KR20110077473A - Flameproof thermoplastic resin composition - Google Patents

Abstract

PURPOSE: An environment-friendly flame retardant thermoplastic resin composition is provided to ensure excellent flame retardancy and to solve problems on gate mark generated in the direct gate type injection. CONSTITUTION: An environment-friendly flame retardant thermoplastic resin composition comprises 100 parts by weight of base resins, 5 ~30 parts by weight of aromatic phosphoric ester compounds, and 0.1~20 parts by weight of aluminum silicate compounds, wherein the base resin comprises 5~40 weight% of rubber-modified copolymer resins, 30~90 weight% of polycarbonate resins, and 1~50 weight% of polyethylene terephthalate resins.

Description

Flameproof Thermoplastic Resin Composition

The present invention relates to a flame retardant thermoplastic resin composition, and more particularly, (A) rubber-modified styrene copolymer resin, (B) polycarbonate resin 30 to 90% by weight and (C) having excellent flame retardancy and processability without containing halogen ) Thermoplastic resin composition of alloy resin of polyethylene terephthalate resin.

In general, rubber-modified styrene-based copolymer resins are used in electrical and electronic products because of their good workability, excellent impact strength, and excellent appearance, and have been manufactured by applying flame retardant resins, especially for devices that emit heat.

Known flame retardant methods most commonly applied to rubber-modified styrenic copolymer resins are a combination of a halogen compound and an antimony compound. However, since the mid-'80s, especially in Europe, the halogen-based flame retardant of polybrominated diphenyl ether structure has been highlighted, and more attention has been paid to the flame-retardant composition of the rubber-modified styrene copolymer resin containing no halogen.

Flame retardants that can replace halogen usually contains phosphorus, silicon, boron or nitrogen, but the above compounds alone have limited flame retardant efficiency for styrene-based copolymer resins, and thus their application is limited.

According to the journal Polymer (published by Elsevier Science, 1975, vol. 16, pp. 615-620), rubber-modified styrenic copolymer resins have no correlation with so-called char during combustion or thermogravimetric analysis (TGA). Due to the relationship, the Limiting Oxygen Index is low. In the case of halogen-based flame retardants having a gas-phase flame retardant, flame retardancy can be easily given regardless of the type of resin, but materials other than halogen-based flame retardants generally require flame retardant action in a solid phase, so that rubber-modified styrene having almost no char content is required. It is difficult to impart flame retardancy with only phosphorus or nitrogen flame retardants to the copolymer resin.

In order to solve the above problems, U.S. Patent Nos. 5,061,745, 5,204,394 and 5,674,924 blended polycarbonate resins and phosphate ester compounds that are easy to form char to rubber-modified styrene copolymer resins to achieve flame retardancy. In this case, however, since the polycarbonate content must be relatively higher than that of the rubber-modified styrene-based copolymer resin, the blend has a problem of having flame retardancy only when at least 60 parts by weight of polycarbonate is used.

US Patent Nos. 4,618,633 and 6,716,900 disclose compositions in which a polyphenylene ether resin having superior char forming ability than polycarbonate is applied to a rubber-modified styrene copolymer resin. However, blends of polyphenylene ether resins and styrene copolymer resins require special care in processing. This is due to a large deviation between the two resins in the processable temperature. The polyphenylene ether resin is an engineering polymer that is difficult to process and needs to be processed at a high temperature, and the styrene copolymer resin is a general-purpose polymer at a relatively low temperature. This is because processing is possible.

In addition, since the polycarbonate and polyphenylene ether resin is expensive compared to other resins, there is a problem in that the production cost increases.

An object of the present invention is to provide a flame-retardant thermoplastic resin composition containing no halogen.

Another object of the present invention is to provide an environmentally friendly flame retardant thermoplastic resin composition.

Still another object of the present invention is to provide a molded article made of a flame retardant thermoplastic resin composition.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above technical problem, the present invention (A) rubber modified styrene-based copolymer resin 5 to 40% by weight; (B) 30 to 90% by weight of a polycarbonate resin; (C) 5 to 30 parts by weight of (D) an aromatic phosphate ester compound, based on 100 parts by weight of a base resin composed of 1 to 50% by weight of polyethylene terephthalate resin; And (E) 0.1 to 20 parts by weight of an aluminum silicate compound to provide a flame retardant thermoplastic resin composition.

In one embodiment of the present invention, the rubber modified styrene copolymer resin (A) is composed of 20 to 100 parts by weight of (a1) styrene-based graft copolymer resin and (a2) 0 to 80 parts by weight of styrene-based copolymer resin Flame retardant thermoplastic resin composition, characterized in that.

In another embodiment of the present invention, the aromatic phosphate ester compound (D) is represented by the following formula (2).

[Formula 2]

In the above formula, R _{1 ,} R _{2 ,} R _{4 ,} and R ₅ are each independently C ₆ ~ C ₂₀ aryl group or a C ₁ ~ C ₍₎ alkyl substituted C ₆ ~ C ₂₀ aryl group and, R ₃ is resorcinol, quinol hydrochloride, a bisphenol -A or bisphenol -S, m is an integer from 0 to 5.

In another embodiment of the present invention, the (E) aluminum silicate compound is at least one selected from the group consisting of kaolinite, nacrite, decite and halosite, flame retardant thermoplastic resin composition.

In order to achieve the above another technical problem, the present invention provides a molded article made of a flame retardant thermoplastic resin composition according to the present invention.

The thermoplastic resin composition according to the present invention is environmentally friendly and excellent in flame retardancy, and in particular, it can solve the gate mark (gate mark) problem that occurs during the injection of the direct gate (direct gate) method.

Hereinafter, the present invention will be described in more detail.

More specifically (A) 5 to 40% by weight of the rubber-modified styrene copolymer resin; (B) 30 to 90% by weight of a polycarbonate resin; (C) 5 to 30 parts by weight of (D) an aromatic phosphate ester compound, based on 100 parts by weight of a base resin composed of 1 to 50% by weight of polyethylene terephthalate resin; And (E) 0.1 to 20 parts by weight of an aluminum silicate compound to provide a flame retardant thermoplastic resin composition.

The present inventors can evaluate the addition of aluminum silicate inorganic filler while applying polyethylene terephthalate resin, which is one of general purpose polymers as polycarbonate, as a char source for the rubber-modified styrenic copolymer resin, to secure excellent flame retardancy and performance. I found it. That is, in the flame retardant thermoplastic resin composition according to the present invention, the polycarbonate resin and the polyethylene terephthalate resin form a char, so that the aromatic aromatic phosphate ester compound and the aluminum silicate inorganic filler are both flame-retardant and help excellent flame retardant without using a halogen flame retardant. By obtaining the effect, it is possible to solve the problem of non-environment of the halogen flame retardant.

The flame retardant thermoplastic resin composition of the present invention is environmentally friendly because it may not use a halogen-based flame retardant.

In addition, the flame-retardant thermoplastic resin composition according to the present invention can solve the gate mark problem that occurs during the injection of the direct gate (direct gate) method.

In general, an injection mold may be classified into a cold runner and a hot runner according to a mold structure. In the case of cold runners, there is no heating device in the mold and the melt passing through the nozzle is cooled immediately, and the injection is divided into the target molding and the sprue. The sprue generated at this time may be discarded or crushed and reprocessed regardless of the target molded product. The hot runner injection mold has a heating device inside the mold to control the melt in the cavity to control the melt so that no sprue is generated at all or the weight of the sprue can be significantly reduced compared to the cold runner. However, the hot runner is injected directly to the surface of the injection molding, so high injection pressure and holding pressure act on the surface of the opposite side of the hot runner mold gate, and a yellowish circular pattern occurs near the opposite surface of the gate and is visually observed. The appearance of the injection molding is not good. This gate mark is because the impact modifier is deformed at the surface of the injection molding and exhibits optically anisotropy. The aluminum silicate compound used in the present invention acts as a buffer for injection pressure and holding pressure at the gate site, thereby causing such a gate mark. Can be solved.

Hereinafter, each component of the resin composition of the present invention will be described in more detail.

(A) rubber modification Styrene series  Copolymer resin

The rubber-modified styrenic copolymer resin used in the present invention refers to a resin polymer in which a grafted rubber polymer is dispersed in a particle form in a matrix (continuous phase) made of a copolymer of vinyl monomers. It is prepared by adding an aromatic vinyl monomer and a vinyl monomer copolymerizable therewith in the presence of a rubbery polymer and polymerizing the same. Such rubber-modified styrene resins can be produced by known polymerization methods such as emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization.

In general, a rubber graft copolymer resin (a1) having a high rubber content and a styrene copolymer resin (a2) containing no rubber are separately prepared, and the two are kneaded according to a use to obtain a rubber-modified styrene copolymer resin. Manufacture. However, in the case of the bulk polymerization, the rubber-modified styrene copolymer resin is produced by only one step reaction process, without separately preparing the graft copolymer resin (a1) and the copolymer resin (a2).

In any of the above polymerization methods, the content of rubber in the final rubber-modified styrene copolymer resin component is preferably 5 to 50 parts by weight.

Examples of the rubber-modified styrene copolymer resins include acrylonitrile-butadiene-styrene copolymer resins (ABS), acrylonitrile-styrene-acryl rubber copolymer resins (ASA), acrylonitrile-ethylene propylene rubber-styrene air Copolymer resins (AES), methyl methacrylate-butadiene-styrene copolymer resins (MBS), and the like.

The rubber-modified styrene-based copolymer resin can be applied to the graft resin alone or in combination of the graft copolymer resin and the copolymer resin, and is preferably blended in consideration of their compatibility. More specifically, in the rubber-modified styrene resin (A), the styrene-acrylonitrile-containing graft copolymer resin (a1) is 20 to 100 parts by weight, and the styrene-acrylonitrile-containing copolymer resin (a2) is 0 to It is suitable to mix | blend at 80 weight part.

In the present invention, the rubber-modified styrenic copolymer resin (A) is used in the range of 5 kPa to 40 kPa in the base resin of (A) + (B) + (C). If the rubber-modified styrene-based copolymer resin (A) is less than 5% by weight of the basic resin of (A) + (B) + (C), the mechanical strength may be lowered. You may not be able to.

Hereinafter, (a1) styrene graft copolymer resin and (a2) styrene copolymer resin, which are components of the rubber-modified styrene copolymer resin (A), according to the present invention will be described in detail.

( a1 ) Styrene system Graft copolymer resin

The styrene graft copolymer resin used in the present invention is prepared by adding and polymerizing an aromatic vinyl monomer capable of graft copolymerization and a monomer copolymerizable with the aromatic vinyl monomer to the rubbery polymer.

Examples of the rubber used for the styrene graft copolymer resin include diene rubbers such as butadiene, styrene-butadiene, acrylonitrile-butadiene, saturated rubbers hydrogenated with the diene rubber, isoprene rubber, and butyl acrylate. Acrylic rubber and ethylene / propylene / diene monomer terpolymer (EPDM), and the like, butadiene rubber, which is a diene rubber, is most preferred. The content of the rubber (rubber polymer) is appropriately 10 to 60 parts by weight based on the styrene-based graft copolymer resin (a1). In consideration of the impact strength and appearance during the preparation of the graft copolymer, the average size of the rubber particles is suitably in the range of 0.05 to 4 μm.

Examples of the aromatic vinyl monomer capable of graft copolymerization to the rubber include styrene, α-methylstyrene, and nuclear substituted styrene. Among them, styrene is most preferable, and the content thereof is 20 to 80 with respect to the graft copolymer resin (a1). Parts by weight are suitable.

Examples of the monomer copolymerizable with the aromatic vinyl monomer include acrylonitrile, methyl methacrylonitrile, methyl methacrylate, N-substituted maleimide, maleic anhydride or a mixture of two or more thereof. Most preferably, the content is 5 to 45 parts by weight with respect to the graft copolymer resin (a1).

( a2 ) Styrene series  Copolymer resin

The styrenic copolymer resin used in the present invention is polymerized in consideration of compatibility in a content equivalent to the proportion of monomers excluding rubber among the components of the graft copolymer.

As the aromatic vinyl monomer used in the styrene copolymer resin, styrene, α-methyl styrene, nuclear substituted styrene and the like may be used, among which styrene is most preferred, and the content of the styrene copolymer resin (a2) 50 to 95 parts by weight is suitable.

Examples of the monomer copolymerizable with the aromatic vinyl monomer include acrylonitrile, methyl methacrylonitrile, methyl methacrylate, N-substituted maleimide, maleic anhydride, and the like, of which acrylonitrile is the most preferable. 5-50 weight part is suitable with respect to silver styrene-type copolymer resin (a2).

(B) polycarbonate resin

The aromatic polycarbonate resin (B) according to the present invention can be prepared by reacting diphenols represented by the following formula (1) with phosgene, halogen formate or carbonic acid diester.

[Formula 1]

Wherein A represents a single bond, C ₁ -C ₅ alkylene, C ₁ -C ₅ alkylidene, C ₅ -C ₆ cycloalkylidene, -S- or -SO _2-

Specific examples of the diphenol of Formula 1 include hydroquinol, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- ( 4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, 2 , 2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane and the like. Among them, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 1,1-bis- (4- Bisphenols such as hydroxyphenyl) -cyclohexane are preferred, and 2,2-bis- (4-hydroxyphenyl) -propane, also called bisphenol-A, is particularly preferable. The polycarbonate resin of the present invention has a weight average molecular weight (M _w ) of 10,000 to 200,000, preferably 15,000 to 80,000.

The polycarbonate resin of the present invention may be a branched chain, preferably 0.05 to 2 mol% of tri- or more polyfunctional compounds, such as trivalent or more, based on the total amount of diphenols used in the polymerization. It can manufacture by adding the compound which has the above phenol group.

In the present invention, the polycarbonate resin (B) is used in the range of 30 to 90% by weight of the basic resin of (A) + (B) + (C). Since the polycarbonate resin plays a role of facilitating flame retardancy impartment, when applied at less than 30% by weight 저하 flame retardancy and mechanical strength decreases.

(C) polyethylene Terephthalate  Suzy

Polyethylene terephthalate resin (C) used in the present invention can be used both a semi-crystalline polyethylene terephthalate resin and an amorphous polyethylene terephthalate resin, these act as a Char Source, rubber modified styrene copolymer A base resin is comprised together with resin X and polycarbonate resin.

In the present invention, the polyethylene terephthalate resin (C) is used in the range of 1 kPa to 50 kPa in the basic resin of (A) + (B) + (C). If the polyethylene terephthalate resin (C) is less than 1 part by weight of the base resin of (A) + (B) + (C), the fluidity of the composition may be lowered, so that the processing temperature should be increased. Can be.

Hereinafter, the polyethylene terephthalate resin (C) according to the present invention is a polybutylene terephthalate (PBT), polycyclohexane terephthalate (PCT), polyethylene naphthalate (PEN) or the like as part of the polyethylene terephthalate resin as necessary or Can replace the whole.

In addition, the polyethylene terephthalate-based resin (C) is not particularly limited, and conventionally used polyethylene terephthalate resin (PET) or a polyethylene terephthalate resin obtained by recycling may be used, and an amorphous polyethylene terephthalate resin is an polyethylene terephthalate or Glycol modified polyethylene terephthalate such as poly (ethylene-1,4-cyclohexanedimethylene terephthalate) (PETG) and the like can be applied.

(D) Aromatic Phosphate Ester Compounds

Used in the present invention 　 The aromatic phosphate ester compound is a compound having the same structure as in formula (2), but the structural formula of the aromatic phosphate ester compound of formula (2) specified below does not limit the scope of the present invention.

The aromatic phosphate ester compound is applied as a flame retardant of the resin composition prepared by the present invention, and may be applied at 5 to 30 parts by weight based on 100 parts by weight of the base resin of (A) + (B) + (C). And preferably 10 to 20 parts by weight. If it is less than 5 parts by weight, it is difficult to achieve flame retardancy, and if it is more than 30 parts by weight, there may be a problem that mechanical strength and heat resistance are lowered.

[Formula 2]

In the above formula, R _{1 ,} R _{2 ,} R _{4 ,} and R ₅ are each independently C ₆ ~ C ₂₀ aryl group or a C ₁ ~ C ₍₎ alkyl substituted C ₆ ~ C ₂₀ aryl group and, R ₃ is resorcinol, quinol hydrochloride, a bisphenol -A or bisphenol -S, m is an integer from 0 to 5.

i) When m is 0, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trigylyl phosphate, tri (2,4,6-trimethylphenyl) phosphate and tri (2,4-dibutyl butylphenyl ) Phosphate, tri (2,6-dibutylbutylphenyl) phosphate,

ii) when m is 1, resorcinol bis (diphenyl phosphate), hydroquinol bis (diphenyl phosphate), bisphenol A-bis (diphenyl phosphate), resorcinol bis (2,6-dibutyl butylphenyl Phosphate), hydroquinolbis (2,6-dimethylphenylphosphate),

iii) when m is 2 or more, it is present in the form of a mixture in the form of oligomers and may be applied alone or as a mixture of the above-mentioned compounds.

The aromatic phosphoric acid ester-based compound may be partially or completely replaced by another phosphorus-containing flame retardant such as phosphonate, phosphinate, phosphazene, or the like.

(E) aluminum Silicate  compound

The aluminum silicate compound used in the present invention is, for example, kaolinite, nacrite, decite, halosite, or the like as the inorganic filler. Preferably, it may be a halosite. Haloysite is composed of aluminum, silicon, hydrogen, oxygen and its chemical formula is Al ₂ Si ₂ O ₅ (OH) ₄ . It is made by the weathering of aluminum silicate minerals, such as feldspar, and has the shape of a fairly small hollow tube with a diameter of about 40 to 200 nanometers.

In the present invention, the halosite is 0.1 to 20 parts by weight based on 100 parts by weight of the base resin 의 (A) + (B) + (C). More preferably, it is 3-15 weight part. If the halosite is less than 0.1 parts by weight, the blending of the polycarbonate and polyethylene terephthalate resin is poor in flame retardancy, and if it exceeds 20 parts by weight, mechanical properties and impact resistance are lowered.

In the thermoplastic resin manufacturing method of the present invention, antidropping agents such as polytetrafluoroethylene, impact modifiers, antioxidants, plasticizers, thermal stabilizers, light stabilizers, compatibilizers, pigments, dyes, inorganic additives or two The above mixture may be added.

The resin composition of this invention can be manufactured by the well-known method of manufacturing a resin composition. For example, the components of the present invention and other additives may be mixed simultaneously, then melt extruded in an extruder and made into pellets.

The composition of the present invention can be used for molding a variety of products, and is particularly suitable for the production of electrical and electronic products, such as the housing of TVs and office automation equipment.

The invention can be better understood by the following examples, which are intended to illustrate the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Preparation and specifications of the base resin, flame retardant additive and compatibilizer used in the following Examples and Comparative Examples are as follows.

(A) Rubber modified styrene resin

Rubber modified styrenic copolymer resin (A) used in Examples and Comparative Examples of the present invention is kneaded 40 parts by weight of the styrene-based graft copolymer resin (a1) and 60 parts by weight of styrene-containing copolymer resin (a2) It is a resin formed by.

(a1) Styrene-based graft copolymer resin: ABS graft copolymer resin

The styrene-based graft copolymer resin (ABS) used in Examples and Comparative Examples of the present invention is a 50 parts by weight of butadiene rubber latex in the solid content in the reactor, 36 parts by weight of styrene, 14 parts by weight of acrylonitrile And 150 parts by weight of deionized water, 1.0 part by weight of potassium oleate, 0.4 part by weight of cumene hydroperoxide, 0.2 part by weight of mercaptan-based chain transfer agent, 0.4 part by weight of glucose, 0.01 part by weight of iron sulfate hydrate, and pyrophosphate sodium salt. 0.3 parts by weight was added, and the reaction was completed at 5 ° C. for 5 hours to prepare a graft copolymer resin latex, and sulfuric acid was added to 0.4 parts by weight based on the solids of the resin to solidify to prepare a powder.

(a2) Styrene copolymer resin: SAN copolymer resin

Styrene copolymer resin (SAN) used in Examples and Comparative Examples of the present invention is styrene as 72 parts by weight of acrylonitrile 28 parts by weight, deionized water 120 parts by weight and azobisisobutyronitrile 0.2 parts by weight, 0.4 parts by weight of tricalcium phosphate and 0.2 parts by weight of mercaptan-based chain transfer agent were added, and the temperature was raised to 90 ° C. at room temperature for 90 minutes, followed by 240 minutes at this temperature to prepare acrylonitrile content 25% by weight. , Dehydrated and dried to prepare a SAN copolymer resin powder. The weight average molecular weight of the styrene-acrylonitrile copolymer resin corresponds to about 180,000 to 200,000.

(B) polycarbonate resin (PC)

Panlite L-1225 Grade from Teijin, Japan, was used.

(C) polyethylene terephthalate resin

The polyester resin used in the embodiment of the present invention was applied to SKYGREEN K2012 Grade manufactured by SK Chemicals as poly (ethylene-1,4-cyclohexanedimethylene terephthalate) (PETG).

(D) Aromatic Phosphate Ester Compounds

Phosphoric acid ester compound used in Examples and Comparative Examples of the present invention was applied to PX-200 grade manufactured by Daihachi Chemical Co., Ltd. as resorcinol bis (di2,6-gyrenylphosphate).

(E) Aluminum silicate compound: halosite (HNT)

Premium ultrafine halloysite manufactured by Imersys was used.

(F) anti-drip agent (PTFE: Polytetrafluoroethylene)

Teflon (trade name) 7AJ of Dupont, USA was used.

[ Example  1 to 4, Comparative Example  1 to 3]

The material of (A) ~ (D) shown above was added to the content as shown in Table 1 below to extrude at a temperature range of 220 ~ 250 ℃ in a conventional twin screw extruder to prepare a pellet.

The prepared pellets were dried at 80 ° C. for 3 hours, and then injected at 80 ° C. under a molding temperature of 230 ° C. and a mold temperature of 60 ° C. to prepare flame-retardant specimens. The prepared specimens were measured for flame retardancy according to the UL 94 flame retardant regulations. Izod impact strength was measured according to ASTM D-256 and MI values were measured according to ASTM D-1238.

In order to measure the color difference of the skin portion of the injection molded product corresponding to the gate, the pellets were prepared by inserting them in the amounts shown in Table 1 below and extruding them at a temperature range of 220 to 250 ° C. in a conventional twin screw extruder. Specimens were fabricated using a submarine gate mold at a molding temperature of 230 ° C and a mold temperature of 60 ° C in an 8 oz injection machine, and the color difference b value was measured according to ASTM D1925.

1 is a TEM image of the injection surface area within 2 cm radius of the gate-compatible injection molding surface of Comparative Example 1, Figure 2 is a TEM image of the injection surface area 4 cm away from the gate-compatible injection molding surface of Comparative Example 1, Figure 3 It is a TEM photograph of the injection surface part within a radius of 2 cm of the gate-compatible injection-molded product surface of 3.

Item Example Comparative Example One 2 3 4 One 2 3 Graft Copolymer (A)
(ABS resin) 15 15 20 20 15 15 20 PC (B) 50 60 70 75 50 60 70 PETG (C) 35 25 10 5 35 25 10 Aromatic Phosphate Ester
PX-200 (D) 10 10 10 10 20 15 15 HNT (E) 5 5 3 3 - - - PTFE (F) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Flame retardancy
(UL 94, 2.5mm thickness) V-0 V-0 V-0 V-0 V-0 Fail V-2 Color difference (b) within 2 cm of the gate-compatible injection surface -1.4 -1.4 -1.3 -1.4 -0.6 -0.5 -0.4 4 cm from the gate-compatible injection surface
Color difference at the point away (b) -1.5 -1.3 -1.3 -1.5 -1.5 -1.4 -1.6

In the case of Examples 1 to 4 using the halosite as shown in the results of Table 1, it can be seen that the color difference value is improved compared to Comparative Examples 1 to 3 not using the halosite.

Within a radius of 2 cm of the surface of the gate-compatible injection molded product of FIG. 1, the graft copolymer (A) component applied within 10 μm from the surface layer to the core is shown to be elliptical rather than spherical. The side is spherical in shape. Moreover, in the injection-injection surface part 4 cm away from the gate corresponding injection-injection surface of FIG.

The graft copolymer (A) component transformed into an elliptical shape within 10 cm from the surface layer at the surface of the injection surface within a radius of 2 cm of the gate-compatible injection surface of FIG. As a result, it means that the color variation of this part was incurred. As a result, a difference between the b-values within a radius of 2 cm of the gate-compatible injection molding surface and a point 4 cm away from the gate-compatible injection molding surface is generated, and thus the color difference is visually identified.

It can be seen that the graft copolymer (A) within 10 μm from the surface layer to the core and at least 10 μm of the core at the injection surface portion of the gate-compatible injection-molded surface of FIG. have. Therefore, in Example 3 to which the halosite is applied, there is no difference in the b value between the gate-compatible injection surface and the gate-compatible injection surface at some distance, and as a result, there is no difference in visual color.

By comparison between the above examples and comparative examples, the present invention provides (A) rubber modified styrene resin, (B) polycarbonate resin, (C) polyethylene terephthalate resin (D) aromatic phosphate ester compound (V) and (E) inorganic By incorporating the component of the halosite, which is a filler, it is possible to manufacture a thermoplastic resin with improved flame retardancy, and in the comparative example, the gate part color difference due to the deformation of the graft copolymer on the surface of the injection molding occurs, but the halosite in the embodiment In the case of application, since the halosite has a buffering effect on the injection pressure, the difference in the b value between the gate part and the part far away from the gate is smaller than that of the comparative example, so that the color difference cannot be visually distinguished. Could.

Simple modifications or changes of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

1 is a TEM image of a portion within a radius of 2 cm of the surface of a gate-compatible injection molding during an injection process of a specimen manufactured by an injection process from a thermoplastic resin composition containing no aluminum silicate compound.

FIG. 2 is a TEM photograph of an injection surface portion 4 cm away from a gate-compatible injection surface during an injection process of a specimen prepared by an injection process from a thermoplastic resin composition containing no aluminum silicate compound.

FIG. 3 is a TEM photograph of a portion within a radius of 2 cm of a surface of a gate-compatible injection molded product during an injection process of a specimen prepared by an injection process from a flame retardant thermoplastic resin composition according to an embodiment of the present invention.

Claims (11)

(A) 5 to 40% by weight of rubber-modified styrene copolymer resin; (B) 30 to 90% by weight of a polycarbonate resin; (C) to 100 parts by weight of a base resin composed of 1 to 50% by weight of polyethylene terephthalate resin (D) 5 to 30 parts by weight of the aromatic phosphate ester compound; And (E) Flame retardant thermoplastic resin composition comprising 0.1 to 20 parts by weight of aluminum silicate compound. The rubber-modified styrenic copolymer resin (A) comprises 20 to 100 parts by weight of (a1) styrene graft copolymer resin and 0 to 80 parts by weight of (a2) styrene copolymer resin. Flame retardant thermoplastic resin composition. According to claim 2, wherein the styrene graft copolymer resin (a1) is 10 to 60 parts by weight of a rubbery polymer, 20 to 80 parts by weight of an aromatic vinyl monomer and 5 to 45 parts by weight of a monomer copolymerizable with the aromatic vinyl monomer. Including wealth, The styrene copolymer resin (a2) is a flame-retardant thermoplastic resin composition, characterized in that 5 to 50 parts by weight of the monomer copolymerizable with the aromatic vinyl monomer in 50 to 95 parts by weight of the aromatic vinyl monomer. The rubbery polymer according to claim 3, wherein the rubbery polymer is a diene rubber, a saturated rubber added with hydrogen to the diene rubber, an isoprene rubber, a chloroprene rubber, an acrylic rubber, and an ethylene / propylene / diene monomer terpolymer (EPDM), Or a mixture of two or more of these, The aromatic vinyl monomer is selected from the group consisting of styrene, α-methylstyrene, nuclear substituted styrene, or a mixture of two or more thereof, The monomer copolymerizable with the aromatic vinyl monomer is selected from the group consisting of acrylonitrile, methyl methacrylonitrile, methyl methacrylate, N-substituted maleimide, maleic anhydride or a mixture of two or more thereof. Flame retardant thermoplastic resin composition. The method of claim 1, wherein the rubber modified styrene resin (A) is acrylonitrile / butadiene / styrene copolymer resin (ABS), acrylonitrile / acrylic rubber / styrene copolymer resin (AAS), acrylonitrile / ethylene Flame retardant thermoplastic resin composition, characterized in that it is selected from the group consisting of propylene rubber / styrene copolymer resin (AES), or a mixture of two or more thereof. The flame retardant thermoplastic resin composition of claim 1, wherein the aromatic phosphate ester compound (D) is represented by the following Chemical Formula 1: [Formula 1]

In the above formula, R _{1 ,} R _{2 ,} R _{4 ,} and R ₅ are each independently C ₆ ~ C ₂₀ aryl group or a C ₁ ~ C ₍₎ alkyl substituted C ₆ ~ C ₂₀ aryl group and, R ₃ is resorcinol, quinol hydrochloride, a bisphenol -A or bisphenol -S, m is an integer from 0 to 5. The flame retardant thermoplastic resin composition of claim 1, wherein the aluminum silicate compound (E) is at least one selected from the group consisting of kaolinite, nacrite, dikite and halosite. The flame retardant thermoplastic resin composition according to claim 1, wherein the (E) aluminum silicate compound is a halosite having a chemical formula of Al ₂ Si ₂ O ₅ (OH) ₄ . The method of claim 1, further comprising a dropping agent, an impact modifier, an antioxidant, a plasticizer, a heat stabilizer, a light stabilizer, a compatibilizer, a pigment, a dye, an inorganic additive, and a mixture of two or more thereof. Flame retardant thermoplastic resin composition. The gate and the gate according to any one of claims 1 to 9, wherein the pellets manufactured from the flame-retardant thermoplastic resin composition are within 2 cm of the radius of the injection-molded surface of the injection molding of the mold to which a hot runner is applied. A flame retardant thermoplastic resin composition characterized in that the difference in color difference b value according to ASTM D1925 standard at the injection surface surface point 4 cm away from the corresponding injection surface is within 0.5. A molded article made of the flame retardant thermoplastic resin composition according to any one of claims 1 to 9.

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