxed with stirring until the disappearance. Thereafter, 4 g of acetic anhydride and 0.6 g of sulfamic acid were added to the reaction mixture, and the mixture was stirred overnight at room temperature. After cooling, the solid in the reaction mixture was removed by filtration, and the solvent was distilled off under reduced pressure. The obtained mixture was dissolved in dichloromethane and washed three times with water, and then the dichloromethane solution was added dropwise to hexane to precipitate a multibranched polyether. This was filtered and dried to obtain 12 g of a multi-branched polyether polyol having a styryl group and an acetyl group. The mass average molecular weight was 3,200, and the styryl group content was 3.5 mmol / gram.

Example 1
A mixed solution consisting of 90 parts of styrene monomer, 500 ppm of the hyperbranched macromonomer (Mm-1) obtained in Reference Example 1 with respect to the styrene monomer, and 10 parts of toluene was prepared, and the styrene monomer as an organic peroxide was further prepared. 300 ppm of t-butylperoxybenzoate was added to the mixture, and bulk polymerization was continuously carried out under the following conditions using the apparatus shown in FIG.

Supply amount of mixed solution: 9 L / hr
Reaction temperature of the stirring reactor (2): 120 ° C
Circulating polymerization line (I) reaction temperature: 120 ° C
Reaction temperature of non-circular polymerization line (II): 130 to 150 ° C
Reflux ratio: R = F1 / F2 = 6
However, F1 shows the flow volume of the mixed solution which recirculates in the circulation polymerization line, and F2 shows the flow volume of the mixed solution which flows out to a non-circulation polymerization line.

  The mixed solution obtained by polymerization was heated to 220 ° C. with a heat exchanger, and after removing volatile components under a reduced pressure of 50 mmHg, pelletized to obtain a polystyrene resin (B-1). Mw by GPC-MALS: 530,000, the logarithm of the molecular weight and the radius of inertia determined from GPC-MALS was 0.39. MFR is 1.0 g / 10 min. Met. A log-log graph of the molecular weight and the radius of inertia determined from GPC-MALS of the obtained polystyrene resin (B-1) is shown in FIG.

  After 40 parts of PPE resin (A-1) and 18 parts of flame retardant (C-1) were added to 40 parts of the resulting polystyrene resin (B-1) and dry blended, 280 using a twin screw extruder. The mixture was melt-mixed at 0 ° C., water-cooled, strand-cut and re-pelletized. Using the re-pelleted sample, a molded article for evaluation was obtained with an injection molding machine (molding temperature 280 ° C.).

Example 2
A polystyrene resin (B-2) was obtained in the same manner as in Example 1 except that the multibranched macromonomer (Mm-2) was used instead of the multibranched macromonomer (Mm-1) in Example 1. Obtained. Mw by GPC-MALS: 490,000. The logarithm of the molecular weight and the radius of inertia determined from GPC-MALS was 0.41. MFR is 0.8 g / 10 min. Met.

  After 40 parts of PPE resin (A-1) and 18 parts of flame retardant (C-1) were added to 40 parts of the obtained polystyrene resin (B-2) and dry blended, 280 using a twin screw extruder. The mixture was melt-mixed at 0 ° C., water-cooled, strand-cut and re-pelletized. Using the re-pelleted sample, a molded article for evaluation was obtained with an injection molding machine (molding temperature 280 ° C.).

Example 3
A polystyrene resin (B-3) was obtained in the same manner as in Example 1 except that the hyperbranched macromonomer (Mm-3) was used instead of the hyperbranched macromonomer (Mm-1) in Example 1. Obtained. Mw by GPC-MALS: 550,000, the logarithm of the molecular weight and the radius of inertia determined from GPC-MALS was 0.40. MFR is 1.2 g / 10 min. Met.

  After 40 parts of PPE resin (A-1) and 18 parts of flame retardant (C-1) were added to 40 parts of the obtained polystyrene resin (B-3) and dry blended, 280 using a twin screw extruder. The mixture was melt-mixed at 0 ° C., water-cooled, strand-cut and re-pelletized. Using the re-pelleted sample, a molded article for evaluation was obtained with an injection molding machine (molding temperature 280 ° C.).

Example 4
A polystyrene resin (B-4) was obtained in the same manner as in Example 1 except that the multibranched macromonomer (Mm-4) was used instead of the multibranched macromonomer (Mm-1) in Example 1. Obtained. Mw by GPC-MALS: 500,000. The logarithm of molecular weight and radius of inertia determined from GPC-MALS was 0.40. MFR is 1.1 g / 10 min. Met.

  After 40 parts of PPE resin (A-1) and 18 parts of flame retardant (C-1) were added to 40 parts of the obtained polystyrene resin (B-4) and dry blended, 280 using a twin screw extruder. The mixture was melt-mixed at 0 ° C., water-cooled, strand-cut and re-pelletized. Using the re-pelleted sample, a molded article for evaluation was obtained with an injection molding machine (molding temperature 280 ° C.).

Example 5
Polystyrene resin (B-5) was used in the same manner as in Example 1 except that the hyperbranched macromonomer (Mm-5) was used instead of the hyperbranched macromonomer (Mm-1) in Example 1. Obtained. Mw by GPC-MALS: 480,000, and the logarithm of molecular weight and inertia radius determined from GPC-MALS was 0.39. MFR is 1.4 g / 10 min. Met.

  After 40 parts of PPE resin (A-1) and 18 parts of flame retardant (C-1) were added to 40 parts of the obtained polystyrene resin (B-5) and dry blended, 280 using a twin screw extruder. The mixture was melt-mixed at 0 ° C., water-cooled, strand-cut and re-pelletized. Using the re-pelleted sample, a molded article for evaluation was obtained with an injection molding machine (molding temperature 280 ° C.).

Example 6
A molded product for evaluation was obtained in the same manner except that the blend ratio of polystyrene resin (B-1) in Example 1 was 70 parts and 30 parts of PPE resin (A-1).

Example 7
A molded product for evaluation was obtained in the same manner except that the blend ratio of polystyrene resin (B-2) in Example 2 was changed to 70 parts and PPE resin (A-1) 30 parts.

Example 8
A molded article for evaluation was obtained in the same manner except that the blend ratio of polystyrene resin (B-3) in Example 3 was 70 parts and 30 parts of PPE resin (A-1).

Example 9
A molded product for evaluation was obtained in the same manner except that the blend ratio of the polystyrene resin (B-4) in Example 4 was 70 parts and 30 parts of PPE resin (A-1).

Example 10
A molded product for evaluation was obtained in the same manner except that the blend ratio of polystyrene resin (B-5) in Example 5 was changed to 70 parts and PPE resin (A-1) 30 parts.

Example 11
The reaction temperature of the stirred reactor (2) of Example 1 is 132 ° C., the reaction temperature of the circulation polymerization line (I) is 145 ° C., the reaction temperature of the non-circulation polymerization line (II) is 150 to 170 ° C., the multi-branched macro A polystyrene resin (B-6) was obtained in the same manner except that the monomer (Mm-1) was changed to 700 ppm with respect to the styrene monomer. Mw by GPC-MALS: 350,000, both logarithms of molecular weight and inertia radius determined from GPC-MALS were 0.35. MFR is 7.0 g / 10 min. Met.

  After 40 parts of PPE resin (A-1) and 18 parts of flame retardant (C-1) were added to 40 parts of the obtained polystyrene resin (B-6) and dry blended, 280 using a twin screw extruder. The mixture was melt-mixed at 0 ° C., water-cooled, strand-cut and re-pelletized. Using the re-pelleted sample, a molded article for evaluation was obtained with an injection molding machine (molding temperature 280 ° C.).

Example 12
A molded product for evaluation was obtained in the same manner except that the blend ratio of polystyrene resin (B-6) in Example 11 was 70 parts and 30 parts of PPE resin (A-1).

Example 13
A polystyrene resin (B-7) was obtained in the same manner except that the multibranched macromonomer (Mm-2) was used instead of the multibranched macromonomer (Mm-1) used in Example 11. Mw by GPC-MALS: 330,000, the logarithm of the molecular weight and the radius of inertia determined from GPC-MALS was 0.37. MFR is 7.2 g / 10 min. Met.

Example 14
A molded product for evaluation was obtained in the same manner except that the blend ratio of polystyrene resin (B-7) in Example 13 was 70 parts and 30 parts of PPE resin (A-1).

Example 15
A polystyrene resin (B-8) was obtained in the same manner except that the multibranched macromonomer (Mm-3) was used instead of the multibranched macromonomer (Mm-1) used in Example 11. Mw by GPC-MALS: 360,000, and the logarithm of the molecular weight and the radius of inertia determined from GPC-MALS was 0.35. MFR is 6.9 g / 10 min. Met.

Example 16
A molded product for evaluation was obtained in the same manner except that the blend ratio of polystyrene resin (B-8) in Example 15 was 70 parts and 30 parts of PPE resin (A-1).

Example 17
A polystyrene resin (B-9) was obtained in the same manner except that the multibranched macromonomer (Mm-4) was used instead of the multibranched macromonomer (Mm-1) used in Example 11. Mw by GPC-MALS: 330,000, both logarithms of molecular weight and inertia radius determined from GPC-MALS were 0.36. MFR is 7.3 g / 10 min. Met.

Example 18
A molded article for evaluation was obtained in the same manner except that the blend ratio of polystyrene resin (B-9) in Example 17 was 70 parts and 30 parts of PPE resin (A-1).

Example 19
A polystyrene resin (B-10) was obtained in the same manner except that the multibranched macromonomer (Mm-5) was used instead of the multibranched macromonomer (Mm-1) used in Example 11. Mw by GPC-MALS: 360,000. The logarithm of molecular weight and radius of inertia determined from GPC-MALS was 0.38. MFR is 6.5 g / 10 min. Met.

Example 20
A molded article for evaluation was obtained in the same manner except that the blend ratio of polystyrene resin (B-10) in Example 17 was 70 parts and 30 parts of PPE resin (A-1).

Comparative Example 1
A mixed solution consisting of 95 parts of styrene monomer and 5 parts of toluene was prepared, and 200 ppm of 2,2-Bis (4,4-di-butyl peroxycyclohexyl) propane was added as an organic peroxide to the styrene monomer. The apparatus shown in 1 was used for continuous bulk polymerization under the following conditions.

Supply amount of mixed solution: 9 L / hr
Reaction temperature of the stirring reactor (2): 115 ° C.
Circulating polymerization line (I) reaction temperature: 120 ° C
Reaction temperature of non-circular polymerization line (II): 130 to 150 ° C
Reflux ratio: R = F1 / F2 = 6
However, F1 shows the flow volume of the mixed solution which recirculates in the circulation polymerization line, and F2 shows the flow volume of the mixed solution which flows out to a non-circulation polymerization line.

  The mixed solution obtained by polymerization was heated to 220 ° C. with a heat exchanger, volatile components were removed under a reduced pressure of 50 mmHg, and pelletized to obtain a polystyrene resin (B′-1). Mw by GPC-MALS: 360,000. The logarithm of the molecular weight and the radius of inertia determined from GPC-MALS was 0.53. MFR is 1.1 g / 10 min. Met.

  After 40 parts of PPE resin (A-1) and 18 parts of flame retardant (C-1) were added and dry blended to 40 parts of the resulting polystyrene resin (B′-1), a twin screw extruder was used. It melt-mixed at 280 degreeC, water-cooled, strand-cut and re-pelletized. Using the re-pelleted sample, a molded article for evaluation was obtained with an injection molding machine (molding temperature 280 ° C.).

Comparative Example 2
In Comparative Example 1, a molded article for evaluation was obtained in the same manner as Comparative Example 1, except that the blend ratio was 70 parts of polystyrene resin (B′-1) and 30 parts of PPE resin (A-1).

Comparative Example 3
A mixed solution consisting of 90 parts of styrene monomer and 10 parts of toluene was prepared and polymerized continuously using the apparatus shown in FIG. 1 under the following conditions.

Supply amount of mixed solution: 9 L / hr
Reaction temperature of the stirring reactor (2): 135 ° C
Circulating polymerization line (I) reaction temperature: 140 ° C
Reaction temperature of non-circulation polymerization line (II): 140-160 ° C
Reflux ratio: R = F1 / F2 = 6
However, F1 shows the flow volume of the mixed solution which recirculates in the circulation polymerization line, and F2 shows the flow volume of the mixed solution which flows out to a non-circulation polymerization line.

  The mixed solution obtained by polymerization was heated to 220 ° C. with a heat exchanger to remove volatile components under a reduced pressure of 50 mmHg, and then pelletized to obtain a polystyrene resin (B′-2). Mw by GPC-MALS: 230,000, the logarithm of the molecular weight and the radius of inertia determined from GPC-MALS was 0.59. MFR is 7.1 g / 10 min. Met.

  After 40 parts of PPE resin (A-1) and 18 parts of flame retardant (C-1) were added to 40 parts of the obtained polystyrene resin (B′-2) and dry blended, using a twin screw extruder. It melt-mixed at 280 degreeC, water-cooled, strand-cut and re-pelletized. Using the re-pelleted sample, a molded article for evaluation was obtained with an injection molding machine (molding temperature 280 ° C.).

Comparative Example 4
In Comparative Example 3, a molded article for evaluation was obtained in the same manner except that the blend ratio was 70 parts of polystyrene-based resin (B′-2) and 30 parts of PPE resin (A-1).

  The evaluation results are shown in Tables 1-6.

  From the above, by blending a specific polystyrene resin having a branched structure with a conventional polyphenylene ether resin, the flame retardancy and mechanical strength of the polyphenylene ether resin have good moldability even in injection molding and the like. It is clear that the oil resistance is not impaired.

It is process drawing which shows one example of the continuous polymerization line incorporating the tubular reactor which has a static mixing element. 4 is a GPC-MALS chromatograph of polystyrene-based resin (B-3) obtained in Example 3. FIG. It is the logarithm graph of the molecular weight of a polystyrene-type resin (B-3) calculated | required from GPC-MALS, and an inertia radius.

Explanation of symbols

(1): Plunger pump (2): Stirred reactor (3), (7): Gear pumps (4) to (6), (8) to (10): Tubular reactor having a static mixing element

Claims (5)

A resin composition comprising a polyphenylene ether resin (A) and a polystyrene resin (B), wherein the polystyrene resin (B) is
It contains a resin obtained by copolymerizing a multi-branched macromonomer (b1) having a plurality of branches and having a plurality of polymerizable double bonds at the tip thereof and a styrenic monomer (b2). A polyphenylene ether resin composition. The polystyrene-based resin (B) has (1) a weight average molecular weight determined by GPC-MALS method of 150,000 to 550,000,
(2) In a log-log graph with the molecular weight determined by the GPC-MALS method as the horizontal axis and the inertial radius as the vertical axis, the slope in the region of the molecular weight of 250,000 to 10 million is 0.30 to 0.45. 1. The polyphenylene ether resin composition according to 1. Furthermore, the polyphenylene ether-type resin composition in any one of Claim 1 or 2 containing a flame retardant (C). A molded article comprising the resin composition according to any one of claims 1 to 3. The molded article according to claim 4, which is obtained by injection molding.

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