KR101981471B1 - Thermoplastic resin composition and molded article comprising the same - Google Patents

Abstract

More particularly, the present invention relates to a thermoplastic resin composition comprising 100 parts by weight of an aromatic vinyl compound-conjugated diene compound-vinyl cyanide copolymer, 10 to 30 parts by weight of a halogen-based flame retardant having a melting point of less than 350 占 폚, And 0.1 to 10 parts by weight of talc having a loss on ignition of less than 50% by weight. The present invention also relates to a molded article comprising the thermoplastic resin composition.
According to the present invention, there is provided an effect of providing a thermoplastic resin composition and a molded article including the thermoplastic resin composition, which can provide a mechanical strength such as impact strength, fluidity and heat resistance equal to or greater than that of the thermoplastic resin composition,

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a thermoplastic resin composition,

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition, and more particularly, to a thermoplastic resin composition capable of reducing molding shrinkage and facilitating large-scale injection while providing mechanical strength such as impact strength, fluidity, and heat resistance.

Acrylonitrile-butadiene-styrene (ABS) resins are widely used in automotive products, electrical and electronic products, automobiles, and automobiles due to the stiffness and chemical resistance of acrylonitrile, butadiene and styrene processability, mechanical strength, It is an amorphous resin widely used for office equipment and the like. Especially, in recent years, home appliances such as TVs and monitors are becoming larger, and the size of injection-molded products is also becoming larger.

However, injection molded articles generally have a problem in that the molded articles are shrunk after molding. In the case of large molded articles, the larger the molding shrinkage ratio, the larger the influence it receives, so that the resin used for large injection molding is improved to have a lower molding shrinkage There is a need.

KR 2004-0097595 A

An object of the present invention is to provide a thermoplastic resin composition which is capable of reducing the molding shrinkage rate and facilitating large-sized injection while providing mechanical strength such as impact strength, fluidity and heat resistance equal to or higher than that of the thermoplastic resin composition.

Another object of the present invention is to provide a molded article comprising the thermoplastic resin composition.

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

In order to attain the above object, the present invention provides a thermoplastic resin composition comprising 100 parts by weight of an aromatic vinyl compound-conjugated diene compound-vinyl cyanide copolymer, 10 to 30 parts by weight of a halogen-based flame retardant having a melting point of less than 350 占 폚, And 0.1 to 10 parts by weight of talc having a loss on ignition of less than 50% by weight based on the total weight of the thermoplastic resin composition.

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

According to the present invention, there is provided an effect of providing a thermoplastic resin composition and a molded article including the thermoplastic resin composition, which can provide a mechanical strength such as impact strength, fluidity and heat resistance equal to or greater than that of the thermoplastic resin composition,

Hereinafter, the present invention will be described in detail.

The present inventors have found that when the aromatic vinyl compound-conjugated diene compound-vinyl cyanide copolymer is incorporated with a flame retardant and a talc having a specific size, it is possible to improve the mold shrinkage rate while preventing deterioration of mechanical properties as well as flame retardancy And the present invention was completed on the basis thereof.

The thermoplastic resin composition according to the present invention will be described in detail as follows.

Wherein the thermoplastic resin composition comprises 100 parts by weight of an aromatic vinyl compound-conjugated diene compound-vinyl cyanide copolymer, 10 to 30 parts by weight of a halogen-based flame retardant having a melting point of less than 350 占 폚 and an average particle diameter of 0.1 to 10 占 퐉, 0.1 to 10 parts by weight of talc having an ignition content of less than 50% by weight.

The conjugated diene compound is not particularly limited as long as it can be used for the copolymerization, and examples thereof include 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-butadiene, isoprene, and derivatives thereof, and 1,3-butadiene can be preferably used. In this case, the mechanical strength and balance of physical properties are excellent.

The conjugated diene compound may be contained in an amount of 5 to 50% by weight, 10 to 40% by weight, or 10 to 30% by weight, based on the copolymer. Within this range, the conjugated diene compound has excellent mechanical properties.

The aromatic vinyl compound may be at least one selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, vinyltoluene and derivatives thereof.

The aromatic vinyl compound may be contained in an amount of, for example, 40 to 80% by weight, 50 to 70% by weight, or 55 to 65% by weight based on the copolymer. Within this range, an excellent balance of mechanical properties and physical properties is obtained.

The vinyl cyan compound may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and derivatives thereof.

The vinyl cyan compound may be contained in an amount of from 1 to 40% by weight, from 5 to 30% by weight, or from 15 to 25% by weight, based on the copolymer, and has an excellent balance of flame retardancy and physical properties within this range.

The aromatic vinyl compound-conjugated diene compound-vinyl cyanide copolymer may be one obtained by emulsion polymerization, bulk polymerization, solution polymerization or suspension polymerization, preferably emulsion-polymerized. In this case, the reaction can be easily controlled It is possible to obtain a polymer having a desired molecular weight distribution.

The halogen-based flame retardant is not particularly limited as long as it can be used in the thermoplastic resin composition, and for example, it may be an aromatic bromine-based flame retardant.

Examples of the halogen-based flame retardant include 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine, decabromodiphenylethane, ethylene bis (tetrabromophthal (Tribromophenyl) cyanurate, tetrabromobisphenol-A bis (allyl ether), bromine substituted polystyrenes, and bis (trimellitic acid) Derivatives, and preferably at least one selected from the group consisting of 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine, tetrabromobisphenol- A, a brominated epoxy oligomer, and a polystyrene in which a part of hydrogen of the phenyl group is substituted with bromine. In this case, there is an effect of excellent mechanical properties and flame retardancy.

The halogen-based flame retardant may, for example, have a halogen content of 80 wt% or less, 40 to 80 wt%, or 45 to 70 wt%, and an excellent balance of flame retardancy and physical properties within this range.

The halogen-based flame retardant may be, for example, a molten flame retardant having a melting point of less than 350 ° C, 150 to 300 ° C, or 170 to 230 ° C, and has an excellent balance of flame retardancy and physical properties within this range.

The halogen-based flame retardant may be included in an amount of 10 to 30 parts by weight, 15 to 30 parts by weight, or 15 to 25 parts by weight based on 100 parts by weight of the base resin, and the flame retardancy is excellent within this range.

The talc means ordinary talc that can be used in the thermoplastic resin composition, and is a monoclinic or orthorhombic silicate-based white mineral of Mg ₃ Si ₄ O ₁₀ (OH) ₂ .

The talc may have an average particle diameter of 1 to 10 占 퐉 or 1 to 7 占 퐉, for example. Within this range, the talc has an excellent effect of improving mechanical properties and mold shrinkage rate, and has an excellent balance of physical properties.

For example, the talc may have a loss on ignition (ASTM D7348) of less than 50 wt%, not more than 30 wt%, or not more than 25 wt%, the thermostability of the thermoplastic resin composition is maintained within the range, This has an excellent effect.

The talc may be included in an amount of 0.1 to 10 parts by weight, or 1 to 10 parts by weight, based on 100 parts by weight of the aromatic vinyl compound-conjugated diene compound-vinyl cyanide copolymer, .

For example, the thermoplastic resin composition may have a molding shrinkage ratio (1/1000, shrinkage in the flow direction) of 6.7 or less, 3.0 to 6.7, or 5.0 to 6.7.

For example, the thermoplastic resin composition may have a thermal deformation temperature of 70 ° C or more, or 70 to 90 ° C.

The thermoplastic resin composition may have a melt index (220 ° C, 10 kg) of 30 to 90 g / 10 min, or 40 to 85 g / 10 min, for example.

Examples of the thermoplastic resin composition include a heat stabilizer, a lubricant, an antioxidant, a light stabilizer, a releasing agent, a pigment, a dye, an antistatic agent, an antibacterial agent, a processing aid, a metal deactivator, And at least one additive selected from the group consisting of an antioxidant and an inhibitor.

The additive may be included in an amount of 0.1 to 10 parts by weight, 1 to 10 parts by weight, or 1 to 5 parts by weight based on 100 parts by weight of the aromatic vinyl compound-conjugated diene compound-vinyl cyan compound copolymer.

The molded article according to the present invention is characterized by comprising the thermoplastic resin composition.

The molded article may be, for example, a large injection molded article.

The large injection molded article may be, for example, a housing of a large home appliance.

The large household appliances may be, for example, a TV, a monitor, a refrigerator, a washing machine, and an air conditioner.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory only and are not to be taken by way of illustration in the practice of the practice of this invention. And it is natural that such variations and modifications are included in the appended claims.

[Example]

Example 1

20 parts by weight of a brominated flame retardant (product name: SR-245, manufactured by Dai-Ich Kogyo Seiyaku Co., Ltd.) and 20 parts by weight of talc having an average particle diameter of 6.5 占 퐉 were added to 100 parts by weight (based on solid content) of an ABS copolymer (product name: HI- And 1 part by weight (ignition loss: 8% by weight or less) of the resin composition were put into an extruder and melted and kneaded at 180 to 230 ° C to prepare a resin composition in the form of pellets. Respectively.

Example 2

The procedure of Example 1 was repeated except that 5 parts by weight of talc having an average particle size of 6.5 mu m (ignition loss of 8 wt% or less) was added.

Example 3

The procedure of Example 1 was repeated, except that 10 parts by weight of talc having an average particle size of 6.5 mu m (ignition loss of 8 wt% or less) was added.

Example 4

The procedure of Example 1 was repeated except that 10 parts by weight of talc having an average particle diameter of 1.5 탆 (ignition loss of 8% by weight or less) was added in place of the talc having an average particle diameter of 6.5 탆.

Example 5

The procedure of Example 1 was repeated, except that 1 part by weight of talc having an average particle size of 10 占 퐉 (ignition loss of 8% by weight or less) was added instead of talc having an average particle diameter of 6.5 占 퐉.

Example 6

The procedure of Example 2 was repeated except that talc having an average particle size of 6.5 mu m (ignition loss weight of 20 wt%) was added in the same amount as the talc having an average particle diameter of 6.5 mu m (ignition loss of 8 wt% or less) Respectively.

Comparative Example 1

The same procedure as in Example 1 was carried out except that talc having an average particle diameter of 6.5 mu m (ignition loss: 8 wt% or less) was not added in Example 1 above.

Comparative Example 2

10 parts by weight of an unhardened bromine flame retardant having an average particle size of 3 占 퐉 (manufactured by Albemarle, product name: SAYTEX 4010, melting point: 350 占 폚) was added in place of talc having an average particle diameter of 6.5 占 퐉 The same procedure as in Example 1 was carried out.

Comparative Example 3

The procedure of Example 1 was repeated, except that 10 parts by weight of calcium carbonate (CaCO ₃ ) having an average particle size of 3 탆 was added instead of talc having an average particle diameter of 6.5 탆 (ignition loss of 8% by weight or less) Respectively.

Comparative Example 4

The same procedure as in Example 1 was conducted except that 5 parts by weight of wollastonite having an average particle size of 5 탆 was added to the talc having an average particle diameter of 6.5 탆 (ignition loss of 8% by weight or less) in Example 1.

Comparative Example 5

Example 1 was carried out in the same manner as in Example 1, except that 5 parts by weight of glass fiber having an average particle diameter of 3 占 퐉 was used instead of talc having an average particle diameter of 6.5 占 퐉 (ignition loss of 8% by weight or less).

Comparative Example 6

Example 1 was carried out in the same manner as in Example 1, except that 15 parts by weight of talc having an average particle diameter of 6.5 mu m (ignition loss of 8 wt% or less) was added.

Comparative Example 7

The same procedure as in Example 3 was carried out except that 20 parts by weight of an unmelted bromine flame retardant (trade name: SAYTEX 4010) was used in place of the bromine flame retardant (manufactured by Dai-Ich Kogyo Seiyaku, product name SR-245) Respectively.

Comparative Example 8

The procedure of Example 1 was repeated except that 5 parts by weight of talc having an average particle diameter of 15 탆 (ignition loss of 8% by weight or less) was added instead of talc having an average particle diameter of 6.5 탆 (ignition loss of 8% The same procedure was followed.

Comparative Example 9

In the same manner as in Example 2 except that talc having an average particle diameter of 6.5 mu m (ignition loss weight of 50 wt%) was added in the same amount as the talc (average ignition loss: 8 wt% or less) having an average particle diameter of 6.5 mu m Respectively.

[Test Example]

The properties of the thermoplastic resin composition specimens obtained in Examples 1 to 6 and Comparative Examples 1 to 9 were measured by the following methods, and the results are shown in Tables 1 and 2, respectively.

How to measure

* Average particle size: The value of d (0.5) was measured using a particle size analyzer.

* Flammability (UL-94): Measured according to the UL-94 vertical burning evaluation method using a specimen of 1.5 mm in thickness.

Loss on ignition (LOI): Loss on ignition (LOI) was measured according to ASTM D7348, Method A, single-step procedure, using macro TGA (Thermogravimetric analysis) Respectively.

[Equation 1]

Ignition loss (weight%) = (weight before heating - weight after heating) / weight before heating X 100

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

Melt Index (g / 10 min): Measured according to standard measurement ASTM D1238 (220 ° C, 10 kg condition) using specimen.

Heat distortion temperature (HDT, ° C): Measured according to standard measurement ASTM D648 using specimens.

* Shrinkage rate (1/1000): Shrinkage in the flow direction was measured according to ISO 2577 using a specimen of 50 mm length, 50 mm width and 3.0 mm thickness.

division Example One 2 3 4 5 6 Flammability V-0 V-0 V-0 V-0 V-0 V-0 Impact strength 15 13 7 9 12 14 Melt Index 82 79 66 62 80 79 Heat distortion temperature 80 80 81 81 81 80 Mold Shrinkage 6.6 6.2 5.8 6.1 6.6 6.5

division Comparative Example One 2 3 4 5 6 7 8 9 Flammability V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Impact strength 18 12 6 15 14 2 5 3 15 Melt Index 80 72 74 75 75 58 60 68 80 Heat distortion temperature 79 81 81 80 80 83 84 82 80 Mold Shrinkage 6.8 6.9 6.8 6.8 6.8 5.7 5.8 6.0 6.8

As shown in Tables 1 and 2, in Examples 1 to 6 prepared according to the present invention, it was confirmed that the heat distortion temperature and the molding shrinkage ratio were improved and the balance of physical properties was superior to Comparative Example 1 in which no talc was added .

On the other hand, in the case of Comparative Example 2 in which the non-fusing flame retardant was added instead of talc, the effect of increasing the flame retardancy was small, but the mold shrinkage rate was increased. In Comparative Examples 3 to 5 in which inorganic substances other than talc were added, It was confirmed that the impact strength was lowered without any improvement in the shrinkage ratio.

In addition, it was confirmed that the impact strength was significantly lowered in Comparative Example 6 in which talc was added in an excessive amount, and in Comparative Example 7 in which talc and unmelted flame retardant were used at the same time, the impact strength was lowered there was.

In addition, in Comparative Example 8, it was confirmed that the mold shrinkage ratio was somewhat improved by increasing the particle size of the talc, but the impact strength was abruptly decreased, and in Comparative Example 9 including the talc having a high ignition loss, I could.

In conclusion, when the thermoplastic resin composition of the present invention contains the aromatic vinyl compound-conjugated diene compound-vinyl cyanide copolymer together with the flame retardant together with the flame retardant having a specific size, the flame retardancy and the mechanical properties are prevented from deteriorating, It is confirmed that a thermoplastic resin composition which can be easily injected into a large size can be realized due to the above characteristics.

Claims (11)

100 parts by weight of an aromatic vinyl compound-conjugated dienic compound-vinyl cyanide copolymer, 10 to 30 parts by weight of a halogen-based flame retardant having a melting point of 280 占 폚 or less and an average particle diameter of 6.5 to 10 占 퐉 and a loss on ignition of 50 weight% And 1 to 5 parts by weight of talc, which is less than 1% by weight, based on the total weight of the thermoplastic resin composition.
Wherein the thermoplastic resin composition has a molding shrinkage ratio (1/1000) of 6.2 to 6.6. The method according to claim 1,
The conjugated diene compound may be 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 Wherein the thermoplastic resin composition is a thermoplastic resin composition. The method according to claim 1,
Wherein the aromatic vinyl compound is at least one selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, vinyltoluene and derivatives thereof. The method according to claim 1,
Wherein the vinyl cyan compound is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and derivatives thereof. The method according to claim 1,
Wherein the halogen-based flame retardant has a halogen content of 80 wt% or less. delete The method according to claim 1,
The thermoplastic resin composition may contain at least one additive selected from the group consisting of a heat stabilizer, a lubricant, an antioxidant, a light stabilizer, a release agent, a pigment, a dye, an antistatic agent, an antibacterial agent, a processing aid, a metal deactivator, The thermoplastic resin composition according to claim 1, 8. The method of claim 7,
Wherein the additive is included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the aromatic vinyl compound-conjugated diene compound-vinyl cyanide copolymer. delete A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 5, 7 or 8. The method according to claim 1,
Wherein the thermoplastic resin composition has a melt index (220 DEG C, 10 kg) of 79 to 82 g / 10 min.