KR102043095B1 - Polycarbonate resin composition and molded article comprising the same - Google Patents

Abstract

The present invention relates to a polycarbonate resin composition and a molded article comprising the same, more specifically, 50 to 80% by weight of a polycarbonate resin having a melt index (300 ° C., 1.2 kg) of more than 10 to less than 70 g / 10 min; 5-20% by weight of an aromatic vinyl compound-conjugated diene compound-vinyl cyan compound copolymer; Phosphorus flame retardant 5-30 wt%; And 0.1 to 7% by weight of a plate-shaped, spherical or mixed inorganic fillers thereof, and a polycarbonate resin composition comprising a molded article including the same.
According to the present invention, there is an effect of providing a polycarbonate resin composition excellent in impact strength, fluidity and flame retardancy, excellent appearance and gloss, and reduced post-shrinkage, and a molded article including the same.

Description

POLYCARBONATE RESIN COMPOSITION AND MOLDED ARTICLE COMPRISING THE SAME

The present invention relates to a polycarbonate resin composition, and more particularly to a polycarbonate resin composition excellent in impact strength, fluidity and flame retardancy, excellent appearance and gloss, and reduced post-shrinkage, and a molded article comprising the same.

Polycarbonate resin has a high impact resistance at room temperature and has excellent mechanical properties such as impact strength, thermal properties such as flame retardancy and heat resistance, and is well known as an amorphous thermoplastic resin having high dimensional stability. It is widely used in various applications such as housing materials for electronic products.

In addition, studies have been conducted to realize more excellent physical properties by reinforcing the polycarbonate resin with various fillers such as inorganic fillers, carbon fibers, and glass fibers, and acrylonitrile-butadiene-styrene copolymers, not polycarbonate resins alone. In addition, researches on resin compositions having improved processability and formability by mixing with are actively underway.

In this regard, molded articles are becoming thinner and larger in recent years, and a high level of appearance quality is required. Particularly, in the case of large parts such as a TV or a refrigerator, post-shrinkage of the resin occurs after injection molding and assembly of the product, and the tightening failure and crack due to the dimensional change and the stress caused by contact with the metal material are increased. Problems such as occurrence, and the like, the development of a material that can reduce post-shrinkage is constantly required.

KR 2011-0057249 A

The present invention relates to a polycarbonate resin composition, and more particularly, to provide a polycarbonate resin composition which is excellent in impact strength, fluidity, and flame retardancy, and has excellent appearance and gloss, and has reduced post-shrinkage.

Moreover, an object of this invention is to provide the molded article containing the said polycarbonate 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 object, the present invention is 50 to 80% by weight of a polycarbonate resin having a melt index (300 ℃, 1.2 kg) is more than 10 to less than 70 g / 10 min; 5-20 wt% of an aromatic vinyl compound-conjugated diene compound-vinylcyan compound copolymer; Phosphorus flame retardant 5-30 wt%; And 0.1 to 7% by weight of the plate-shaped, spherical or mixed inorganic fillers thereof; provides a polycarbonate resin composition comprising a.

The present invention also provides a molded article comprising the polycarbonate resin composition.

According to the present invention, there is an effect of providing a polycarbonate resin composition excellent in impact strength, fluidity and flame retardancy, excellent appearance and glossiness, and reduced post-shrinkage, and a molded article including the same.

Hereinafter, the present invention will be described in detail.

The present inventors have excellent impact strength, fluidity, flame retardancy, appearance and gloss when the polycarbonate resin composition includes a polycarbonate resin having a certain range of melt index and an inorganic filler having a specific form, and also reduces post-shrinkage. The present invention was completed based on this finding.

Looking at the polycarbonate resin composition according to the present invention in detail.

The polycarbonate resin composition may be 50 to 80% by weight of a polycarbonate resin having a melt index (300 ° C., 1.2 kg) of more than 10 to less than 70 g / 10 min; 5-20 wt% of an aromatic vinyl compound-conjugated diene compound-vinylcyan compound copolymer; Phosphorus flame retardant 5-30 wt%; And 0.1 to 7% by weight of plate-like, spherical or mixed inorganic fillers thereof.

The polycarbonate resin is not particularly limited, but may be, for example, a resin polymerized including a bisphenol-based monomer and a carbonate precursor.

Examples of the bispinol monomers include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide and bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BPA), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ), 2,2-bis (4-hydroxy-3 , 5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2 , 2-bis (4-hydroxy-3chlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl ) Propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane and α, ω-bis [3- (ο-hydroxyphenyl) propyl] Polydimethylsiloxane It may be at least one selected from the group consisting of acids.

The carbonate precursor is, for example, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis ( Diphenyl) carbonate, carbonyl chloride (phosgene), triphosgene, diphosgene, carbonyl bromide, and bishaloformate.

The polycarbonate resin may have, for example, a melt index (300 ° C., 1.2 kg) of greater than 10 to less than 70 g / 10 min, 15 to 50 g / 10 min, or 15 to 45 g / 10 min, within this range. Excellent workability and formability, excellent balance of physical properties. The melt index means a melt index measured under the conditions of standard measurement ASTM D1238 (300 ° C., 1.2 kg).

For example, the polycarbonate resin may be included in an amount of 50 to 80% by weight, 60 to 80% by weight, or 70 to 80% by weight with respect to the polycarbonate resin composition. , Appearance and gloss is excellent effect.

The aromatic vinyl compound-conjugated diene compound-vinyl cyan compound copolymer may be, for example, a graft copolymer in which an aromatic vinyl compound and a vinyl cyan compound are grafted to a polymerized rubber polymer including a conjugated diene compound.

As the graft polymerization, for example, emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization may be used, and preferably, a method of emulsion polymerization may be used, in which case the impact strength and the balance of physical properties are excellent.

The conjugated diene compound is 1 selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene It may be a species or more, preferably 1,3-butadiene, in this case there is an excellent effect of the mechanical and physical properties balance.

The aromatic vinyl compound may be, for example, one or more selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, and vinyltoluene, wherein the vinyl cyan compound is, for example, acryl It may be at least one selected from the group consisting of ronitrile, methacrylonitrile and ethacrylonitrile.

The aromatic vinyl compound-conjugated diene compound-vinyl cyan compound copolymer may be included in an example of 5 to 20% by weight, 5 to 15% by weight, or 6 to 12% by weight based on the polycarbonate resin composition. Impact strength and fluidity are excellent in the inside.

The aromatic vinyl compound-conjugated diene compound-vinyl cyan compound copolymer may form an alloy with the polycarbonate resin as an example. In this case, the mechanical properties are excellent.

The phosphorus flame retardant is not particularly limited as long as it can be included in the polycarbonate resin composition, for example, may be an aromatic phosphate ester compound.

The aromatic phosphate ester compound may be at least one selected from the group consisting of, for example, bisphenol A diphosphate, bisphenol A bis (dialkyl phosphate), and bisphenol A bis (diaryl phosphate).

The alkyl group may be, for example, an alkyl group having 1 to 20 carbon atoms, or 1 to 15 carbon atoms, and the aryl group may be, for example, an aryl group having 6 to 30 carbon atoms or 6 to 20 carbon atoms.

For example, the phosphorus-based flame retardant may be included in an amount of 5 to 30 wt%, 10 to 25 wt%, or 10 to 20 wt% with respect to the polycarbonate resin composition, and excellent flame retardancy within this range, but excellent balance of physical properties There is.

Inorganic filler of the present invention is characterized in that the plate-like, spherical or a mixture thereof. Glass fiber, which is a typical representative inorganic filler, has a problem of protruding to the surface even when only a small amount is used in the needle-like structure, and thus the use of the glass fiber is excluded. In addition, in addition to the glass fiber, the inorganic filler having a needle-like structure excludes its use in the present invention for the same reason as described above.

The plate shape may be understood as a flat shape that is commonly recognized, and means a flat and even shape with almost no height at the top and bottom surfaces, and the top and bottom planes and sides are not limited.

The spherical shape may be understood as a sphere having a spherical shape that is commonly recognized, and means a shape including an ellipsoid of 0.3 or less, 0.2 or less, or 0.1 or less.

The plate-shaped and spherical inorganic fillers may each have an average particle diameter of 10 μm or less. In particular, the plate-shaped inorganic filler may have an average particle diameter of 8 μm or less, 5 μm or less, or 0.01 to 4 μm, and the spherical inorganic filler may have an average particle diameter of 8 μm or less, 6 μm or less, or 2 to 6 μm. Within each of these ranges, post-shrinkage reduction and clean and beautiful appearance and formability are excellent.

The plate-shaped inorganic filler may be at least one selected from the group consisting of, for example, talc, mica, wollastonite, calcium carbonate, wood powder and chalk, and preferably talc and mica. ), Wollastonite, and the like, specific examples may be talc including SiO ₂ , MgO, Al ₂ O ₃ , Fe ₂ O ₃ , CaO, and the spherical inorganic filler may be, for example, glass beads. bead), in this case the effect is excellent in appearance and gloss.

The plate-shaped inorganic filler may have a density of, for example, 0.1 to 10 g / cm ³ , 1 to 8 g / cm ³ , or 1 to 5 g / cm ³ , and post-shrinkage is reduced within this range, and impact strength Excellent effect.

The plate-shaped and spherical inorganic fillers may be included, for example, 0.1 to 7% by weight, 0.5 to 6% by weight, or 1 to 5% by weight with respect to the polycarbonate resin composition, with post-shrinkage reduction within this range, Clean and beautiful appearance and formability is excellent effect.

Mixing of the plate-shaped and spherical inorganic fillers may be included, for example, in the range of 0.1 to 7 wt%, 0.5 to 6 wt%, or 1 to 5 wt% with respect to the polycarbonate resin composition, and with post-shrinkage reduction within this range. Clean and beautiful appearance and formability is excellent.

For example, the polycarbonate resin composition may have a post-shrinkage ratio (1/1000) of 5 or less, 4.99 or less, or 1 to 4.99.

For example, the polycarbonate resin composition may have glossiness of 92 or more, 94 or more, or 94 to 99.

The molded article of the present invention is characterized by comprising the polycarbonate resin composition.

The molded article may be, for example, an injection molded article, and in particular, may be a large injection molded article.

The mall injection molded article may be, for example, a housing of an electric / electronic product such as a TV, a refrigerator, a washing machine, and the like.

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

EXAMPLE

Examples 1-8 and Comparative Examples 1-6

Polycarbonate resin, acrylonitrile-butadiene-styrene copolymer, phosphorus flame retardant and inorganic filler were mixed using a mixer in the content (% by weight) shown in Table 1 below, and melted at a temperature of 230 to 270 ° C. using a twin screw extruder. And kneading to prepare a resin composition in the form of pellets. A specimen for measuring physical properties was prepared by injecting the prepared resin composition in pellet form.

[Test Example]

The physical properties of the polycarbonate resin composition specimens obtained in Examples 1 to 8 and Comparative Examples 1 to 6 were measured by the following methods, and the results are shown in Tables 1 and 2, respectively.

How to measure

* Average particle size: The particle size was measured using a particle measuring instrument (CHDF, MATEC APPLIED SCIENCE).

* Notched Izod Impact Strength (kg · cm / cm): Measured according to the standard measurement ASTM D256 using a 1/8 "specimen.

* Melt Index (Melt Index, g / 10 min): Measured according to the standard measurement ASTM D1238 (250 ° C., 2.16 kg conditions) using the specimen.

* Post-shrinkage rate (1/1000): Measures the change in post-shrinkage by comparing the size of the specimen after 10 days with the size of the initially injected specimen according to the standard measurement ISO 294-4 / ASTM D955, using a 3D optical scope instrument It was.

* Glossiness: Measured at 45 ° using a Gloss meter.

* Appearance evaluation: Visually assess whether the molded specimens are filled with fillers, etc., and if they do not protrude at all, ◎, partially protruded but difficult to identify with the naked eye ○, partially protruded and can be visually identified In this case, the description is divided by ×.

* Flame retardancy: measured in accordance with UL-94 test standards using a 1.5 mm thick specimen.

division Example One 2 3 4 5 6 7 8 PC 1 76 74 72 76 74 72 - - PC 2 - - - - - - 74 74 ABS 8 8 8 8 8 8 8 8 Phosphorus Flame Retardant 15 15 15 15 15 15 15 15 weapon
Filler Plate One 3 5 - - - 3 - rectangle - - - One 3 5 - 3 * Properties Impact strength 14 14 12 13 13 12 12 13 Melt index 28 27 27 28 26 26 35 34 Post-shrinkage 4.98 4.75 4.59 4.99 4.81 4.62 4.77 4.83 Glossiness 97 95 94 97 96 95 96 96 Appearance evaluation ◎ ○ ○ ◎ ◎ ○ ◎ ◎ Flame retardant V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0

division Comparative example One 2 3 4 5 6 PC 1 77 69 69 74 - - PC 3 - - - - 74 - PC 4 - - - - - 74 ABS 8 8 8 8 8 8 Phosphorus Flame Retardant 15 15 15 15 15 15 weapon
Filler Plate - 8 - - 3 3 rectangle - - 8 - - - Needle-shaped - - - 3 - - * Properties Impact strength 15 9 9 13 19 5 Melt index 28 25 23 27 18 46 Post-shrinkage 5.39 4.51 4.57 4.79 4.87 4.92 Glossiness 97 90 91 95 95 97 Appearance evaluation ◎ △ △ × ○ ◎ Flame retardant V-0 V-0 V-0 V-0 V-0 V-2

Each component of the said Table 1 and 2 is as follows.

* PC 1: Polycarbonate resin (product name LUPOY PC 1300-22) of melt index 22 g / 10 min (300 degreeC, 1.2 kg)

* PC 2: Polycarbonate resin (product name LUPOY PC UF1004D manufactured by LG Chemical Co., Ltd.) with a melt index of 40 g / 10 min (300 ° C, 1.2 kg)

* PC 3: Polycarbonate resin (product name LUPOY PC 1300-03) of melt index 10 g / 10 min (300 degreeC, 1.2 kg)

* PC 4: Polycarbonate resin (product name LUPOY PC 1080-70, manufactured by LG Chem) having a melt index of 70 g / 10 min (300 ° C, 1.2 kg)

* ABS: Acrylonitrile-butadiene-styrene copolymer (manufactured by LG Chem, product name DP270E)

* Phosphorus flame retardant: Bisphenol A diphosphate (manufactured by Adeka, BPADP)

* Plate-shaped inorganic fillers: talc with SiO ₂ , MgO, Al ₂ O ₃ , Fe ₂ O ₃ , CaO component, average particle diameter (95 wt%) 3.3 μm or less, density 2.8 g / cm ³ (manufactured by Koch)

* Spherical inorganic filler: glass beads having an average particle diameter of 4 μm (manufactured by Sovitec)

* Acicular inorganic filler: 4 mm long chopped glass fiber coated with amino silane (manufactured by Owens Corning)

As shown in Table 1, in Examples 1 to 8 prepared according to the present invention, the impact strength, melt index, gloss, appearance and flame retardancy are all excellent, compared to Comparative Example 1 that does not include an inorganic filler It was confirmed that the shrinkage was significantly reduced to about 8 to 15%.

On the other hand, in Comparative Examples 2 and 3 containing an excessive amount of plate-shaped and spherical inorganic fillers, it was confirmed that the impact strength, melt index, glossiness and appearance were all reduced, and in the case of Comparative Example 4 including the needle-shaped inorganic fillers on the surface It was confirmed that the glass fiber protrudes as a whole and the appearance characteristics are very poor. In addition, in the case of Comparative Example 5 containing a polycarbonate resin having a low melt index, the melt index of the resin composition was significantly lowered, resulting in poor moldability, and in Comparative Example 6 including a polycarbonate resin having a high melt index, impact strength and flame retardancy were very high. It was confirmed that the poor.

In conclusion, the present inventors from the above examples and comparative examples using a polycarbonate resin having a range of melt index and an inorganic filler having a specific form, while excellent impact strength, fluidity, flame retardancy, appearance and gloss, It was confirmed that the polycarbonate resin composition having reduced post-shrinkage and a molded article including the same may be realized.

Claims (13)

70 to 80% by weight of a polycarbonate resin having a melt index (300 ° C., 1.2 kg) of 15 to 45 g / 10 min; Aromatic vinyl compound-conjugated diene compound-vinylcyan compound copolymer 6-12 wt%; 10 to 20 wt% phosphorous flame retardant; And 1 to 5% by weight of plate-shaped, spherical or mixed inorganic fillers (excluding glass fiber); and having a post-shrinkage ratio (1/1000) of 4.99 or less and glossiness of 94 or more. . The method of claim 1,
The aromatic vinyl compound-conjugated diene compound-vinyl cyan compound copolymer is a polycarbonate characterized in that the graft copolymer in which an aromatic vinyl compound and a vinyl cyan compound are grafted to a rubberized polymer including a conjugated diene compound. Resin composition. The method of claim 1,
The conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene Polycarbonate resin composition, characterized in that. The method of claim 1,
The aromatic vinyl compound is at least one member selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene and vinyltoluene. The method of claim 1,
The vinyl cyan compound is at least one member selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile. The method of claim 1,
The phosphorus flame retardant polycarbonate resin composition, characterized in that the aromatic phosphate ester compound. The method of claim 6,
The aromatic phosphate ester compound is at least one member selected from the group consisting of bisphenol A diphosphate, bisphenol A bis (dialkyl phosphate) and bisphenol A bis (diaryl phosphate). The method of claim 1,
The plate-shaped and spherical inorganic filler is a polycarbonate resin composition, characterized in that each has an average particle diameter of 10 ㎛ or less. The method of claim 1,
The plate-type inorganic filler is polycarbonate resin composition, characterized in that at least one selected from the group consisting of talc (mica), mica (mica), wollastonite, calcium carbonate, wood powder and chalk. The method of claim 1,
The spherical inorganic filler is a polycarbonate resin composition, characterized in that the glass bead (glass bead). delete delete A molded article comprising the polycarbonate resin composition according to any one of claims 1 to 10.