KR101788365B1 - Polycarbonate stryrene based copolymer alloy composition and injection molding - Google Patents

Abstract

The present invention relates to a polycarbonate-styrenic copolymer alloy composition and a molded article thereof, and, in accordance with the present invention, a mixture of a polycarbonate resin and a flaky filler-pigment is used as a pigment of a styrene- By using a potassium silicate-dye mixture (aka Marble pigment) as a pigment to provide a spot marble pattern, the mechanical strength required for the polycarbonate-styrene type copolymer alloy composition, dimensional stability after molding, workability, A styrene-based copolymer alloy composition capable of providing a spot marble color under improved whiteness while providing a high gloss, processability and surface gloss, and a molded article obtained therefrom.

Description

TECHNICAL FIELD [0001] The present invention relates to a polycarbonate styrene-based copolymer alloy composition and an injection molding,

More particularly, the present invention relates to a polycarbonate-styrenic copolymer alloy composition and a molded article thereof, and more particularly to a polycarbonate-styrenic copolymer composition and a molded article thereof, which uses a mixture of a polycarbonate resin and a flaky filler- styrene-based copolymer alloy composition by using a mixture of a potassium silicate-dye as a pigment for providing a spot marble pattern, while providing mechanical strength, dimensional stability after molding, workability, post-processability and surface gloss required for a polycarbonate- At the same time, a polycarbonate-styrofoam that can provide a spot marble pattern under improved whiteness

Polycarbonate resins are amorphous and thermoplastic plastics and have excellent mechanical and thermal properties. Has high impact resistance at room temperature, excellent thermal stability, and high dimensional stability. Research has been carried out on reinforcing the polycarbonate resin with various fillers such as an inorganic filler, carbon fiber and glass fiber to realize excellent physical properties. In addition, research on a resin composition which is improved not only by polycarbonate resin but also by mixing with a styrenic copolymer to improve workability is actively under way.

Polycarbonate resins are widely used for various applications due to the above properties. In recent years, there has been an increasing demand for applying various colors to a polycarbonate resin to realize various appearance. Accordingly, researches on materials having chromatic, pearl, or artificial marble patterns are also in progress. Among them, the artificial marble pattern is collectively referred to as a marble color, and the related prior arts have a problem in that the physical properties at the time of processing are deteriorated and the marble pattern is not expressed well on the appearance (refer to related US Pat. No. 5,905,122, US Patent No. 5,489,665 , Korean Patent Laid-Open Publication No. 2001-84285, and Korean Patent Laid-Open No. 2001-28128).

In order to solve the problems of the prior art described above, the present invention relates to a pigment which provides a spot marble pattern after injection molding using a mixture of a plate-like filler and a pigment as a pigment of a polycarbonate resin and a styrenic copolymer alloy By using the mixture of potassium silicate-dyes, it is possible to provide the polycarbonate-styrenic copolymer composition with mechanical strength, dimensional stability after molding, workability, post-processability and surface gloss, Styrene-based copolymer solid composition capable of providing an improved whiteness and a molded article obtained therefrom.

In order to achieve the above object,

Styrene-based copolymer alloy composition characterized in that it comprises a polycarbonate resin, a styrenic copolymer, a plate-like filler-pigment mixture, and a potassium silicate-dye mixture.

In addition,

Supplying a main flask of a twin screw extruder with 40 to 80% by weight of a polycarbonate resin, 5 to 20% by weight of a styrenic copolymer, and 0 to 20% by weight of a phosphorus flame retardant, ;

Supplying the resulting extrudate to a main hopper of a twin-screw extruder, supplying the potassium silicate-dye mixture to a sider and subjecting the extrudate to secondary extrusion at 220 to 290 ° C; And

Forming a spot-marble color molded product by injection molding obtained by secondary extrusion; A method of manufacturing a molded article is provided.

Furthermore, the present invention relates to a process for producing a spot (s), which is produced from the above-mentioned method, characterized in that the plate-like filler-pigment of the polycarbonate resin and the styrenic copolymer is dispersed and the potassium silicate- Thereby providing a spot marble color injection molded article.

According to the present invention there is provided a process for the preparation of a pigment mixture comprising a mixture of a potassium silicate-pigment as a pigment for providing a spot marble pattern after injection molding using a mixture of a polycarbonate resin and a flaky filler-pigment as an aloyi pigment of a styrenic copolymer alloy By using the mixture, the spot marble pattern is provided under the improved whiteness while providing the mechanical strength required for the polycarbonate-styrenic copolymer alloy composition, dimensional stability after molding, workability, post-processability and surface gloss. And the post-injection process (post-coating process) can be omitted or reduced, thereby providing an economical polycarbonate-styrene-based copolymer alloy composition and a molded article obtained therefrom.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph of a spot marble color molded article obtained by injection molding the alloy composition of Example 1. FIG.
Fig. 2 is a photograph of a spot marble color molded product obtained by injection molding the alloy composition of Comparative Example 2. Fig.

Hereinafter, the present invention will be described in detail.

The polycarbonate-styrene type copolymer alloy composition of the present invention is characterized by comprising a polycarbonate resin, a styrenic copolymer, a flaky filler-pigment mixture, and a potassium silicate-dye mixture.

For example, the polycarbonate resin is contained in a range of 40 to 85% by weight, or 50 to 70% by weight, based on 100% by weight of the total of the above-mentioned alloy composition. Within this range, The marble color is visible on the exterior after injection, minimizing the overall resin color change of the alloy.

The term " spot marble color " refers to a spot shape in which marble patterns are dot-dispersed unless otherwise specified.

The polycarbonate resin is, for example, a linear resin having MI (300 ° C, 1.2 kg load) of 3-30 g / 10 min as measured by ASTM D1238 in consideration of thermal stability and workability of the composition May be preferable for constituting the styrenic copolymer and the alloy.

As the styrenic copolymer, for example, a rubber-modified acrylonitrile-styrene copolymer such as a butadiene-acrylonitrile-styrene copolymer or an acrylate-acrylonitrile-styrene copolymer is used, May be preferred for constituting the alloy.

The styrenic copolymer may be, for example, an acrylonitrile-butadiene-styrene copolymer containing a diene rubber content of 20 to 70 wt%, a styrene monomer of 10 to 50 wt%, and an acrylonitrile monomer of 5 to 30 wt%.

The styrenic copolymer is contained in an amount of 5 to 20% by weight or 5 to 15% by weight of 100% by weight of the total of the above-mentioned free-radical copolymer. Within this range, the styrene- The marble color is visible on the exterior after injection, minimizing the overall resin color change of the alloy.

The flake-like filler-pigment mixture may include, for example, 10 to 40% by weight, 15 to 30% by weight, or 17 to 25% by weight of 100% by weight of the total of the alloy composition, And the Izod impact strength equivalent to that of a resin containing no existing marble pigment, and the spot marble color can be minimized by changing the resin color of the alloy while being exposed to the appearance after injection .

The term "plate-like filler-pigment mixture" refers to simple mixing of a plate-like filler and a pigment unless otherwise specified, and refers to a form obtained by dyeing a dye on a plate-shaped filler contained in an alloy resin composition .

The plate-like filler is not particularly limited as long as it is a plate type filler. For example, it may be at least one selected from talc and glass flakes, and the use of a material having a diameter of 50 to 700 탆, or 50 to 500 탆, Or the distortion of the product can be prevented and the dispersibility of the marble pigment in the alloy can be improved.

As the pigment, for example, a plate-type filler selected from the group including various organic binder including Acryl series can be used. For reference, the acrylic binder can serve to attach the plate-like filler and the pigment.

The mixing ratio of the platelet-like filler to the pigment is not specified, but may be mixed at a weight ratio of 1:99 to 99: 1, for example.

The term " pigment ", unless otherwise specified, refers to a substance that does not dissolve in water and is present in the form of a dispersion, and includes the following dyes (chromophores that are soluble in water and exhibit color, chromophore A substance consisting of a matrix).

The term " potassium silicate-dye mixture " may refer to a simple mixture of a potassium silicate inorganic filler and a dye or a dye-coated form on a potassium silicate inorganic filler, unless otherwise specified. The potassium silicate inorganic filler phase Coated with a dye is more preferable for realizing a spot marble color.

The potassium silicate inorganic filler may be, for example, a potassium silicate filler such as hydrous aluminum potassium silicate, and the dye may be a dye capable of achieving various desired spot marbles.

The mixing ratio of the potassium silicate inorganic filler to the dye may be, for example, 1: 99 to 99: 1 by weight.

The potassium silicate-dye mixture is contained in an amount of 0.01 to 5% by weight, or 0.05 to 2% by weight, based on 100% by weight of the total composition of the composition. The improved whiteness degree of the polycarbonate resin and the styrenic copolymer, Tensile strength, and Izod impact strength, and the spot marble color can be exposed to the exterior after injection, minimizing changes in resin color of the alloy.

For example, the potassium silicate-dye mixture may have a total diameter of less than 1 mm, or less than 0.5 mm, in view of whiteness and the like.

If necessary, the above-mentioned alloy composition may contain a flame retardant.

Examples of the flame retardant include resorcinol bis (diphenylphosphate), bisphenol A bis (diphenylphosphate), and N, N'-bis [di- (2,6-xylyl) phosphoryl] -piperazine Can be contained in the range of 3 to 20% by weight, or 5 to 15% by weight, based on 100% by weight of the total of the alloy composition, and the V0-rated flame retardancy measured by the UL94 method within this range .

The flame retardant is, for example,

[Chemical Formula 1]

로 표시되는 화합물일 수 있다.

. ≪ / RTI >

The composition may further include at least one additive selected from the group consisting of a plasticizer, a coupling agent, a heat stabilizer, a light stabilizer, an inorganic filler, a releasing agent, a lubricant, a dispersing agent,

In the present invention, a spot-marble color molded product can be produced using the above composition. An example of a production method is as follows:

That is, 40 to 80% by weight of a polycarbonate resin, 5 to 20% by weight of a styrenic copolymer, and 0 to 20% by weight of a phosphorus flame retardant are supplied to a main hopper of a twin screw extruder, ; Supplying the resulting extrudate to a main hopper of a twin-screw extruder, supplying the potassium silicate-dye mixture to a sider and subjecting the extrudate to secondary extrusion at 220 to 290 ° C; And producing injection molded and spot marble color molded articles obtained by secondary extrusion.

A mixture of a flaky filler and a pigment may be added to the main hopper or cider of the extruder during the primary extrusion.

For example, the spot marble color molded product may provide a whiteness (color difference, L value) of 72.3 to 75.4.

According to the present invention, there is provided a method for producing a spot (s), which is produced from the above-described method, characterized in that a plate-like filler-pigment is dispersed in an aliquot of a polycarbonate resin and a styrenic copolymer and a potassium silicate- It is possible to provide a spot marble color injection molded article.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention, but the present invention is not limited thereto.

[Example]

The specifications of each component used in the following examples and comparative examples are as follows:

Polycarbonate (PC): A linear polycarbonate resin having MI (300 ° C, 1.2 kg load) of 3-30 g / 10 min as measured by ASTM D1238

* Styrenic copolymer (ABS): An acrylonitrile / butadiene / styrene resin containing 20 to 70 wt% of diene rubber, 10 to 50 wt% of styrene monomer, and 5 to 30 wt% of acrylonitrile monomer

* Phosphorous Flame Retardant (BDP): Compound

[Chemical Formula 1]

* Mixture of Potassium Silicate-Dye 1 (Marble Pigment 1): Potassium aluminum silicate (aka mica) is used as a potassium silicate inorganic filler, and various organic substances (benzopyran, Polyphenols) at a weight ratio of 10: 90 as a pigment material having a total diameter of 1 mm.

* Potassium silicate-dye mixture 2 (Marble pigment 2): Potassium aluminum silicate is used as the potassium silicate inorganic filler, and the inorganic filler is coated with the above organic material as a dye at a weight ratio of 10:90, 0.5 mm.

* Plate-like filler-Dyestuff mixture (pigment): Plate-like filler that is added as a pigment to impart talc and whiteness, mixed with a substance that forms an inorganic oxide (ex. TiO2) at a weight ratio of 10:90.

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

The compositions of Examples 1 to 3 and Comparative Examples 1 to 4 in the following table were prepared by mixing all components except the marble pigment of the material components shown in the following Table 1 in a main hopper of a twin-screw extruder Then, 1 part by weight of antioxidant and lubricant were added per 100 parts by weight of the total composition, and the mixture was melted and kneaded at a temperature range of 220 to 290 ° C and extruded.

The resulting extrudate was put into a main hopper in a twin-screw extruder and Marble Pigment 1 or Marble Pigment 2 was added to a sider and melt-kneaded at 220-290 ° C Extruded and pelletized. The pellets were dried at 80 ° C for 4 hours or more, injection molded, and the specimens were allowed to stand at room temperature for 48 hours. The properties of the specimens were evaluated as follows.

≪ Evaluation of physical properties &

Tensile strength and elongation (kg / mm 2): A 1/8 "specimen was measured according to the ASTM D638 method.

Flexural Strength and Elastic Modulus (kg / cm 2): A 1/8 "specimen was measured according to the ASTM D638 method.

Impact strength (kg.cm/cm): A 1/8 "specimen was measured according to ASTM D256 method.

* Whiteness (appearance evaluation, yellowing index): Disk specimen (1.5 mm) was injected and L value was measured using a colorimeter. Appearance was further confirmed by visual inspection.

* Flame Retardancy Grade: The flame retardancy grade was measured according to UL94V method.

The measurement results are shown in Table 2 below.

Category (wt%) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 PC 60 60 60 60 60 60 60 ABS 10 10 10 10 10 10 10 BDP 10 10 10 10 10 10 10 Marble Pigment 1 - - - - 0.7 - 0.5 Marble Pigment 2 0.5 - 1.0 - - 0.3 - Pigment 19.5 20 19.0 20 19.3 19.7 19.5

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Whiteness (L) 72.3 84.5 75.4 85.0 65.0 78.5 73.0 The tensile strength 590 590 590 590 580 585 585 Flexural strength 42,000 42,000 42,000 42,000 42,000 42,000 42,000 Impact strength 7.1 7.0 7.0 7.1 7.0 7.0 7.0 Flammability rating 1.0mm V-0 1.0mm V-0 1.0mm V-0 1.0mm V-0 1.0mm V-0 1.0mnm V-0 1.0mm V-0

As shown in the above Table 2, the examples in which an appropriate amount of a polycarbonate resin and a styrenic copolymer in combination of a pigment (a mixture of a plate-like filler and a pigment) and a Marble pigment 2 (a dye-coated form on a potassium silicate inorganic filler) 1 to 3, whiteness was improved while maintaining mechanical strength such as tensile strength, flexural strength and impact strength, and flame retardancy grade V0 (1.0 mm) was confirmed. From these whiteness values, And spot marbles were formed. Also, the amount of the marble pigment used was found to be the whiteness maintained within a suitable range and the highest content of spot marble particles.

On the other hand, in Comparative Example 1 in which the marble pigment was not used and the additional extrusion process was not performed, the mechanical strength was maintained at about 1-3, but the whiteness was 85.0,

In Comparative Examples 2 and 4, in which Marble Pigment 1 (diameter: 1 mm) was used instead of Marble Pigment 2 (0.5 mm in diameter) instead of Marble Pigment 1 (0.5 mm in diameter), the mechanical strength was 580, As a result, it was confirmed that the spot pattern of the desired level was not displayed.

In Comparative Example 3 in which the amount of the marble pigment was less than the proper level, there was no significant change in the mechanical strength and whiteness was superior to the excess, but the spot marble particle feeling was judged by naked eyes.

As a result, according to the present invention, a mixture of a polycarbonate resin and a flaky filler-pigment as a pigment of a styrenic copolymer alloy is used as a pigment to provide a spot marble pattern after injection molding. In the case of the polycarbonate-styrene type copolymer alloy composition prepared by using the mixture (aka Marble pigment), it was confirmed that a molded article having a spot marble color was produced at the time of molded article production (see FIG. 1) It is possible to reduce cost incurred by painting and to provide economical efficiency.

<Additional Experimental Example>

In Example 1, the same experiment as in Example 1 was repeated except that the marble pigment was further extruded into a main hopper instead of a sider of a twin-screw extruder, and physical properties were measured.

As a result, the whiteness (L value) was 66.1, the mechanical strength was maintained as the tensile strength was 590 kg / mm 2, the Izod impact strength was 7.0 kg.cm/cm, and the flame retardancy was 1.0 mm-V0. However, Poor whiteness was observed in the marble color molded article.

From this, it was found that the extrusion of the marble pigment is performed by two stages of extrusion, in particular using a twin screw extruder for further extrusion, and that the injection of the marble pigment through the cider, rather than the main hopper, is more effective.

Claims (17)

From 0.01 to 5% by weight of a potassium silicate-dye mixture, from 40 to 81.99% by weight of a polycarbonate resin, from 5 to 20% by weight of a styrenic copolymer, from 10 to 40%
The styrenic copolymer is an acrylonitrile-butadiene-styrene copolymer comprising 20 to 70% by weight of diene rubber, 10 to 50% by weight of styrene monomer and 5 to 30% by weight of acrylonitrile,
Wherein the platy filler-pigment mixture has a weight ratio of the platy filler to the pigment of from 1:99 to 10:90 and the potassium silicate-dye mixture has a weight ratio of potassium silicate to dye of from 1:99 to 10:90
Polycarbonate-styrenic copolymer solid compositions. delete The method according to claim 1,
Wherein the polycarbonate resin is a linear resin having MI (300 DEG C, 1.2 kg load) of 3 to 30 g / 10 min as measured according to ASTM D1238
Polycarbonate-styrenic copolymer solid compositions. delete delete delete The method according to claim 1,
Wherein the plate-shaped filler is at least one selected from talc and glass flakes and has a diameter of 50 to 700 탆
Polycarbonate-styrenic copolymer solid compositions. delete The method according to claim 1,
Characterized in that the potassium silicate-dye mixture is a potassium silicate inorganic filler-dye application type
Polycarbonate-styrenic copolymer solid compositions. 10. The method of claim 9,
Wherein the potassium silicate inorganic filler is a hydrated aluminum potassium silicate
Polycarbonate-styrenic copolymer solid compositions. delete The method according to claim 1,
Characterized in that the potassium silicate-dye mixture has a diameter of less than 1 mm
Polycarbonate-styrenic copolymer solid compositions. The method according to claim 1,
The aliphatic composition may be selected from the group consisting of resorcinol bis (diphenylphosphate), bisphenol A bis (diphenylphosphate), and N, N'-bis [di- (2,6-xylyl) Characterized in that the flame retardant comprises at least one selected from the group consisting of 3 to 20% by weight of the total 100% by weight of the composition
Polycarbonate-styrenic copolymer solid compositions. The method according to claim 1,
The composition can be used as a plasticizer, a coupling agent, a heat stabilizer, a light stabilizer, an inorganic filler, a release agent, a lubricant, a dispersant, And at least one additive selected from the group consisting of
Polycarbonate-styrenic copolymer solid compositions. The main hopper of the twin-screw extruder is fed with 40 to 80% by weight of a polycarbonate resin, 5 to 20% by weight of a styrenic copolymer and 0 to 20% by weight of a phosphorus flame retardant, step;
Supplying the resulting extrudate to a main hopper of a twin-screw extruder, supplying 0.01 to 5% by weight of a potassium silicate-dye mixture to the cider and secondary extruding at 220 to 290 ° C; And
Injection molding the extrudate obtained by the secondary extrusion and producing a spot marble color molded product,
In the primary extrusion, 10 to 40% by weight of a plate-like filler-pigment mixture is fed into the main hopper or cider of the twin-screw extruder,
The styrenic copolymer is an acrylonitrile-butadiene-styrene copolymer comprising 20 to 70% by weight of diene rubber, 10 to 50% by weight of styrene monomer and 5 to 30% by weight of acrylonitrile,
Wherein the weight ratio of the platelet-like filler to the pigment is 1:99 to 10:90, and the weight ratio of the potassium silicate-dye mixture to the potassium silicate-dye is 1:99 to 10:90.
A method of manufacturing a spot marble color molded article.
delete delete

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