JP2011153259A - Resin composition and molding using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which is excellent in appearance properties and has a good balance between moldability and heat resistance, and from which a molding having practically sufficient strength is produced, and to provide a molding using the composition. <P>SOLUTION: The resin composition includes: (A) 10-90 pts.mass of a polyphenylene ether; (B) 90-10 pts.mass of a rubber-modified polystyrene and a homopolystyrene; (C) 0-40 pts.mass of a phosphorus compound as a flame retardant; (D) 0.05-1.0 pts.mass of a mold-releasing agent; and (E) a pigment-based colorant. The rubber-modified polystyrene is composed of HIPS(a) and HIPS(b) each being a high impact polystyrene containing rubber particles, wherein the weight ratio of HIPS(a) to HIPS(b) is 98/2 to 70/30. The configuration of the rubber particles in the HIPS(a) is composed of one polystyrene core (unicellular structure). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin composition and a molded body using the same.

  Conventionally, a mixed resin (hereinafter also referred to as a “modified PPE resin”) based on a polyphenylene ether (hereinafter also referred to as “PPE”) resin and a styrene resin has a mixing ratio of the PPE resin and the styrene resin. Depending on the range, from styrene resin alone to PPE resin alone, it exhibits predetermined heat resistance, and furthermore, electrical characteristics, dimensional stability, impact resistance, acid resistance, alkali resistance, low water absorption and low It is known to be excellent in specific gravity.

In addition, the modified PPE resin is known to be excellent in terms of environment and safety and health because it can be made flame retardant without using harmful halogen compounds or antimony trioxide.
Therefore, the modified PPE resin is used for various electric / electronic parts, office equipment parts, exterior materials, industrial products, and the like.

By the way, in recent years, attempts have been made to increase the value of products using exterior members having high gloss in home appliances such as televisions.
In general, after molding the exterior material using a normal resin material, by applying a clear coating on the surface, a technology to obtain a decorative exterior material is known, but as a recent trend, Attempts have been made to obtain an exterior material having decorative properties without painting by using a resin material having high gloss.
Unpainted and decorative exterior materials are inevitably an important quality control item because the appearance of the molded product is an important quality control item, and resin materials that do not cause such defects are greatly affected by molding. Expectations are growing.
In order to meet the demand for the molded body as described above, for example, Patent Document 1 discloses a technique for obtaining a resin composition having high glossiness by blending a specific organic dye into the resin composition. It is disclosed.

JP 2005-132970 A

However, the technique described in Patent Document 1 is still insufficient as a resin composition having sufficient characteristics for producing various molded articles having high appearance quality.
That is, mold contamination (mold deposit, transfer of resin dye to mold) occurs when molding the exterior material, and defects in the molded product (whitening, fogging, color tone anisotropy, uneven color) occur. It is.

  Therefore, in the present invention, in order to solve the problems occurring at the time of molding and the problems of the obtained molded body, it has excellent appearance characteristics, has a good balance between molding processability and heat resistance, and is practically sufficient. An object of the present invention is to provide a resin composition capable of producing a molded article having a sufficient mechanical strength and a molded article using the same.

In order to solve the above-mentioned problems, the present inventors have intensively studied the results of (A) polyphenylene ether, (B) rubber-modified polystyrene and homopolystyrene, (C) a phosphorus compound as a flame retardant, (D) a release agent, (E ) It is a polyphenylene ether-based resin composition containing a pigment-based colorant, and the above-mentioned problem can be solved by combining two types of HIPS having different rubber particle forms as the (B) rubber-modified polystyrene, The present invention has been completed.
That is, the present invention is as follows.

[1]
When the total of the following (A) + (B) + (C) is 100 parts by mass,
(A) 10 to 90 parts by mass of polyphenylene ether,
(B) 90 to 10 parts by mass of rubber-modified polystyrene and homopolystyrene,
(C) 0 to 40 parts by mass of a phosphorus compound as a flame retardant,
(D) 0.05 to 1.0 parts by weight of release agent,
(E) containing a pigment-based colorant,
The rubber-modified polystyrene is composed of HIPS (a) and HIPS (b), which are high-impact polystyrene containing rubber particles, and the weight ratio of HIPS (a) / HIPS (b) is 98/2 to 70/30. ,
HIPS (a) includes those in which the rubber particles have a single polystyrene core (single cell structure), and the rubber particles have an average particle size of 0.1 to 0.5 μm,
HIPS (b) includes the rubber particles having a salami structure (multi-cell structure), and the rubber particles have an average particle diameter of 0.9 to 4 μm.
Resin composition.

[2]
The resin composition as described in [1] above, which contains 0.05 to 0.8 parts by mass of (D) with respect to a total of 100 parts by mass of (A) + (B) + (C).

[3]
[1] or [2], wherein (D) the release agent contains one or more selected from the group consisting of metal salts of higher fatty acids, higher fatty acid amides and / or bisamides, higher fatty acid esters, and paraffin wax. Resin composition.

[4]
The resin composition according to any one of [1] to [3], wherein the (D) release agent contains a metal salt of a higher fatty acid.

[5]
Said [1] thru | or [4] containing 0.1-5 mass parts of said (E) pigment type colorants with respect to a total of 100 mass parts of said (A) + said (B) + said (C). The resin composition as described in any one of these.

[6]
The flame retardant (C) is
Formula (I) below

Or the following formula (II)

Containing a condensed phosphate ester represented by
Any one of [1] to [5] above, wherein 3 to 35 parts by mass of the flame retardant (C) is contained with respect to 100 parts by mass of (A) + (B) + (C). The resin composition as described in 1.
(In the formula, Q1, Q2, Q3 and Q4 represent hydrogen or an alkyl group having 1 to 6 carbon atoms, R1, R2, R3 and R4 represent hydrogen or a methyl group. N represents an integer of 1 or more. n1, n2 represents an integer of 0-2, and m1, m2, m3, m4 represents an integer of 1-3.)

[7]
The flame retardant (C) is represented by the following formula (I)

Containing a condensed phosphate ester represented by
Any one of [1] to [6] above, wherein 5 to 30 parts by mass of the flame retardant (C) is contained with respect to a total of 100 parts by mass of (A) + (B) + (C). The resin composition as described in 1.
(In the formula, Q1, Q2, Q3 and Q4 represent hydrogen or an alkyl group having 1 to 6 carbon atoms, R1, R2, R3 and R4 represent hydrogen or a methyl group. N represents an integer of 1 or more. n1, n2 represents an integer of 0-2, and m1, m2, m3, m4 represents an integer of 1-3.)

[8]
The molded object using the resin composition as described in any one of said [1] thru | or [7].

[9]
The molded product according to [8], which is a molded product for exteriors of a television, a video, and an office machine.

  According to the present invention, a machine that solves the problems that occur during molding and the problems of the resulting molded body, has excellent appearance characteristics, has a good balance between molding processability and heat resistance, and is practically sufficient. Resin composition capable of producing a molded article having sufficient strength and a molded article using the same are obtained.

It is a photography photograph of the transmission electron microscope which shows the rubber particle shape in the resin composition of this embodiment.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
In addition, this invention is not restrict | limited to the following embodiment, A various deformation | transformation can be implemented within the range of the summary.

(Resin composition)
The resin composition of the present embodiment is
When the total of the following (A) + (B) + (C) is 100 parts by mass,
(A) Polyphenylene ether: 10 to 90 parts by mass,
(B) Rubber-modified polystyrene and homopolystyrene: 90 to 10 parts by mass,
(C) Phosphorus compound as a flame retardant: 0 to 40 parts by mass,
(D) Release agent: 0.05 to 1.0 part by mass,
(E) a pigment-based colorant;
Is a resin composition containing
Here, the (B) rubber-modified polystyrene is composed of HIPS (a) and HIPS (b), which are high-impact polystyrene containing rubber particles, and the weight ratio of HIPS (a) / HIPS (b) is 98/2. ~ 70/30.
HIPS (a): The rubber particles are mainly composed of one polystyrene core (single cell structure), and the rubber particles have an average particle diameter of 0.1 to 0.5 μm.
Here, “mainly” means that 90% or more, preferably 95% or more of the rubber particles are composed of one polystyrene core (single cell structure).
HIPS (b): The rubber particles are mainly composed of a salami structure, and the rubber particles have an average particle size of 0.9 to 4 μm.
Here, “mainly” means that 80% or more, preferably 90% or more, more preferably 95% or more of the rubber particles have a salami structure (multiple cell structure).

Hereinafter, each component of the resin composition will be described in detail.
((A) polyphenylene ether)
(A) The polyphenylene ether is a homopolymer or a copolymer that is a repeating structure unit represented by the following formula (III) and / or (IV).

  In formulas (III) and (IV), R1, R2, R3, R4, R5, and R6 are each independently hydrogen, halogen, an alkyl group having 1 to 4 carbon atoms, or aryl having 6 to 12 carbon atoms. Any one selected from the group consisting of groups.

Examples of the homopolymer of polyphenylene ether include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, and 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, and poly (2-methyl-6-chloroethyl-1,4-pheny) Down) ether, and the like.
Poly (2,6-dimethyl-1,4-phenylene) ether is preferred from the viewpoint of availability and price.

  In the polyphenylene ether homopolymer here, some of the structural units in the repeating unit structure are 2- (dialkylaminomethyl) -6-methylphenylene ether structural unit and / or 2- (N-alkyl-N). Those having a structure substituted with a structural unit of -phenylaminomethyl) -6-methylphenylene ether are also included.

  When polyphenylene ether is melt-kneaded, the molecular weight of polyphenylene ether changes due to heat, but from the viewpoint of facilitating stable adjustment to the desired molecular weight without excessively increasing or decreasing the molecular weight. , Some structural units of poly (2,6-dimethyl-1,4-phenylene) ether are 2- (dialkylaminomethyl) -6-methylphenylene ether structural units and / or 2- (N-alkyl-N Copolymers substituted with -phenylaminomethyl) -6-methylphenylene ether structural units are preferred.

  On the other hand, a copolymer of polyphenylene ether is a copolymer having a phenylene ether structure as a main structural unit, and the copolymer is a structural unit represented by the above formula (III) and / or (IV). Can be used.

  Specific examples of the copolymer of polyphenylene ether include, but are not limited to, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and o-cresol, And a (ternary) copolymer of 2,6-dimethylphenol, 2,3,6-trimethylphenol and o-cresol.

From a practical viewpoint, the reduced viscosity (ηsp / c) measured with a chloroform solution at 30 ° C. is preferably 0.3 to 0.7, more preferably 0.4 to 0.6, and [weight The ratio of (average molecular weight / number average molecular weight) is preferably 1.8 to 5.0, more preferably 2.2 to 3.5, poly (2,6-dimethyl-1,4-phenylene) ) Ether can be suitably used.
The polyphenylene ether having such physical properties and characteristics is suitable from the viewpoint of the balance between the molding fluidity (ease of molding) of the resin composition and mechanical properties such as impact resistance and chemical resistance.
In addition, the weight average molecular weight and the number average molecular weight in this specification are values calculated on the basis of the molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

Furthermore, in the present embodiment, as the (A) polyphenylene ether resin, a modified polyphenylene ether obtained by modifying a part or all of the polyphenylene ether with an unsaturated carboxylic acid or a derivative thereof can also be used.
Such modified polyphenylene ethers are described in JP-A-2-276823, JP-A-63-108059, JP-A-59-59724, etc., for example, in the presence or absence of a radical initiator. Under the condition, an unsaturated carboxylic acid or a derivative thereof is melt-kneaded with polyphenylene ether, and these are reacted.
The modified polyphenylene ether can also be obtained by dissolving polyphenylene ether and an unsaturated carboxylic acid or derivative thereof in an organic solvent in the presence or absence of a radical initiator and reacting in such a solution.

Examples of unsaturated carboxylic acids or derivatives thereof that modify polyphenylene ether include maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid and endo-cis-bicyclo ( 2,2,1) -5-heptene-2,3-dicarboxylic acid, ester compounds and amide compounds of these monocarboxylic acids, and acid anhydrides, ester compounds, amide compounds and imide compounds of these dicarboxylic acids And acrylic acid and methacrylic acid.
Moreover, although it is saturated carboxylic acid, the compound which itself can thermally decompose at the reaction temperature at the time of manufacturing modified polyphenylene ether, and can become unsaturated carboxylic acid and its derivative (s) can also be used. Examples of such compounds include, but are not limited to, malic acid and citric acid.
Said polyphenylene ether resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of (A) polyphenylene ether is 10 to 90 when the total of (A) polyphenylene ether, (B) rubber-modified polystyrene and homopolystyrene described later, and (C) flame retardant described later is 100 parts by mass. It is a mass part, Preferably it is 20-80 mass parts, More preferably, it is 30-60 mass parts.

((B) rubber-modified polystyrene and homopolystyrene)
The rubber-modified polystyrene in the component (B) is a polymer obtained by polymerizing a styrene compound and a compound copolymerizable with the styrene compound in the presence of a rubbery polymer.
Examples of the styrenic compound include, but are not limited to, styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, and ethylstyrene. Of these, styrene is preferred.
The compounds copolymerizable with the styrene compound are not limited to the following, but include, for example, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; An acid anhydride such as an acid may be mentioned.
The amount of the compound copolymerizable with the styrene compound is preferably 20% by mass or less, more preferably 15% by mass or less, based on the total amount with the styrene compound.

Examples of the rubbery polymer include, but are not limited to, conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, and ethylene-propylene copolymer rubbers.
Examples thereof include polybutadiene, styrene-butadiene random copolymer, and styrene-butadiene block copolymer, and rubber components obtained by partially or almost completely hydrogenating them.

The rubber-modified polystyrene is high impact polystyrene (HIPS), and a styrene-butadiene block copolymer is suitable as the rubbery polymer constituting the HIPS.
As the form of rubber particles of the rubbery polymer constituting the HIPS, there are two types, a salami structure (multiple cell structure) and a polystyrene core (single cell structure).

The “salami structure” means that rubber particles (salami sausage cross-sectional shape) are dispersed in a polystyrene matrix, and a plurality of polystyrene particles are embedded in a honeycomb shape in the rubber particle phase having a thin outer layer. Structure.
The “polystyrene core” is a core-shell structure in which rubber particles having a single cell structure are dispersed in a polystyrene matrix.
The rubber-modified polystyrene can be produced by a bulk polymerization method or a bulk suspension polymerization method, and the rubber particle form can be controlled by controlling the stirring state in the polymerization step, the mixing state at the time of rubber particle production, and the like.
The form of the rubber particles can be observed by using a transmission electron micrograph of a sample prepared by staining an ultrathin section well known to those skilled in the art with an osmium tetroxide aqueous solution.
FIG. 1 shows a photograph of rubber particles taken at a magnification of 10000 with a transmission electron microscope. The rubber particle form of a salami structure (multiple cell structure) and a polystyrene core (single cell structure) in the resin composition. An example of The lower scale in FIG. 1 indicates 1 μm.

The form of the rubber particles of HIPS used in this embodiment is a mixture composed of HIPS (a) which is a polystyrene core and HIPS (b) which is a salami structure.
The mass ratio of HIPS (a) / HIPS (b) is 98/2 to 70/30, preferably 96/4 to 80/20, and more preferably 94/6 to 85/15.
The resin composition of the present embodiment is excellent in colorability and surface characteristics due to the above combined range.
In addition, the above two types of HIPS (a) and HIPS (b) are used in combination by making two types of HIPS separately and blending them with an extruder or the like when melt-kneading the resin composition, or by polymerizing the HIPS. Or by mixing with a machine.
The colorability of the resin composition can be evaluated by color, and the surface characteristics can be evaluated by the presence or absence of whitening, cloudiness, and flow marks.

HIPS (a): The rubber particles have a form of 90% or more, preferably 95% or more of the rubber particles composed of one polystyrene core (single cell structure), and an average particle size of 0.1 to 0.5 μm. The thickness is preferably 0.2 to 0.4 μm. The rubber content in 100 mass% of HIPS (a) is preferably 3 to 20 mass%. By controlling the form of the rubber particles within the above range, the resin composition of the present embodiment has excellent colorability and surface characteristics.
HIPS (b): The form of the rubber particles is 80% or more, preferably 90% or more, more preferably 95% or more of the rubber particles having a salami structure (multi-cell structure), and an average particle size of 0.9 to 4 0.0 μm, preferably 1.2 to 2 μm.
The rubber content in 100 mass% of HIPS (b) is preferably 3 to 20 mass%. The average particle size of the rubber particles of HIPS can be measured using a laser particle size meter.
The average particle diameter of the rubber particles of HIPS can be measured using a conventionally known laser diffraction / scattering particle size distribution measuring apparatus, and is measured based on the volume-based particle diameter.
Further, a 3% by mass methyl ethyl ketone solution of rubber-modified polystyrene can be used.

Moreover, the resin composition excellent in coloring property and surface characteristics can be obtained by controlling not only the form of the rubber particles in the resin composition but also the rubber content.
The rubber content is preferably 1 to 15% by mass and more preferably 4 to 10% by mass in 100% by mass of the total amount of (B) rubber-modified polystyrene and homopolystyrene.
The rubber content can be controlled by adjusting the rubber content of (B) rubber-modified polystyrene and adjusting the ratio of rubber-modified polystyrene and homopolystyrene.
Specifically, the rubber content is controlled by diluting the rubber in the rubber-modified polystyrene with homopolystyrene.
For example, when the rubber content in rubber-modified polystyrene (HIPS) is 15% by mass, the total rubber content can be 7.5% by mass by blending at a ratio of rubber-modified polystyrene / homopolystyrene = 50/50. , 30/70 ratio, the total rubber content can be 4.5% by mass.
That is, when HIPS having a rubber content of 15% by mass is used as the rubber-modified polystyrene in the component (B), the rubber content is 1 to 15 in the total amount of 100% by mass of the (B) rubber-modified polystyrene and homopolystyrene. In order to obtain a mass%, HIPS / homopolystyrene = 7/93 to 100/0 may be blended. In order to obtain a rubber content of 4 to 10% by mass, HIPS / homopolystyrene = 27/73. What is necessary is just to mix | blend by the ratio of -67/23.
In addition, what is necessary is just to adjust suitably content of homopolystyrene according to the rubber content in the objective rubber | gum content and the rubber modified polystyrene (HIPS) to be used, and content may be 0 as mentioned above.

  By controlling the above-mentioned rubber particle morphology and rubber content within the above ranges, the resulting resin composition has excellent colorability and surface characteristics with little color unevenness and flow marks, and further self-tapping. Because of its excellent properties and surface hardness, it is more useful for decorative applications. Color unevenness can be evaluated by a color anisotropy test described later.

  The content of the (B) rubber-modified polystyrene and homopolystyrene is 90 to 90 when the total of (A) polyphenylene ether resin, (B) rubber-modified polystyrene and homopolystyrene, and (C) the flame retardant is 100 parts by mass. 10 parts by mass, preferably 80 to 20 parts by mass, more preferably 60 to 30 parts by mass.

  As described above, when the total of (A) polyphenylene ether resin, (B) rubber-modified polystyrene and homopolystyrene, and (C) flame retardant is 100 parts by mass, the content of (A) polyphenylene ether resin is 10 to 90 parts by mass, preferably 20 to 80 parts by mass, and more preferably 30 to 60 parts by mass.

  The ratio of (A) polyphenylene ether resin to (B) rubber-modified polystyrene and homopolystyrene takes into account the heat resistance and flame retardancy of the target resin composition, and the like. In order to improve the balance, it is preferable to relatively increase the content of (A) polyphenylene ether resin, and in order to obtain excellent molding fluidity, the content of (B) rubber-modified polystyrene and homopolystyrene is reduced. A relatively large amount is preferable, and these contents may be appropriately set according to required characteristics.

((C) Phosphorus flame retardant)
Although it does not restrict | limit as (C) phosphorus flame retardant which comprises the resin composition of this embodiment below, For example, the following organic phosphate ester compound is mentioned.
Examples of the organic phosphate compound include triphenyl phosphate, phenyl bisdodecyl phosphate, phenyl bisneopentyl phosphate, phenyl bis (3,5,5′-trimethyl-hexyl phosphate), ethyl diphenyl phosphate, 2-ethylhexyl di ( p-tolyl) phosphate, bis- (2-ethylhexyl) p-tolyl phosphate, tolyl phosphate, bis- (2-ethylhexyl) phenyl phosphate, tri- (nonylphenyl) phosphate, di (dodecyl) p-tolyl phosphate, tri Cresyl phosphate, dibutylphenyl phosphate, 2-chloroethyldiphenyl phosphate, p-tolylbis (2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphe Ruphosphate, bisphenol A bis (diphenyl phosphate), diphenyl- (3-hydroxyphenyl) phosphate, bisphenol A bis (dicresyl phosphate), resorcin bis (diphenyl phosphate), resorcin bis (dixylenyl phosphate), (Aromatic) condensed phosphorus from 2-naphthyl diphenyl phosphate, 1-naphthyl diphenyl phosphate and di (2-naphthyl) phenyl, and phenols such as phosphate tresorcinol and bisphenol A (bifunctional phenol, polyfunctional phenol, etc.) An acid ester compound is mentioned.
These may be used alone or in combination of two or more.

  Among the above-mentioned (C) phosphorus-based flame retardants, from the viewpoint of excellent heat resistance and capable of significantly suppressing fuming during injection molding and adhesion of the flame retardant to the mold, preferably an aromatic condensed phosphate ester compound, More preferably, it is an aromatic condensed phosphate compound containing as a main component an (aromatic) condensed phosphate compound represented by the following formula (I) or formula (II). In this case, the “main component” means 50% by mass or more.

  In the above formulas (I) and (II), Q1, Q2, Q3 and Q4 represent hydrogen or an alkyl group having 1 to 6 carbon atoms, R1, R2, R3 and R4 represent hydrogen or a methyl group, and n is 1 N1 and n2 are integers of 0 to 2, and m1, m2, m3, and m4 are integers of 1 to 3.

  (C) As a phosphorus flame retardant, you may use a commercial item, but it is not restrict | limited to the following, For example, Daihachi Chemical Co., Ltd. brand name CR-741, CR-747, CR733S, PX-200 Is mentioned.

Among the above formulas (I) and (II), the condensed phosphoric acid ester represented by the above formula (I) is effective in generating black foreign matters due to decomposition and dehydration reaction in melt kneading in the resin composition production process. This is preferable because the water absorption of the resin composition can be reduced.
In addition, the condensed phosphate ester represented by the above formula (I) is preferable from this viewpoint because the resin composition obtained has excellent surface hardness and self-tapping characteristics.

  More preferably, Q1, Q2, Q3 and Q4 in the formula (I) are hydrogen or a methyl group, R1 and R2 are hydrogen, R3 and R4 are methyl groups, and n is 1 to 3 (particularly 1) Condensed phosphoric acid ester 1) is contained in an amount of 50% by mass or more when the condensed phosphoric acid ester contained in the resin composition is 100% by mass.

The acid value of the condensed phosphate ester compound is preferably less than 0.1.
Here, the acid value is a value represented by the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the sample in accordance with JIS K2501.
When the acid value of the condensed phosphate ester compound is within the above range, the mold is less likely to be corroded during molding of the target resin composition, and the condensed phosphate ester compound generates gas during processing due to easy decomposability. It can suppress significantly and can improve the electrical property of a resin composition further.

  (C) A phosphorus flame retardant may be used individually by 1 type among the various compounds mentioned above, and may use 2 or more types together.

Moreover, (C) phosphorus flame retardant is added according to the required flame retardance level, and the total amount of the above (A) component and (B) component and (C) flame retardant is 100 parts by mass. When it is 0-40 mass parts, Preferably it is 3-35 mass parts, More preferably, it is 5-30 mass parts.
(C) A flame retardant effect is acquired by adding 3 mass parts or more of phosphorus type flame retardants with respect to 100 mass parts of (A) + (B) + (C).
On the other hand, the mechanical strength and heat resistance of the resin composition can be suppressed to a practically sufficient level by setting it to 40 parts by mass or less, and the mechanical strength of the resin composition can be reduced to 35 parts by mass or less. The decrease in heat resistance can be suppressed to a more practical level.
In addition, in order to sufficiently exhibit the above-described advantageous effects, (C) a phosphorus-based flame retardant containing 3 to 35 parts by mass of a condensed phosphate ester represented by the above formula (I) or (II) as a main component Thus, it is preferable to produce the target resin composition.

((D) mold release agent)
(D) Examples of the mold release agent include metal salts of higher fatty acids, higher fatty acid amides and / or bisamides, higher fatty acid esters, paraffin wax, and polyolefin.
The metal salt of a higher fatty acid is a salt of a higher fatty acid and a metal hydroxide. For example, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate and the like are preferably used.
Higher fatty acid amides and / or bisamides are monoamides, bisamides, and the like of higher fatty acids, and for example, stearic acid amide, oleic acid amide, ethylene bisstearic acid amide and the like are preferable.

  The higher fatty acid ester is a higher fatty acid ester comprising a higher fatty acid and a monohydric alcohol having 1 to 20 carbon atoms, a dihydric alcohol, and a trihydric or higher polyhydric alcohol, such as methyl laurate, methyl myristate, and palmitic acid. Methyl acetate, methyl stearate, methyl oleate, methyl behenate, methyl montanate, isopropyl myristate, isopropyl palmitate, butyl laurate, butyl stearate, octyl palmitate, octyl stearate, lauryl laurate, stearyl stearate , Ethylene glycol dilaurate, ethylene glycol dipalmitate, ethylene glycol distearate, ethylene glycol dimontanate, propylene glycol monolaurate, propylene glycol monostearate 1,3-propanediol dilaurate, 1,3-propanediol distearate, 1,3-propanediol dimontanate, 1,4-butanediol dilaurate, 1,4-butanediol distearate, 1,4 -Butanediol dimontanate, glycerin monopalmitate, glycerin monostearate, glycerin monopartanate, glycerin dipalmitate, glycerin distearate, glycerin dioleate, glycerin tristearate, glycerin trioleate, pentaerythritol monopalmiate Tate, pentaerythritol monostearate, pentaerythritol dipalmitate, pentaerythritol distearate, pentaerythritol tripalmitate, pentaerythritol tristearate DOO, pentaerythritol tetrastearate, and the like.

  Examples of the higher fatty acid include stearic acid, behenic acid, lauric acid, palmitic acid, myristic acid, capric acid, oleic acid, behenic acid, montanic acid, coconut oil fatty acid, palm oil fatty acid, and beef tallow fatty acid. Higher fatty acids having 4 to 30 carbon atoms.

  Paraffin wax is a wax having 20 to 48 carbon atoms which is solid at normal temperature mainly composed of a linear saturated hydrocarbon, contains n-paraffin as a main component, and contains a small amount of i-paraffin and naphthene. It is. These can use what is generally marketed.

Polyolefin is ethylene homopolymer (homopolymer) or copolymer (copolymer).
The polyolefin-based resin that can be used in the present embodiment is not limited to the following. For example, low-density polyethylene, linear low-density polyethylene, high-density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, and Ethylene-α-olefin copolymers such as ethylene-octene copolymer, and ethylene- (meta) such as ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, and ethylene-ethyl acrylate-methyl methacrylate copolymer. ) Acrylic acid ester copolymer.

  From the viewpoint of ensuring good moldability, higher fatty acid metal salts and higher fatty acid amides and / or bisamides are preferred, and zinc stearate, calcium stearate, magnesium stearate, calcium montanate, and ethylene bis stearamide are particularly preferred. .

Content of (D) mold release agent in the resin composition of this embodiment is 0.05-1 when the sum total of (A) component + (B) component + (C) component mentioned above is 100 mass parts. 0.0 part by mass.
(D) When the content of the release agent is less than 0.05 parts by mass, the effect of improving the appearance cannot be sufficiently obtained. When the content exceeds 1.0 parts by mass, (D) the release agent is poorly dispersed. Cause bleed-out and lower heat-resistant temperature.

((E) Pigment colorant)
The resin composition of the present embodiment contains (E) a pigment-based colorant.
(E) As the pigment-based colorant, a pigment-based colorant such as carbon black can be used, and a desired color can be obtained by various combinations, and an inorganic pigment and an organic pigment may be used in combination.
In addition, 0.1 parts by mass or more of (E) pigment-based colorant is contained with respect to 100 parts by mass in total of (A) polyphenylene ether, (B) rubber-modified polystyrene and homopolystyrene, and (C) phosphorus-based flame retardant ( Preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more (addition), more preferably 0.5 parts by mass or more (addition). Even more preferred.
(E) By making content (addition amount) of a pigment-type colorant into 0.1 mass part or more, the resin composition excellent in coloring property is obtained.
On the other hand, the upper limit of the content (addition amount) is preferably 5 parts by mass, more preferably 3 parts by mass, from the viewpoint of the effect on the economy and composition characteristics, and it is more preferably about 1 part by mass. Is more preferable.
In addition, by using a dye in combination with the above-described (E) pigment-based colorant, a polyphenylene ether-based resin composition having excellent colorability, less color unevenness in the welded portion, and less appearance defect due to MD (mold deposit) can be obtained. Therefore, it is preferable.

((F) Hydrogenated block copolymer)
The resin composition of this embodiment may further contain (F) a hydrogenated block copolymer.
A hydrogenated block copolymer is a copolymer obtained by hydrogenating a block copolymer of a vinyl aromatic monomer and a conjugated diene monomer.
For example, a block copolymer obtained by hydrogenating a polymer block of vinyl aromatic monomer units and a polymer block of conjugated diene monomer units, containing no or almost no random copolymer portion. And hydrogenated block copolymers obtained by hydrogenating the above.
As commercial products, Clayton G (trade name) manufactured by Clayton Polymer Co., Ltd., Tuftec (trade name) manufactured by Asahi Kasei Co., Ltd., and Septon (trade name) manufactured by Kuraray are known.

  Other random hydrogenated block copolymers include, for example, hydrogenated hydrogenated random copolymer blocks consisting of conjugated diene monomer units and vinyl aromatic monomer units (non-hydrogenated). A copolymer is mentioned. As a commercial product, SOE (trade name) of Asahi Kasei Corporation is known.

(F) It is preferable that a hydrogenated block copolymer contains 40 mass% or more of vinyl aromatic monomer units from a viewpoint of improving compatibility with PPE and a styrene-type resin, More preferably, 50- 85 mass%, More preferably, it contains 55-80 mass%.
That is, (F) hydrogenated block copolymer is a water having 40% by mass or more of polymer blocks composed of vinyl aromatic monomer units and 60% by mass or less of polymer blocks containing conjugated diene monomer units. A block copolymer is preferred.
By making the polymer block content of the vinyl aromatic monomer unit within the above range, the resin composition of the present embodiment has more excellent appearance characteristics, mechanical strength and molding processability. The balance will be even better.
From the viewpoint of ensuring better colorability and molding processability, the vinyl aromatic monomer unit component is preferably 60 to 80% by mass with respect to the block copolymer.

The weight average molecular weight of the hydrogenated block copolymer is preferably 30,000 to 1,000,000.
Thereby, the resin composition of the present embodiment has a good balance between mechanical strength and moldability.
In the resin composition of the present embodiment, the weight average molecular weight of the hydrogenated block copolymer is from the viewpoint of ensuring higher mechanical strength and further improving the balance between impact absorption and molding processability. 40,000 to 500,000 are preferable, 50,000 to 300,000 are more preferable, and 70,000 to 200,000 are more preferable.
The weight average molecular weight can be measured by gel permeation chromatography (GPC method).
Further, the hydrogenated block copolymer exhibits a more excellent effect when used in combination with the polyolefin resin which is the above-mentioned (D) release agent.

The resin composition of the present embodiment is a predetermined additive within a range that does not impair the desired effect of the present embodiment, but is not limited to the following, for example, a stabilizer such as a plasticizer, an antioxidant, an ultraviolet absorber, You may contain an antistatic agent, a mold release agent, a lubricant, and other resin.
Further, by adding various known flame retardants and flame retardant aids, for example, a tetrafluoroethylene homopolymer (polytetrafluoroethylene), a copolymer containing tetrafluoroethylene, silicone oil and silicone resin, it becomes more difficult. Flammability can be improved.

[Method for producing resin composition]
Although it does not specifically limit about the method of manufacturing the resin composition of this embodiment, Generally, it can manufacture by melt-kneading using an extruder.
In particular, a method using a twin screw extruder capable of adding raw material components during the production process is preferable from the viewpoint of securing high productivity and obtaining a good resin composition.
The kneading temperature may be in accordance with the preferred processing temperatures of (A) and (B) to be the base resin, and is generally in the range of 240 to 360 ° C, preferably in the range of 260 to 320 ° C.
In the resin composition of this embodiment, all the components may be melt-kneaded all together, but the above-mentioned (A) and (B) or the above-mentioned (A), (B) and (C) are previously melt-kneaded. In addition, other components may be added in a later step.
A pellet-shaped intermediate composition that has been melt-kneaded in advance may be obtained, and the resin composition may be produced in two stages in which the other components are added using another kneading apparatus in the next step.

[Molded product using resin composition]
The resin composition of the present embodiment can be processed into a molded product by a general molding method such as an injection molding method or an extrusion molding method.
In particular, the temperature of the mold surface is raised above the vicinity of the heat deformation temperature of the injection resin, and is kept above the heat deformation temperature between the resin injection and the pressure holding process. The heat cycle molding method, in which the temperature is lowered, the resin is cooled, and the molded product is taken out, is excellent as a method for obtaining a molded product in which the weld line is not noticeable and the appearance characteristics are good.

A conventionally known polyphenylene ether resin composition has a noticeable weld line even when a molded product is obtained by a heat cycle molding method, and color unevenness occurs at the weld portion, so that practically sufficient appearance characteristics can be obtained. In addition, it has a drawback that the value as a product is lowered.
Since the molded body according to this embodiment is molded using the above-described resin composition, appearance characteristics (colorability, surface characteristics, etc.) that cannot be said to be sufficient in conventional resin compositions. , Practical level releasability (such as deposits on the mold during injection molding), molding processability and flame retardancy are excellent.
Furthermore, since it is possible to remarkably prevent fogging, whitening and flow marks on the surface of the molded body during molding, a desired molded body can be obtained.
As a result, the molded article according to the present embodiment can be suitably used even in applications (for example, TV exterior bodies) in which decorativeness and appearance characteristics with high glossiness are particularly required.

  Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.

[Components constituting the resin compositions of Examples and Comparative Examples]
(A) Polyphenylene ether (PPE)
Poly-2,6-dimethyl-1,4-phenylene ether (manufactured by Asahi Kasei Plastics Singapore, Zyron S201A).

(B) Rubber-modified polystyrene (HIPS) and homopolystyrene (GPPS)
<HIPS (a)>
(A-1): The rubber particles are composed of one polystyrene core (single cell structure) with 95% or more of the rubber particles, the rubber particles have an average particle diameter of 0.3 μm, and the rubber content is a styrene-butadiene block. 15% by mass of copolymer
(A-2): The rubber particles are composed of one polystyrene core (single cell structure) with 95% or more of the rubber particles, the average particle diameter of the rubber particles is 0.6 μm, and the rubber content is a styrene-butadiene block. 15% by mass of copolymer
<HIPS (b)>
(B-1): 90% or more of the rubber particles have a salami structure (multiple cell structure), the rubber particles have an average particle diameter of 1.5 μm, and the rubber content is 12% by mass of polybutadiene.
(B-2): 90% or more of the rubber particles have a salami structure (multiple cell structure), the rubber particles have an average particle diameter of 0.7 μm, and the rubber content is 12% by mass of polybutadiene.
(B-3): 90% or more of the rubber particles have a salami structure (multiple cell structure), the rubber particles have an average particle diameter of 1.0 μm, and the rubber content is 12% by mass of polybutadiene.
(B-4): 90% or more of the rubber particles have a salami structure (multiple cell structure), the rubber particles have an average particle diameter of 3.4 μm, and the rubber content is 12% by mass of polybutadiene.
<GPPS>
Homopolystyrene (PSJ polystyrene 680, manufactured by PS Japan) was used.
The average particle size of the rubber particles was measured using a laser diffraction / scattering particle size distribution measuring device “LA-910 (manufactured by Horiba, Ltd.)”.

(C) Phosphorus flame retardant (C-1: BDP in Table 1): Condensed phosphate ester (CR-741, large, acid value = 0.05 based on bisdiphenyl phosphate (BDP) of bisphenol A Hachi Chemical Co., Ltd.) was used.
(C-2: TPP in Table 1): Triphenyl phosphate (TPP, manufactured by Daihachi Chemical Co., Ltd.) was used.

(D) Mold release agent (D-1) Zinc stearate (Daiwa Chemical Industry Co., Ltd. Die Wax Z)
(D-2) Magnesium stearate (Daiwa Chemical Industry Co., Ltd. Die Wax M)
(D-3) EBS (Kao Corporation Kao Wax EB / FF)
(D-4) LD-PE (Suntech (registered trademark) M2004 of Asahi Kasei Chemicals Corporation)
(D-5): Ethylene-propylene copolymer (Tafmer (registered trademark) P-0680 manufactured by Mitsui Chemicals, Inc.)

(E) Pigment-based colorant (E-1) Carbon black (Mitsubishi Chemical Corporation, Mitsubishi Carbon Black # 960)
(E-2) Organic dye A red dye, a yellow dye, a green dye, and a purple dye were used in combination at the ratio shown below.
Red dye: SOLVENT RED 179 0.1 part by weight Yellow dye: DISPERSE YELLOW 160 0.1 part by weight Green dye: SOLVENT GREEN 3 0.15 part by weight Purple dye: SOLVENT VIOLET 13 0.65 part by weight

(F) Hydrogenated block copolymer (SEBS)
A hydrogenated block copolymer of a styrene / butadiene block copolymer (Clayton Polymer Co., Ltd., Clayton (registered trademark) G1651) was used.

[Evaluation method of resin composition]
((1) Whitening and cloudiness)
Using a two-point pin-gate flat plate mold with a weld line at the center of a 150 mm × 150 mm × 2 mm flat plate with specular gloss, the flat plate is injection molded under the conditions of a heating cylinder temperature of 240 ° C. and a mold temperature of 60 ° C. It was prepared and visually evaluated for whitening and fogging of the vicinity of the gate and other flat plates.
<Whitening> O (good) that does not cause appearance defects that whiten on the flat plate surface, O to Δ that occurs in 1 to 2 places, Δ (ordinary) that occurs in 3 to 7 places, 8 to 15 What occurred in several places was evaluated in five stages: Δ to x, and those in 15 or more places x (bad).
<Haze> O (Good) if the surface of the flat plate is almost inconspicuous, ○ ~ △ is slightly noticeable, △ (normal) is slightly noticeable, △ ~ x is slightly noticeable, x is clearly noticeable Evaluation was made on a five-point scale.

((2) Color anisotropy)
Using a two-point pin-gate flat plate mold with a weld line at the center of a 150 mm × 150 mm × 2 mm flat plate with specular gloss, the flat plate is injection molded under the conditions of a heating cylinder temperature of 240 ° C. and a mold temperature of 60 ° C. The color of the weld line was determined visually.
Anisotropy can not be confirmed ○ (good), slightly noticeable ○ ~ △, slightly noticeable △ (normal), slightly noticeable △ ~ ×, clearly noticeable × (bad) evaluated.

((3) Self-tapping strength)
A molded body with a boss with a thickness of 3 mm and an inner diameter of 3.6 mmφ is injection-molded on a 150 mm × 150 mm × 3 mm flat plate, and a 4 mmφ tapping screw is tightened in the boss opening. Torque in increments of 1 kg · cm from 15 kg · cm Was repeatedly tightened and expressed as torque (kg · cm) when the tapping portion collapsed and idled.
A self-tapping strength of about 30 was judged to be practically sufficient.

((4) Deposits on mold surface (mold deposit; MD))
A mold for producing a flat plate of 50 mm × 90 mm × 2.5 mm having a specular gloss is used, and the mold for producing the flat plate is full under the conditions of a heating cylinder temperature of 260 ° C. and a mold temperature of 60 ° C. After producing 30 sheets under the condition of shorting 10 to 20 mm without filling, the state of specular gloss of the mold was visually evaluated.
The evaluation was made in three stages, with ○ (good) indicating that the deposits were hardly conspicuous on the mirror surface of the short-circuited part, Δ (normal) being slightly conspicuous, and x (bad) being clearly conspicuous.

((5) Flame resistance)
Based on the UL-94 vertical combustion test, measurement was performed using a 1.6 mm-thickness injection-molded test piece, and the total combustion time at the 10th flame contact and the presence or absence of dripping at the time of combustion were evaluated.
V-0: An average burning time of 5 seconds or less, a maximum burning time of 10 seconds or less, and no flaming dripping.
V-1: An average burning time of 25 seconds or less, a maximum burning time of 30 seconds or less, and no flaming dripping.
V-2: An average combustion time of 25 seconds or less, a maximum combustion time of 30 seconds or less, and there is a flaming dripping.
HB: Those not corresponding to the above three items and those that burned up to the clamp holding the test piece.
The average burning time (seconds) is the average burning time of two samples, that is, the extinguishing time after 10 times of flame contact. It represents the burning time of the test piece that continued to burn for the longest time.

((6) HDT (flatwise (° C)))
Based on ISO-75-2, measurement was performed under 1.80 Pa.

[Examples 1 to 12], [Comparative Examples 1 to 10]
Materials were blended in the proportions (parts by mass) shown in Table 1 below, and melt mixing was performed using a co-rotating twin-screw extruder combined with a kneading disk having a screw diameter of 40 mm to prepare a resin composition.
A part of polyphenylene ether (PPE), homopolystyrene (GPPS) or HIPS and 0.2 parts by mass of tris (2,4-di-t-butylphenyl) phosphite as a stabilizer are introduced from the upstream inlet of the extruder. Then, HIPS, a colorant, and a release agent were pre-blended and side-fed from the middle inlet of the extruder, and a flame retardant was injected and added from the downstream of the extruder.
The operating conditions of the extruder were as follows: the upstream temperature of the heating cylinder was 300 ° C., the downstream temperature was 270 ° C., the screw rotation speed was 400 rpm, melt kneading while vacuum devolatilizing from the vent port, the strand was cooled and cut, and the resin composition Pellets were obtained.
Next, physical property test pieces for evaluation were molded by injection molding under the conditions of a maximum set temperature of 220 ° C. and a mold temperature of 60 ° C. by using the obtained resin composition pellets.
Evaluation was performed by the test methods (1) to (6) described above.
The evaluation results are shown in Table 1 below.

  As shown in Table 1, each of Examples 1 to 12 had good appearance characteristics, practically sufficient mechanical strength, and good flame retardancy, heat resistance, and moldability. It was.

  The resin composition of the present invention and a molded article using the resin composition are industrially used for applications requiring appearance such as televisions, videos, exterior molded articles for office machines, PCs, printers, copying machines, game machines, telephones, adapters, etc. With the availability of

Claims (9)

When the total of the following (A) + (B) + (C) is 100 parts by mass,
(A) 10 to 90 parts by mass of polyphenylene ether,
(B) 90 to 10 parts by mass of rubber-modified polystyrene and homopolystyrene,
(C) 0 to 40 parts by mass of a phosphorus compound as a flame retardant,
(D) 0.05 to 1.0 parts by weight of release agent,
(E) containing a pigment-based colorant,
The rubber-modified polystyrene is composed of HIPS (a) and HIPS (b), which are high-impact polystyrene containing rubber particles, and the weight ratio of HIPS (a) / HIPS (b) is 98/2 to 70/30. ,
HIPS (a) includes those in which the rubber particles have a single polystyrene core (single cell structure), and the rubber particles have an average particle size of 0.1 to 0.5 μm,
HIPS (b) includes the rubber particles having a salami structure (multi-cell structure), and the rubber particles have an average particle diameter of 0.9 to 4 μm.
Resin composition. For a total of 100 parts by mass of (A) + (B) + (C),
The resin composition according to claim 1, containing 0.05 to 0.8 part by mass of (D).   The resin composition according to claim 1 or 2, wherein the (D) release agent contains one or more selected from the group consisting of metal salts of higher fatty acids, higher fatty acid amides and / or bisamides, higher fatty acid esters, and paraffin wax. object.   The resin composition according to any one of claims 1 to 3, wherein the (D) release agent contains a metal salt of a higher fatty acid. For a total of 100 parts by mass of (A) + (B) + (C),
The resin composition as described in any one of Claims 1 thru | or 4 which contains the said (E) pigment-type colorant 0.1-5 mass parts. The flame retardant (C) is
Formula (I) below
Or the following formula (II)
Containing a condensed phosphate ester represented by
The said (C) flame retardant is contained in any one of Claims 1 thru | or 5 with respect to a total of 100 mass parts of said (A) + said (B) + said (C). The resin composition as described.
(In the formula, Q1, Q2, Q3 and Q4 represent hydrogen or an alkyl group having 1 to 6 carbon atoms, R1, R2, R3 and R4 represent hydrogen or a methyl group. N represents an integer of 1 or more. n1, n2 represents an integer of 0-2, and m1, m2, m3, m4 represents an integer of 1-3.) The flame retardant (C) is represented by the following formula (I)
Containing a condensed phosphate ester represented by
The said (C) flame retardant is contained in any one of Claims 1 thru | or 6 with respect to a total of 100 mass parts of said (A) + said (B) + said (C). The resin composition as described.
(In the formula, Q1, Q2, Q3 and Q4 represent hydrogen or an alkyl group having 1 to 6 carbon atoms, R1, R2, R3 and R4 represent hydrogen or a methyl group. N represents an integer of 1 or more. n1, n2 represents an integer of 0-2, and m1, m2, m3, m4 represents an integer of 1-3.)   The molded object using the resin composition as described in any one of Claims 1 thru | or 7.   The molded article according to claim 8, which is an outer molded article for a television, a video, or an office machine.