KR102060559B1 - Flame retardant polycarbonate composition having processability and molded rpoduct using the same - Google Patents

Abstract

The present invention relates to a flame retardant polycarbonate resin composition and a molded article using the same having excellent processability, and more specifically, (a) 60 to 80 wt% of a polycarbonate resin; (b) 1 to 10% by weight of alkyl (meth) acrylate-vinylaromatic compound-vinylcyan compound copolymer resin; (c) 1 to 10% by weight of vinylaromatic compound-vinylcyan compound copolymer resin; (d) 1 to 10% by weight of silicone-acrylic impact modifier; (e) 3 to 20% by weight of a liquid phosphorous flame retardant; (f) 0.1 to 0.7 wt% of fluorinated olefin resin; And (g) 0 to 5% by weight of an additive; flame retardant polycarbonate resin composition, characterized in that it comprises a molded article using the same.
According to the present invention, by reducing the amount of fluorinated olefin resin used to solve the unbalance of the strain during injection molding to improve the workability, flame retardant polycarbonate resin composition excellent in workability with significantly improved flame retardancy, fluidity, mechanical properties, heat resistance, and weather resistance and using the same There is an effect of providing a molded article.

Description

Flame retardant polycarbonate resin composition excellent in processability and molded article using the same {FLAME RETARDANT POLYCARBONATE COMPOSITION HAVING PROCESSABILITY AND MOLDED RPODUCT USING THE SAME}

The present invention relates to a flame retardant polycarbonate resin composition excellent in workability and a molded article using the same. More specifically, flame retardant polycarbonate having excellent flame retardancy, fluidity, mechanical properties, heat resistance, and weather resistance, while reducing the amount of fluorinated olefin resin to improve processability. It relates to a resin composition and a molded article using the same.

Polycarbonate (PC) resin is prepared by condensation polymerization of aromatic diol monomers such as bisphenol A and carbonate precursors such as phosgene, and has excellent impact strength, stiffness and heat resistance, as well as excellent injection workability. Although it is applied to a wide range of fields such as automobile parts, building materials, optical parts, etc., there are disadvantages in that the flame retardancy is not excellent and the hydrolysis resistance and weather resistance are weak.

In order to solve this problem, we tried to improve the heat resistance, impact strength and flame retardancy by adding rubber, flame retardant or teflon to polycarbonate, but when the excessive amount of flame retardant is used, the heat resistance is lowered. In this case, char is formed during combustion, and thus a drip phenomenon is generated. Therefore, when Teflon is added to prevent this, flame retardancy is improved, but a problem of deterioration of the processability and transparency is caused due to unbalance of strain during extrusion injection.

Korean Patent Publication No. 2014-0069035

In order to solve the problems of the prior art as described above, the present invention provides a flame retardant polycarbonate resin composition excellent in flame retardancy, fluidity, mechanical properties, heat resistance, and weather resistance while improving the processability by reducing the amount of fluorinated olefin resin used to provide a molded article using the same For the purpose of

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

In order to achieve the above object, the present substrate (a) 60 to 80% by weight of a polycarbonate resin; (b) 1 to 10% by weight of alkyl (meth) acrylate-vinylaromatic compound-vinylcyan compound copolymer resin; (c) 1 to 10% by weight of vinylaromatic compound-vinylcyan compound copolymer resin; (d) 1 to 10% by weight of silicone-acrylic impact modifier; (e) 3 to 20% by weight of a liquid phosphorous flame retardant; (f) 0.1 to 0.7 wt% of fluorinated olefin resin; And (g) 0 to 5% by weight of an additive; provides a flame retardant polycarbonate resin composition comprising.

The present invention also provides a molded article prepared from the flame retardant polycarbonate resin composition.

As described above, according to the present invention, the flame-retardant polycarbonate resin composition has significantly improved flame retardancy, fluidity, mechanical properties, heat resistance, and weather resistance while eliminating the imbalance of strain during extrusion injection to improve workability by reducing the amount of fluorinated olefin resin. It works.

Hereinafter, the present description will be described in detail.

The flame retardant polycarbonate resin composition of the present disclosure comprises (a) 60 to 80 wt% of a polycarbonate resin; (b) 1 to 10% by weight of alkyl (meth) acrylate-vinylaromatic compound-vinylcyan compound copolymer resin; (c) 1 to 10% by weight of vinylaromatic compound-vinylcyan compound copolymer resin; (d) 1 to 10% by weight of silicone-acrylic impact modifier; (e) 3 to 20% by weight of a liquid phosphorous flame retardant; (f) 0.1 to 0.7 wt% of fluorinated olefin resin; And (g) 0 to 5% by weight of additives, characterized in that it comprises within this range, by reducing the amount of fluorinated olefin resin used to solve the imbalance of the strain during extrusion injection to improve the workability, but also flame retardancy, fluidity, mechanical properties, There is a markedly improved effect of heat resistance and weather resistance.

The (a) polycarbonate resin may be, for example, 65 to 80% by weight, or 70 to 77% by weight, and excellent tensile strength and elongation within this range.

For example, the polycarbonate resin (a) may have a melt index (250 ° C., 2.16 kg) of 3 to 30 g / 10 minutes, 10 to 30 g / 10 minutes, or 20 to 30 g / 10 minutes, within this range. Excellent workability in the

The (b) alkyl (meth) acrylate-vinylaromatic compound-vinyl cyan compound copolymer resin may be, for example, 2 to 8% by weight, or 3 to 5% by weight, and the effect of excellent impact strength within this range is excellent. have.

The (b) alkyl (meth) acrylate-vinylaromatic compound-vinyl cyan compound copolymer resin is, for example, 20 to 80% by weight of an alkyl (meth) acrylate compound, 10 to 70% by weight of a vinylaromatic compound and vinyl cyan compound 1 To 20 weight percent; Or 30 to 70% by weight of an alkyl (meth) acrylate compound, 20 to 60% by weight of a vinylaromatic compound and 5 to 15% by weight of a vinyl cyan compound; and within this range, the impact strength and fluidity are excellent.

The resin (b) may be, for example, a weight average molecular weight of 100,000 to 200,000 g / mol, 110,000 to 180,000 g / mol, or 120,000 to 160,000 g / mol, and within this range, fluidity, mechanical properties, colorability and weather resistance Excellent effect.

The alkyl (meth) acrylate compound is, for example, ethyl acrylate, ethyl methacrylate, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, propyl acrylate, propyl methacrylate, and 2- It may be at least one selected from the group consisting of ethylhexyl acrylate.

The (c) vinylaromatic compound-vinyl cyan compound copolymer resin may be, for example, 2 to 8% by weight, or 2 to 5% by weight, and has excellent heat resistance and mechanical strength within this range.

The (c) vinylaromatic compound-vinylcyan compound copolymer resin may include, for example, 60 to 80% by weight of vinylaromatic compound and 20 to 40% by weight of vinylcyan compound, and within this range, impact strength and physical property balance. Has an excellent effect.

The resin (c) may be, for example, a weight average molecular weight of 100,000 to 200,000 g / mol, 110,000 to 180,000 g / mol, or 120,000 to 160,000 g / mol, and within this range, tensile strength, flexural strength, fluidity and physical properties. The effect is excellent in balance.

In the (b) resin and (c) resin, the vinylaromatic compound may be at least one selected from the group consisting of styrene, α-methylstyrene, o-ethylstyrene, p-ethylstyrene, and vinyltoluene.

In the (b) resin and (c) resin, the vinyl cyan compound may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.

The (d) silicone-acrylic impact modifier may be, for example, 1 to 6% by weight, or 2 to 5% by weight, and within this range, impact strength, tensile strength and weather resistance are all excellent.

The (d) silicone-acrylic impact modifier may include, for example, a silicone core and a shell surrounding the silicone-acrylic impact modifier, and in this case, excellent impact strength and weather resistance.

The (d) silicone-acrylic impact modifier is, for example, 10 to 60% by weight of silicone and 40 to 90% by weight of alkyl (meth) acrylate monomer, or 20 to 40% by weight of silicone and alkyl (meth) acrylate monomer 60 To 80% by weight may be included, in this case, the impact strength, tensile strength, flexural rigidity and weather resistance is excellent effect.

The alkyl (meth) acrylate monomers are, for example, ethyl acrylate, ethyl methacrylate, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, propyl acrylate, propyl methacrylate, and 2 It may be at least one selected from the group consisting of ethylhexyl acrylate.

The (e) liquid phosphorus flame retardant may be, for example, 7 to 17% by weight, or 10 to 15% by weight, and has excellent flowability and flame retardancy within this range.

The liquid phosphorus-based flame retardant (e) may be in a liquid state, for example, at 20 ° C. and 1.01325 bar, and has excellent flowability within this range, thereby improving workability.

The liquid phosphorus-based flame retardant (e) is for example trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixenyl phosphate, resorcinol bis (diphenyl phosphate), phenyl diresosinol phosphate, bisphenol 1 selected from the group consisting of diphenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, phenyl di (isopropylphenyl) phosphate, triisophenyl phosphate, diphenylphosphate, resorcinol diphosphate, and aromatic polyphosphate It may be more than one species.

The (f) fluorinated olefin resin may be, for example, 0.2 to 0.5% by weight, or 0.2 to 0.4% by weight, in which the imbalance of the strain is reduced during injection molding, thereby improving workability and improving mechanical properties, particularly impact strength. It works.

The (f) fluorinated olefin resin may include, for example, polytetrafluoroethylene, and in another example, polytetrafluoroethylene, a mixture of polytetrafluoroethylene and styrene-acrylonitrile, or polytetrafluoroethylene And a mixture of polymethyl methacrylate; and within this range, there is an effect of excellent workability and mechanical properties, particularly impact strength.

The (f) fluorinated olefin resin may include, for example, 10% by weight, 30% by weight, or 45% by weight or more of polytetrafluoroethylene. Within this range, workability and flame retardancy may be prevented by preventing char formation in polycarbonate. Excellent effect.

In another example, the (f) fluorinated olefin resin may include 10 to 90% by weight, 30 to 70% by weight, or 45 to 55% by weight of polytetrafluoroethylene, and 10 to 90% by weight of styrene-acrylonitrile, and 30 to 30% by weight. It may contain 70% by weight, or 45 to 55% by weight, and within this range to prevent the process and the formation of char of the polycarbonate has an effect of excellent flame retardancy.

The (g) additive may be, for example, 0.1 to 3% by weight, or 0.5 to 2% by weight, and has an excellent balance of physical properties while maintaining physical properties of the flame retardant polycarbonate resin composition within this range.

The additive (g) may be at least one selected from the group consisting of UV stabilizers, lubricants, antioxidants, pigments, and inorganic fillers.

The flame retardant polycarbonate resin composition has an impact strength of 30 kgf · cm / cm or more, 40 kgf · cm / cm or more, or 50 to 80 kgf · cm /, measured according to ASTM D256 (3.2 mm, 23 ° C.), for example. may be at least cm.

The flame retardant polycarbonate resin composition may be, for example, 60% or more, 70% or more, or 70 to 100% weather resistance measured according to UL 746C.

The flame retardant polycarbonate resin composition of the present disclosure comprises (a) 60 to 80 wt% of a polycarbonate resin; (b) 1 to 10% by weight of alkyl (meth) acrylate-vinylaromatic compound-vinylcyan compound copolymer resin; (c) 1 to 10% by weight of vinylaromatic compound-vinylcyan compound copolymer resin; (d) 1 to 10% by weight of silicone-acrylic impact modifier; (e) 3 to 20% by weight of a liquid phosphorous flame retardant; (f) 0.1 to 0.7 wt% of fluorinated olefin resin; And (g) 0 to 5% by weight of additives; may be prepared by the step of extrusion after melt kneading.

For example, the melt kneading may be performed at 230 to 270 ° C, or 240 to 260 ° C.

Provided is a molded article prepared by including the flame retardant polycarbonate resin composition of the present disclosure.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

EXAMPLE

The compound used in the following Example and the comparative example is as follows.

* PC (Polycarbonate): Polycarbonate chip (LG DOW company) with melt index of 15 g / 10 minutes

* Si-PC (silicone-containing polycarbonate): Si-PC polymer chip (Samyang) with melt index (1.2kg, 300 ℃) 3g / 10min

* ASA: ASA927 (LG Chemistry)

SAN: SAN 81HF (LG Chemistry)

* Si-Rubber (impact enhancer): S-2001 (Mitsubishi Rayon Company)

* Liquid Phosphorus Flame Retardant: Bisphenol-Adiphosphate Compound (ADECA)

* UV stabilizer: UV5411 (Sifine)

Polytetrafluoroethylene: Teflon-G (50% by weight of SAN and 50% by weight of Teflon; Posera)

* Additive: LC102N (Lion CHEMTEC)

          IRGANOX-1076 (BASF)

          IRGAFOX-168 (BASF)

Example  1 to 4 and Comparative example  1 to 5

Each component is added to the corresponding content as shown in Table 1, followed by mixing uniformly with a mixer (super mixer), then twin-screw extruder (twin-screw extruder), melted and kneaded at 240 ~ 260 ℃ extruded After processing and pelletizing and drying at 80 ° C. for at least 4 hours, and standing at room temperature for 1 day, the specimen was injected using ENGEL to prepare a flame retardant polycarbonate resin composition specimen. In Table 1, additives used 0.2% by weight of LC102N (Lion CHEMTEC), 0.2% by weight of IRGANOX-1076 (BASF), and 0.1% by weight of IRGAFOX-168 (BASF).

[Test Example]

Properties of the flame retardant polycarbonate resins prepared in Examples 1 to 4 and Comparative Examples 1 to 5 were measured by the following method, and the results are shown in Table 1 below.

* Melt Flow Index (MFI, g / 10min): Measured according to ASTM D1238 (250 ° C, 2.16 kg).

* Tensile strength (kgf / cm ² ) and elongation (%): measured according to ASTM D638 (thickness of 3.2mm, 23 ℃).

* Flexural Strength (kg / cm ² ): measured in accordance with ASTM D790 (thickness of 3.2mm, 23 ℃).

* Flexural modulus (kg / cm ² ): was measured according to ASTM D790 (sample thickness 3.2mm, 23 ℃).

* Izod impact strength (1/4 ", kgfcm / cm): Measured in accordance with ASTM D256 (sample thickness 3.2mm, 23 ℃).

* Flame retardancy: It was measured by UL-94 flame retardancy test method, which is a method of evaluating flame retardancy from drip property by burning time after attaching flame (ignition source) of burner to a fixed size specimen vertically for 10 seconds. The burning time is the time that the specimen continues flame burning after the flame (ignition source) is far away, and the flammability of the cotton by drip is about 300mm below the lower end of the specimen. Determined by being flammable, flame retardant grades are divided into V-0, V-1 and V-2.

* HDT (° C, heat deflection temperature): measured according to ASTM D648.

* Extrudeability: When extruded, the compound powder mixed in the hopper is formed into pellets under the condition that it can be cut out by 3-10 strains by heat and pressure and cooled down by cold water. If not, it is very difficult to strain the cutting machine and create the desired extrusion environment. Therefore, it was judged as good or bad depending on whether the strain was easily caught by the cutting machine and the extrusion workability was good.

* Weatherability (%): The test was carried out with a weatherometer specified in ISO 105. The irradiation intensity of the xenon arc beam was set at 0.35 W / m 2, the wavelength of 340 nm, and the black panel temperature of 63 ° C. for 1000 hours, and then the impact strength was measured by measuring the impact strength according to ASTM D256 before and after irradiation.

division Example Comparative example One 2 3 4 One 2 3 4 5 PC 76.75 74.75 74.75 72.75 79.25 79.00 73 - 79.75 Si-PC 73 ASA 4 4 4 4 4 4 4 4 4 SAN 3 3 3 3 3 3 3 3 3 Si-rubber 3 5 3 5 0 0 7 6 0 additive 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Flame retardant 12 12 14 14 12 12 12 13 12 UV Stabilizer 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Teflon 0.25 0.25 0.25 0.25 0.75 One 0 0 0.25 additive 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 The tensile strength 670 580 630 630 650 650 650 590 650 Elongation 40 106 70 88 90 90 90 20 90 Flexural strength 1080 950 1050 940 1000 1000 1000 900 1000 Impact strength 70 50 68 51 7.5 7.5 7.5 13 8 HDT 93 94 90 91 94.6 94.3 94.3 93.9 94.5 Flame retardant V-0 V-1 V-0 V-0 flame
Drip V-1 flame
Drip V-0 fire
Flower Drip Weather resistance 80 100 70 90 45 55 48 60 50 Extrusion
Workability Good Good Good Good Good Bad Good Good Good MFI 16 13 20 15 19 19 12 9 13 curve
Modulus 22,000 22,000 24,000 24,000 29,000 29,000 21,000 22,000 21,000

As shown in Table 1, Examples 1 to 4 prepared by the present substrate was excellent in weather resistance, but also excellent in mechanical properties such as tensile strength, elongation, flexural strength, flexural modulus, and impact strength, and flame retardancy and thermal deformation temperature. , Melt flow index, and extrusion workability were also excellent.

On the other hand, Comparative Examples 1, 2 and 5, which do not contain Si-rubber as an impact modifier, had a sharp drop in impact strength and weather resistance, and Comparative Example 3 without Teflon had poor impact strength, flame retardancy and weather resistance, and Teflon. Excessive Comparative Example 2 contained extruded workability

In addition, in Comparative Example 4 using a polycarbonate containing silicon instead of polycarbonate, the flexural modulus, tensile strength and elongation were decreased.

Claims (13)

(a) 60 to 80 weight percent of a polycarbonate resin;
(b) 1 to 10% by weight of alkyl (meth) acrylate-vinylaromatic compound-vinylcyan compound copolymer resin;
(c) 1 to 10% by weight of vinylaromatic compound-vinylcyan compound copolymer resin;
(d) 3 to 5% by weight of silicone-acrylic impact modifier;
(e) 3 to 20% by weight of a liquid phosphorous flame retardant;
(f) 0.1 to 0.7 wt% of fluorinated olefin resin; And
(g) 0-5% by weight of additives;
Including,
A flame-retardant polycarbonate resin composition characterized by weather resistance of 70% or more, measured according to UL 746C.
The method of claim 1,
The polycarbonate resin (a) is flame retardant polycarbonate resin composition, characterized in that the melt index (250 ℃, 2.16kg) is 3 to 30 g / 10 minutes.
The method of claim 1,
The (b) alkyl (meth) acrylate-vinylaromatic compound-vinyl cyan compound copolymer resin is 20 to 80% by weight alkyl (meth) acrylate rubber, 10 to 70% by weight vinyl aromatic compound and 1 to 20 vinyl cyan compound Flame retardant polycarbonate resin composition comprising a weight percent.
The method of claim 1,
The flame retardant polycarbonate resin composition of (c) the vinylaromatic compound-vinylcyan compound copolymer comprises 60 to 80 wt% of the vinylaromatic compound and 20 to 40 wt% of the vinylcyan compound.
The method of claim 1,
The (d) silicone-acrylic impact modifier is a flame-retardant polycarbonate resin composition characterized in that it comprises a silicone core and a shell surrounding the shell containing an alkyl (meth) acrylate monomer.
The method of claim 1,
The (e) liquid-based phosphorous flame retardant is a flame retardant polycarbonate resin composition, characterized in that the liquid state at 20 ℃, 1.01325 bar.
The method of claim 6,
(E) The liquid phosphorus-based flame retardant is trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixenyl phosphate, resorcinol bis (diphenyl phosphate), phenyl diresorcinol phosphate, bisphenol diphenyl At least one member selected from the group consisting of phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, phenyl di (isopropylphenyl) phosphate, triisophenyl phosphate, diphenyl phosphate, resorcinol diphosphate, and aromatic polyphosphate Flame retardant polycarbonate resin composition, characterized in that.
The method of claim 1,
(F) The fluorinated olefin resin is a flame retardant polycarbonate resin composition, characterized in that it comprises polytetrafluoroethylene.
The method of claim 1,
The (g) additive is a flame retardant polycarbonate resin composition, characterized in that at least one selected from the group consisting of UV stabilizers, lubricants, antioxidants, pigments and inorganic fillers.
The method of claim 1,
The flame-retardant polycarbonate resin composition is a flame-retardant polycarbonate resin composition characterized in that the impact strength measured based on ASTM D256 (3.2mm, 23 ℃) 30 kgf · cm / cm or more.
delete (a) 60 to 80 weight percent of a polycarbonate resin; (b) 1 to 10% by weight of alkyl (meth) acrylate-vinylaromatic compound-vinylcyan compound copolymer resin; (c) 1 to 10% by weight of vinylaromatic compound-vinylcyan compound copolymer resin; (d) 3 to 5% by weight of silicone-acrylic impact modifier; (e) 3 to 20% by weight of a liquid phosphorous flame retardant; (f) 0.1 to 0.7 wt% of fluorinated olefin resin; And (g) 0 to 5% by weight of the additives; melt-kneading and extruding, and characterized in that the weather resistance measured according to UL 746C 70% or more method for producing a flame retardant polycarbonate resin composition.
A molded article comprising the flame retardant polycarbonate resin composition according to any one of claims 1 to 10.