KR101772738B1 - Polycarbonate flame retardant resin composition and injection molding product - Google Patents

Abstract

According to the present invention, there is provided a polycarbonate flame retardant resin composition and a polycarbonate flame retardant resin composition comprising a polycarbonate flame retardant resin reinforced with wollastonite and reinforced with a specific impact modifier and, if necessary, an acrylic copolymer, The present invention can provide a rigidity by reinforcing the wollastonite talc and improve the impact and toughness caused by a high amount of inorganic material reinforcement to improve the product breakage or breakage which occurred in the customer reliability test, A polycarbonate flame retardant resin composition capable of optimizing warpage characteristics and surface smoothness by injecting a nucleating agent and an article obtained from the polycarbonate flame retardant resin composition.

Description

[0001] The present invention relates to a polycarbonate flame retardant resin composition and an injection molding product,

The present invention relates to a polycarbonate flame retardant resin composition and articles of manufacture, and more particularly, to a polycarbonate flame retardant resin composition reinforced with wollastonite talc, which comprises a specific impact modifier and, if necessary, an acrylic copolymer in combination , And reinforced with wollastonite to improve the impact and toughness degradation caused by the high content of inorganic reinforcement, thereby improving the product cracking or breakage that occurred during the customer's reliability test, To a polycarbonate flame retardant resin composition and a specimen which can optimize a flexural characteristic and a surface smoothness.

Talc-reinforced polycarbonate (PC) materials, which are generally used as housings for electric and electronic products such as notebook computers, are excellent in warpage and surface smoothness, but impact and toughness are rapidly deteriorated when a high content is used.

For example, wollastonite is used when using a polycarbonate material containing a high content of an inorganic material for a notebook housing. However, wollastonite has a shape of acicular shape with a very large aspect ratio (aspect ratio), so that warping occurs and surface smoothness is lowered. For this reason, wollastonite and talc are mixed at an appropriate ratio, but it is difficult to optimize the impact and bending properties by mixing only these two kinds of inorganic materials.

Therefore, it is necessary to study a technique for optimizing the impact characteristics, the bending properties, and the surface smoothness.

It is therefore an object of the present invention to provide a polycarbonate flame retardant resin composition which solves the above problems and which comprises a polycarbonate flame retardant resin reinforced with wollastonite talc and a specific impact modifier and optionally an acrylic copolymer in combination, And it is possible to improve the breakage and breakage of the product which occurred in the customer reliability test by improving the impact and toughness lowering caused by the high content of inorganic reinforcement. Further, by injecting the specific nucleating agent, A polycarbonate flame retardant resin composition capable of optimizing smoothness and an article obtained therefrom.

According to the present invention,

A polycarbonate flame retardant resin composition reinforced with wollastonite and talc,

And at least one activator selected from the group consisting of polyethylene wax, refined esters of montan wax, and an impact modifier. The present invention also provides a polycarbonate flame retardant resin composition.

The present invention also provides a molded article comprising the polycarbonate flame retardant resin composition described above.

According to the present invention, there is provided a polycarbonate flame retardant resin composition comprising a wollastonite-reinforced polycarbonate flame retardant resin and a specific impact modifier and, if necessary, an acrylic copolymer in combination, to provide stiffness by reinforcing wollastonite with talc, The polycarbonate which can optimize the warp characteristics and the surface smoothness by injecting a specific nucleating agent can be improved by improving the impact and toughness caused by the polycarbonate It has the effect of providing the flame retardant resin composition and the article obtained therefrom.

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

The polycarbonate flame retardant resin composition of the present invention is a polycarbonate flame retardant resin composition reinforced with wollastonite and talc including at least one selected from polyethylene wax and refined esters of montan wax and an impact modifier .

If the aspect ratio of the wollastonite is too low, the stiffness is low and it may be difficult to apply. For example, it is preferable to use a material having a high aspect ratio of 5 to 14 or 9 to 13 in aspect ratio (L / D).

The wollastonite is surface-treated with an olefin-based compound to provide an effect on impact characteristics. For example, the wollastonite is surface-treated with 0.1-2 wt% or 0.1-1.5 wt% of polyolefin with respect to 100 wt% .

The wollastonite may be, for example, 5-30% by weight, or 10-20% by weight, And it is possible to effectively prevent the warpage of the product within this range and to satisfy the rigidity in combination with the talc.

The talc includes, for example, a mixed metal oxide having a particle size (d50) of less than or equal to 5 microns, or less than or equal to 3.3 microns and a density of 2.5 to 2.8 g / cm3, or 2.78 to 2.8 g / can do. If the particle shape of the talc is not fine, there may be a disadvantage that the impact property is deteriorated.

The mixed metal oxide may include at least two of SiO2, MgO, Al2O3, Fe2O3, and CaO, and may further include at least one of SiO2 and MgO as a residual oxide.

The talc is included, for example, in the range of 5-20% by weight, or 7-12% by weight of the total 100% by weight of the composition, effectively preventing warpage of the product within this range, Can be satisfied.

The polycarbonate resin may be a resin having a melt index (300 DEG C, 1.2 kg load) of 1 to 80 g / 10 min, or 3 to 70 g / 10 min.

The polycarbonate resin as an example, contained within the 50-70% by weight of a total of 100% by weight of the composition, or 55 to 65% by weight, is effective to exert a flame retardant and flow within this range.

As another example, the polycarbonate resin may be a mixture of a polycarbonate resin and a bisphenol-based polydimethylsiloxane copolymer having a melt index (300 DEG C, 1.2 kg load) of 1 to 80 g / 10 minutes.

45 to 55% by weight or 45 to 50% by weight of a polycarbonate resin having a melt index (300 DEG C, 1.2 kg load) of 1 to 80 g / 10 minutes among the total 100% by weight of the composition and bisphenol- 5-15% by weight of the siloxane copolymer, or 10-15% by weight of the siloxane copolymer.

The lubricant may be at least one selected from, for example, polyethylene wax, and refined esters of montan wax.

The lubricant may be included, for example, in the range of 0.1-5 wt%, or 0.1-1 wt%, based on 100 wt% of the total composition, and may provide optimized warpage characteristics and surface smoothness within this range.

The impact modifier may be, for example, a silicone-acrylic rubber-containing acrylic compound or a silicone-acrylic rubber-containing compound having a silicone-vinyl-based core-shell structure.

Examples of the acrylic rubber include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate and 2-ethylhexyl methacrylate. And the silicone rubber may be prepared from cyclosiloxane and may be, for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, Trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane, and the like.

The content of the rubber is in the range of 20 to 80% by weight with respect to the impact modifier of the present invention, and if it is included in the above range, the impact reinforcing effect can be maximized and the fluidity can be remarkably improved.

As a specific example of the impact modifier, the Metablen series of MRC Company, for example, Metablen S-2001, Metablen S-2006 containing a silicone-acrylic rubber may be used. For reference, acrylonitrile-butadiene-styrene resin, methyl methacrylate-butadiene-styrene resin, methyl methacrylate-acrylonitrile-butadiene-styrene resin and the like, known as impact modifiers in the art, Alternative use is possible within a range that satisfies strength and thermal stability.

For example, the impact modifier may be contained in an amount of from 1 to 10% by weight, or from 3 to 7% by weight, based on 100% by weight of the total composition, and sufficient impact resistance against impact reduction by the additive within the above range can be secured.

Further, the composition may be an ethylene- (meth) acrylate copolymer And an ethylene-butyl acrylate-glycidyl methacrylate terpolymer.

The acrylic copolymer may contain an ethylene monomer in an amount of 0.1 to 5% by weight.

As a specific example, the acrylic copolymer may be an ethylene-methacrylate copolymer.

The acrylic copolymer may be used in combination with the impact modifier to improve impact and toughness, and to improve product breakage or breakage occurring in a customer reliability test.

The acrylic copolymer may be contained in an amount of 1-5 wt% or 1-3 wt% of the total 100 wt% of the composition.

The flame retardancy in the polycarbonate flame retardant resin composition of the present invention can be provided, for example, from an aromatic phosphate-based flame retardant.

Specific examples of the aromatic phosphate-based flame retardant include resorcinol bis (diphenylphosphate), bisphenol A bis (diphenylphosphate), and N, N'-bis [di- (2,6-xylyl) - piperazine. ≪ / RTI >

More specific examples of the aromatic phosphate-based flame retardant include:

[Chemical Formula 1]

로 표시되는 화합물일 수 있다.

. ≪ / RTI >

The aromatic phosphate-based flame retardant is included in the range of 5 to 15% by weight, or 7 to 12% by weight, based on 100% by weight of the total composition, and has a V-0 rating It is possible to provide an optimized flame retardant effect and at the same time to lower the temperature rise due to shear during the injection molding in the above range.

The composition may contain additives such as a lubricant, a colorant, a releasing agent, a pigment, a dye, an antistatic agent, an antimicrobial agent, a processing aid, a metal deactivator, a suppressing agent, a fluorine antistatic agent, And a coupling agent And at least one additive selected from the group consisting of:

The composition may be applied at 250-300 占 폚 in the extrusion molding section, 250-300 占 폚 in the injection molding section, and 60-100 占 폚 in the mold section.

For reference, when a twin-screw extruder is used for extrusion, the lubricant may be added to the main hopper of the twin-screw extruder together with other components, and the wollastonite may be separately introduced into the sider of the twin-screw extruder.

According to the present invention, it is possible to provide an injection molded article containing the above-mentioned composition.

According to the present invention, a molded article comprising the polycarbonate flame retardant resin composition described above can be provided.

The molded article may be provided by extrusion molding, injection molding or the like, and a specific example thereof may be a housing of an electrical and electronic product which requires both a bending property and a surface smoothness together with a notebook computer.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited thereto.

Examples 1 to 5, Comparative Examples 1 to 2

Components having composition ratios as shown in the following Table 1 were added and mixed in a super mixer. Components other than the component B were fed into the main hopper of the twin-screw extruder, and the component B was fed to a sider of a twin- And the mixture was kneaded and kneaded at 280 DEG C, and the kneaded composition was prepared in the form of pellets with a pelletizer. The composition of the pellets was dried at 120 ° C for 8 hours or more in a hot-air drier, and then a physical property specimen was prepared at an injection temperature of 200 to 280 ° C and a mold temperature of 60 to 100 ° C using an 80MT ENGEL extruder.

For reference, the materials used in the experiments are as follows:

≪ (A) Bisphenol A polycarbonate resin (PC) >

The polycarbonate resin was a polymer of bisphenol A, and its melt index (MI) was measured as weight (g) measured at 300 DEG C temperature and 1.2 kg load for 10 minutes in accordance with ASTM D1238. As a result, an aromatic polycarbonate resin having a melt index of 3 g / 10 min ((A) -1), 22 g / 10 min (A) -2 and 70 g / 10 min (A) -3 was used, respectively. (A) -4 was a PC copolymer of bisphenol A / polydimethylsiloxane (BPA / PDMS) manufactured by Samyang Corporation.

<(B) Wollastonite>

A wollastonite (NYGLOS 4W NYCO Co., Ltd.) surface-treated with an aspect ratio (?) Of 9, a olefin compound of 0.5wt%, a width (D) of 7 占 퐉, a length of 63 占 퐉,

[Formula 1] Aspect ratio (?) = L / D

(Where L is the length of the wollastonite and D is the length of the longest side of the section).

<(C) Talc>

95% of Koch Co. used talc having a particle size (d50) of 3.3 μm or less and a density of 2.8 g / cm 3 and a mixed metal oxide component of SiO 2, MgO, Al 2 O 3, Fe 2 O 3 and CaO.

<(D) Impact reinforcement>

Metablen S-2001, a product name of MRC, was used as a silicone-acrylic impact modifier which is a silicone-vinyl based core-shell structure.

<(E) Ethylene Acrylate Copolymer>

As the ethylene-methacrylate copolymer, Elvaloy 1330AC manufactured by DuPont was used.

&Lt; (F) Flow modifier and flame retardant aid >

As the aromatic phosphate of Adeka, the product name FP-600 was used.

&Lt; (G) -1 >

As the pentaerythritol tetrastaurate compound of Faci, the product name PETS-AHS was used.

<(G) -2 Lubricant>

The product Licowax E was used as a Montan ester system of Clariant.

&Lt; (G) -3 Lubricant >

Hi-wax 405MP was used as the polyethylene system of Mitsui.

division Example Comparative Example One 2 3 4 5 One 2 A A-1 40 A-2 57.6 57.6 57.6 47.6 56.6 57.6 A-3 20 A-4 10 B 15 15 15 15 15 25 15 C 10 10 10 10 10 - 10 D 7 7 7 7 3 8 7 E 1.6 F 10 10 10 10 10 10 10 G-1 0.4 0.4 G-2 0.4 0.2 0.2 0.2 G-3 0.4 0.2 0.2 0.2

The physical properties of the specimens of Examples 1 to 5 and Comparative Examples 1 and 2 were measured by the following test examples, and the results are summarized in Table 2 below.

Test example: Measurement of physical properties

The tensile strength, flexural strength, flexural modulus, impact strength, melt index, spiral (flexural characteristic), surface impact, appearance and surface smoothness of the articles prepared in Examples 1 to 5 and Comparative Examples 1 and 2 were measured by the following methods The results are summarized together in Table 2 below.

Tensile strength (kg / cm 2): ASTM D638 (specimen thickness 3.2 mm, 23 캜).

Flexural Strength and Flexural Modulus (kg / cm2): ASTM D790 (specimen thickness 3.2 mm, 23 캜).

Impact strength (kg.cm/cm): ASTM D256 (specimen thickness 3.2 mm, 23 캜).

* Melt flow index (MI): ASTM D1238 (260 占 폚, 2.16 kg).

Spiral (cm): Measured at injection temperature of 270 ° C, holding pressure of 1000 bar, 1.5 mm specimen.

* Surface Impact (J): Measured according to the method specified in ASTM D3763 (specimen thickness 1.5 mm, 23 캜).

* Appearance and Surface Smoothness: Gas marks on the surface and surface smoothness were visually observed. The +++ in the table was clean without any gas marks on the exterior of the specimen, with no warpage of the surface at all, and gas marks and warpage gradually increased with + And it was classified as a state in which the marks were visible and the distortion was considerably severe.

* Flame Retardancy: Measured according to the UL94V method with a 1.2 mm thick standard, V-0 rating was confirmed in all of Examples 1 to 5 and Comparative Examples 1 and 2.

As shown in the above Table 2, the wollastonite-reinforced polycarbonate flame retardant resin composition according to the present invention comprises at least one selected from a polyethylene wax and refined esters of montan wax, and an impact modifier The polycarbonate flame retardant resin compositions (Examples 1 to 5) containing the polycarbonate resin have balanced physical properties in melt index, spiral, surface impact, appearance and surface smoothness as well as mechanical properties such as tensile strength, flexural strength, flexural modulus and impact strength Respectively.

On the other hand, in the case of the polycarbonate flame retardant resin composition (Comparative Example 1) in which the content of wollastonite was significantly higher than that of Example 1 and the amount of talc was not included and the above-mentioned lubricant was replaced by pentaerythritol tetrastearate lubricant, appearance and surface smoothness Poor,

In the case of the polycarbonate flame retardant resin composition (Comparative Example 2) in which wollastonite and talc were compounded in place of the above-mentioned lubricant type and replaced with a pentaerythritol tetrastearate lubricant as in Example 1, the surface impact value was poor.

&Lt; Additional Comparative Example 1 &

In Example 1, D was replaced by a copolymer (see D 'below) prepared by emulsion polymerization comprising 60 parts by weight of a rubbery polymer having a rubbery average particle size of 0.3 탆, 30 parts by weight of styrene and 10 parts by weight of acrylonitrile The same experiment as in Example 1 was repeated.

& Lt; (D) Impact modifier &gt;: Metablen S-2001, a product name of MRC, was used as a silicone-acrylic impact modifier having a silicone-vinyl core-shell structure.

& Lt; (D ') Impact modifier &gt;: DP270E manufactured by LG Chem was used as an acrylonitrile-butadiene-styrene copolymer.

As a result, a tensile strength of 550 kg / cm 2, a flexural strength of 960 kg / cm 2, a flexural modulus of 54,500 kg / cm 2, an impact strength of 5.5 kg.cm/cm, a melt index of 17 g / 10 min, 6.5 J, and the appearance and surface smoothness were symbol +, and it was confirmed that the impact properties of Example 1 were lowered.

&Lt; Reference Example 1 &

The same experiment as in Example 1 was repeated except that B in Example 1 was replaced with B 'shown below.

<(B) Wollastonite>

A wollastonite (NYGLOS 4W NYCO Co., Ltd.) surface-treated with an aspect ratio (?) Of 9, a olefin compound of 0.5wt%, a width (D) of 7 占 퐉, a length of 63 占 퐉,

<(B ') Wollastonite>

A wollastonite (NYAD 5000, NYCO Co., Ltd.) surface-treated with a width (D) of 3 μm, a length (L) of 9 μm, an aspect ratio (δ) of 3 calculated by the following formula 1, and 0.5 wt% of an olefin compound was used.

As a result, the tensile strength was 500 kg / cm 2, the flexural strength was 930 kg / cm 2, the flexural modulus was 38,000 kg / cm 2, the impact strength was 4.0 kg.cm/cm, the melt index was 20 g / 10 min, , The surface impact was 4 J, and the appearance and surface smoothness were symbol ++. Thus, it was confirmed that the flexural modulus and impact properties of Example 1 were poor.

Claims (15)

A polycarbonate flame retardant resin composition reinforced with wollastonite and talc,
Polyethylene wax and refined esters of montan wax, and an impact modifier, wherein the wollastonite has been surface-treated with 0.1 to 2% by weight of a polyolefin compound based on 100% by weight of total wollastonite Featured
Polycarbonate flame retardant resin composition. The method according to claim 1,
Wherein the wollastonite has an aspect ratio of 5 to 14
Polycarbonate flame retardant resin composition. The method according to claim 1,
Wherein the wollastonite is in the range of 5-30 % by weight of the total 100% by weight of the composition
Polycarbonate flame retardant resin composition. The method according to claim 1,
Characterized in that the talc has a particle size (d50) of 5 탆 or less, a density of 2.5 to 2.8 g / cm 3 and a mixed metal oxide
Polycarbonate flame retardant resin composition. The method according to claim 1,
The talc may comprise from 5 to 20% by weight of the total composition 100% &Lt; / RTI &gt;
Polycarbonate flame retardant resin composition. The method according to claim 1,
Wherein the polycarbonate resin is a polycarbonate resin having a melt index (300 DEG C, 1.2 kg load) of 1 to 80 g / 10 min, wherein 50 to 70 wt% &Lt; / RTI &gt;
Polycarbonate flame retardant resin composition. The method according to claim 1,
The polycarbonate resin is a mixture of a polycarbonate resin and a bisphenol-based polydimethylsiloxane copolymer having a melt index (300 DEG C, 1.2 kg load) of 1 to 80 g / 10 min, and has a melt index (300 DEG C, A load of 1.2 kg) of 1 to 80 g / 10 minutes, and 5 to 15% by weight of a bisphenol-based polydimethylsiloxane copolymer.
Polycarbonate flame retardant resin composition. The method according to claim 1,
Wherein the lubricant is in the range of 0.1-5% by weight of the total 100% by weight of the composition
Polycarbonate flame retardant resin composition. The method according to claim 1,
Wherein the impact modifier is a silicone-acrylic rubber-containing compound having a core-shell structure of a silicone-vinyl system
Polycarbonate flame retardant resin composition. The method according to claim 1,
Wherein the impact modifier is in the range of 1-10% by weight of the total 100% by weight of the composition
Polycarbonate flame retardant resin composition. The method according to claim 1,
Wherein said composition comprises 1-5 wt% of at least one acrylic copolymer selected from ethylene- (meth) acrylate copolymer and ethylene-butyl acrylate-glycidyl methacrylate terpolymer in 100 wt% of the total composition Characterized by
Polycarbonate flame retardant resin composition. The method according to claim 1,
The flame retardancy of the composition can be improved by the addition of resorcinol bis (diphenylphosphate), bisphenol A bis (diphenylphosphate), and N, N'-bis [di- (2,6-xylyl) phosphoryl] -piperazine Characterized in that it is provided in an amount of 5-15% by weight of the total 100% by weight of the composition, based on one or more aromatic phosphate-based flame retardants selected from the group consisting of
Polycarbonate flame retardant resin composition. The method according to claim 1,
The composition is characterized by containing one or more additives selected from a lubricant, a colorant, a releasing agent, a pigment, a dye, an antistatic agent, an antibacterial agent, a processing aid, a metal deactivator, a suppressing agent, a fluorine antistatic agent, To
Polycarbonate flame retardant resin composition. A molded article comprising the polycarbonate flame retardant resin composition of claim 1. 15. The method of claim 14,
Characterized in that the molded article is a housing of an electric / electronic product
Shaped article.