KR102045966B1

KR102045966B1 - Thermoplastic resin composition and molded article comprising the same

Info

Publication number: KR102045966B1
Application number: KR1020150147786A
Authority: KR
Inventors: 이주형; 김성룡; 김서화; 최정안
Original assignee: 주식회사 엘지화학
Priority date: 2015-10-23
Filing date: 2015-10-23
Publication date: 2019-11-18
Also published as: KR20170047552A

Abstract

The present invention relates to a thermoplastic resin composition, and more particularly, (a-1) a graft in which an aromatic vinyl compound and a vinyl cyan compound are grafted to a conjugated diene rubbery polymer having an average particle diameter of 0.03 or more and less than 0.2 µm. 1 to 25 wt% of the copolymer, (a-2) 10 to 45 wt% of the graft copolymer grafted with an aromatic vinyl compound and a vinyl cyan compound to a conjugated diene rubbery polymer having an average particle diameter of 0.2 to 0.5 μm, and (b) 100 parts by weight of a base resin comprising 50 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer; And (c) relates to a thermoplastic resin composition and a molded article comprising the same comprising 0.1 to 2.5 parts by weight of the metal activity inhibitor.
According to the present invention, there is an effect of providing a thermoplastic resin composition and a molded article including the same, having mechanical properties equal to or higher, excellent in color and plating adhesion, and maintaining appearance quality even under various external environmental changes.

Description

Thermoplastic resin composition and molded article including the same {THERMOPLASTIC RESIN COMPOSITION AND MOLDED ARTICLE COMPRISING THE SAME}

The present invention relates to a thermoplastic resin composition, and more particularly, to a thermoplastic resin composition having an equivalent or more mechanical properties, excellent color and plating adhesion, and maintaining appearance quality even under various external environmental changes, and a molded article including the same. will be.

Acrylonitrile-Butadiene-Styrene (hereinafter referred to as ABS) resins are used in automotive, electrical, and electrical It is widely used in electronic products and office equipment.

Such ABS resins are often subjected to plating treatment. The plating process is performed in order of degreasing, etching, neutralization, catalysis, activation, chemical plating, and electroplating. The etching process is a process of dissolving the rubber portion in the ABS resin to impart unevenness to the surface, the hole formed by melting the rubber through this process acts as an anchoring (anchoring) site to have a physical bonding force with the plating film.

In this case, when the physical bonding strength to the plating film, that is, the plating adhesion is not sufficient, there is a problem that the plating layer is separated from the ABS resin base layer by an external environment change such as temperature change. Such plating swelling is a major quality control target in the plating industry. Thus, conventionally, the method of improving the adhesion of the rubber and the content of the rubber and monomers, the molecular weight increase, etc. are mainly used as a method for improving the adhesion, these methods eventually have a problem of lowering the mechanical properties and fluidity of the ABS resin. Therefore, in the plating industry, there is an urgent need for improvement of the plating reliability of the ABS resin.

KR 1322145 B1

The present invention relates to a thermoplastic resin composition, and more particularly, to provide a thermoplastic resin composition having an equivalent or more mechanical properties, excellent color and plating adhesion, and maintaining appearance quality even under various external environmental changes. .

Moreover, an object of this invention is to provide the molded article containing the said thermoplastic 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 (a-1) graft copolymer 1 to which an aromatic vinyl compound and a vinyl cyan compound are grafted to a conjugated diene rubbery polymer having an average particle diameter of rubber of 0.03 or more and less than 0.2 µm. 25% by weight, (a-2) 10 to 45% by weight of a graft copolymer grafted with an aromatic vinyl compound and a vinyl cyan compound to a conjugated diene-based rubbery polymer having an average particle diameter of 0.2 to 0.5 µm and (b) aromatic 100 parts by weight of a base resin including 50 to 80% by weight of a vinyl compound-vinylcyan compound copolymer; And (c) provides a thermoplastic resin composition comprising 0.1 to 2.5 parts by weight of the metal activity inhibitor.

In another aspect, the present invention provides a molded article comprising the thermoplastic resin composition.

According to the present invention, there is an effect of providing a thermoplastic resin composition and a molded article including the same, having excellent mechanical properties or the like, excellent color and plating adhesion, and maintaining appearance quality even under various external environmental changes.

Hereinafter, the present invention will be described in detail.

The inventors of the present invention have completed the present invention by using graft copolymers having different sizes of rubber and including metal activity inhibitors in a certain amount, thereby improving plating related properties of the thermoplastic resin composition for plating. .

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

The thermoplastic resin composition (a-1) 1 to 25% by weight of a graft copolymer grafted with an aromatic vinyl compound and a vinyl cyan compound in a conjugated diene rubbery polymer having an average particle diameter of rubber of 0.03 or more and less than 0.2 µm, ( a-2) 10 to 45% by weight of a graft copolymer in which an aromatic vinyl compound and a vinyl cyan compound are grafted to a conjugated diene rubber polymer having an average particle diameter of 0.2 to 0.5 µm and (b) an aromatic vinyl compound-vinyl cyan 100 parts by weight of the base resin including 50 to 80% by weight of the compound copolymer; And (c) 0.1 to 2.5 parts by weight of the metal activity inhibitor.

The conjugated diene rubber polymers of (a-1) and (a-2) are each composed of butadiene polymer, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene copolymer and derived polymers thereof It may be at least one selected from the group, preferably butadiene polymer can be used, in this case there is an excellent effect of the balance of mechanical strength and physical properties.

The conjugated diene rubber polymer of (a-1) may have an average particle diameter of, for example, 0.03 to less than 0.2 μm, 0.05 to 0.18 μm, or 0.07 to 0.15 μm, and have excellent mechanical properties and plating adhesion within this range. It works.

The conjugated diene rubber polymer of (a-1) may be included in an example of 20 to 80% by weight, 30 to 75% by weight, or 45 to 70% by weight based on the (a-1) graft copolymer, Within this range, the mechanical properties are very excellent.

The conjugated diene-based rubbery polymer of (a-2) may have, for example, an average particle diameter of 0.2 to 0.5 μm, 0.23 to 0.45 μm, or 0.25 to 0.4 μm, and excellent mechanical properties and plating adhesion within this range. have.

The conjugated diene-based rubbery polymer of (a-2) may be included in 20 to 80% by weight, 30 to 75% by weight, or 45 to 70% by weight relative to the (a-2) graft copolymer, Within this range, the mechanical properties are very excellent.

The aromatic vinyl compounds of (a-1), (a-2) and (b) are, for example, styrene, α-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, vinyltoluene, and the like. It may be at least one selected from the group consisting of derivatives, and preferably styrene may be used, in which case the mechanical and balance properties are excellent.

The aromatic vinyl compound included in the graft copolymers (a-1) and (a-2) is, for example, 10 to 70 wt% based on each of the (a-1) and (a-2) graft copolymers, It may be included in 15 to 65% by weight, or 20 to 60% by weight, there is an excellent effect of the fluidity and physical properties balance within this range.

The aromatic vinyl compound included in the (b) aromatic vinyl compound-vinyl cyan compound copolymer may be included, for example, in an amount of 60 to 90 wt%, 60 to 85 wt%, or 65 to 80 wt% based on the (b) copolymer. It can be, and within this range there is an effect of excellent mechanical and physical properties balance.

The vinyl cyan compound of (a-1), (a-2) and (b) may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and derivatives thereof, for example. have.

The vinyl cyan compound included in the graft copolymers (a-1) and (a-2) may be, for example, 1 wt% to 30 wt% with respect to the graft copolymers (a-1) and (a-2), It may be included in 3 to 25% by weight, or 5 to 20% by weight, the plating adhesion and appearance quality is excellent within this range.

The vinyl cyan compound included in the (b) aromatic vinyl compound-vinyl cyan compound copolymer is, for example, 10 to 40% by weight, 15 to 40% by weight, or 20 to 35% by weight based on the (b) copolymer. The plating adhesion can be excellent in this range. In particular, when the content of the vinyl cyan compound does not reach the proper content, under etching occurs during the etching process, so that unevenness is not sufficiently provided on the surface of the resin, and when the content exceeds the proper content, overetching ( over-etching) causes a significant decrease in plating adhesion, so it is important to be included within the content range.

The graft copolymers (a-1) and (a-2) may be, for example, emulsion polymerization, bulk polymerization, solution polymerization or suspension polymerization, preferably emulsion polymerization, in which case the control of the reaction is It has an easy effect.

The graft copolymer (a-1) may be included in an amount of 1 to 25% by weight, 5 to 20% by weight, or 5 to 15% by weight with respect to the base resin, for example. Excellent effect.

The graft copolymer (a-2) may be included in an amount of 10 to 45% by weight, 10 to 35% by weight, or 15 to 30% by weight with respect to the base resin, for example. Excellent effect.

The copolymer (b) may be, for example, one prepared by emulsion polymerization or bulk polymerization. Preferably, the copolymer (b) is bulk polymerization.

The copolymer (b) may have, for example, a weight average molecular weight of 50,000 to 200,000 g / mol, 60,000 to 190,000 g / mol, or 70,000 to 180,000 g / mol, and within this range, the effect of excellent impact strength and workability is excellent. have.

The (b) copolymer may be included, for example, 50 to 80% by weight, 55 to 80% by weight, or 60 to 80% by weight with respect to the base resin, within this range has excellent effect of plating adhesion and balance of physical properties have.

The (c) metal activity inhibitor may be, for example, a phenolic compound represented by Formula 1 below.

The w may be, for example, an integer of 1 to 50, an integer of 5 to 40, or an integer of 10 to 30.

The x and y may be an integer of 1 to 20, an integer of 1 to 10, or an integer of 1 to 6, for example.

Z may be, for example, an integer of 1 to 100, an integer of 5 to 80, or an integer of 10 to 50.

The phenolic compound represented by Formula 1 may be, for example, a phenolic compound represented by Formula 2 below.

The R may be, for example, a bonding, an alkylene group having 1 to 30 carbon atoms, a cycloalkylene group having 5 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, and an alkylarylene group having 6 to 30 carbon atoms.

R may be, for example, an alkylene group having 1 to 20 carbon atoms.

The (c) metal activity inhibitor is, for example, 1-N ', 12-N'-bis (2-hydroxybenzoyl) dodecanedihydrazide (1-N', 12-N'-bis (2-hydroxybenzoyl) dodecanedihydrazide ), 3- (salicyloylamino) -1,2,4-triazole and 1,2-bis (3,5-di-t-butyl 4-hydroxyhydrocinnamoyl) hydrazine (1,2-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamoly) hydrazine) may be one or more selected from the group consisting of, in this case compatible with the resin At the same time, it has an excellent effect of suppressing the metal activity of the plated metal and excellent plating adhesion.

(C) the metal activity inhibitor may be included, for example, 0.1 to 2.5 parts by weight, 0.1 to 2.3 parts by weight, or 0.1 to 2 parts by weight with respect to 100 parts by weight of the base resin, and excellent plating adhesion within this range, It is effective in preventing discoloration.

For example, the thermoplastic resin composition may have a melt index (220 ° C., 10 kg) of 5 to 40 g / 10 min, 7 to 35 g / 10 min, or 10 to 30 g / 10 min, and processability within this range. And the physical property balance is excellent effect.

For example, the thermoplastic resin composition may have a plating adhesion of 7.5 N / cm or more, 7.5 to 9.2 N / cm, or 8.0 to 9.2 N / cm, and has excellent weather resistance within this range.

The thermoplastic resin composition may be, for example, a material for plating.

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

The molded article may be, for example, an injection molded article, and in particular, may be an automobile interior or exterior material.

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

Example 1

(a-1) 10 g by weight of an ABS graft copolymer having an average particle diameter of rubber (manufactured by LG Chemical, product name DP229M), (a-2) an ABS graft copolymer having an average particle diameter of 0.3 μm of rubber ( To 100 parts by weight of a base resin consisting of 70% by weight of a SAN resin (manufactured by LG Chemical, product name 95HCI) manufactured by LG Chemical, product name DP270M) and 20% by weight of (b) bulk polymerization, (c) a metal activity inhibitor ( 0.1 parts by weight of ADK STAB CDA-6) manufactured by ADEKA Co., Ltd. was added to a twin screw extruder, and melted and kneaded at 220 ° C. to prepare a resin composition in pellet form. Specimens were prepared, and the specimens were plated with a uniform thickness of 30 μm or more by using a conventional plating method.

Example 2

In Example 1, (c) was carried out in the same manner as in Example 1, except that 1 part by weight of the metal activity inhibitor.

Example 3

In Example 1, (c) was carried out in the same manner as in Example 1, except that 2 parts by weight of the metal activity inhibitor.

Example 4

In Example 2, 100 parts by weight of the base resin consisting of (a-1) 5% by weight of the ABS graft copolymer, (a-2) 20% by weight of the ABS graft copolymer and (b) 75% by weight of the SAN resin The same procedure as in Example 2 was conducted except for the one.

Example 5

In Example 2, 100 parts by weight of the base resin consisting of (a-1) 15% by weight of the ABS graft copolymer, (a-2) 20% by weight of the ABS graft copolymer and (b) 65% by weight of the SAN resin The same procedure as in Example 2 was conducted except for the one.

Example 6

In Example 2, 100 parts by weight of the base resin consisting of (a-1) 10% by weight of the ABS graft copolymer, (a-2) 15% by weight of the ABS graft copolymer and (b) 75% by weight of the SAN resin The same procedure as in Example 2 was conducted except for the one.

Example 7

In Example 2, 100 parts by weight of the base resin consisting of (a-1) 10% by weight of the ABS graft copolymer, (a-2) 30% by weight of the ABS graft copolymer and (b) 60% by weight of the SAN resin The same procedure as in Example 2 was conducted except for the one.

Comparative Example 1

In Example 1, (c) was carried out in the same manner as in Example 1, except that the metal activity inhibitor was not added.

Comparative Example 2

In Example 1, (c) was carried out in the same manner as in Example 1, except that 3 parts by weight of the metal activity inhibitor.

Comparative Example 3

In Example 1, (c) was carried out in the same manner as in Example 1, except that 0.05 parts by weight of the metal activity inhibitor.

Comparative Example 4

In Example 2, 100 parts by weight of the base resin consisting of (a-1) 30% by weight of the ABS graft copolymer, (a-2) 20% by weight of the ABS graft copolymer and (b) 50% by weight of the SAN resin The same procedure as in Example 2 was conducted except for the one.

Comparative Example 5

In Example 2, 100 parts by weight of the base resin consisting of (a-1) 10% by weight of the ABS graft copolymer, (a-2) 5% by weight of the ABS graft copolymer and (b) 85% by weight of the SAN resin The same procedure as in Example 2 was conducted except for the one.

Comparative Example 6

In Example 2, the same amount of (A-2) ABS graft copolymer (A-3) ABS graft copolymer (product name MA201 manufactured by LG Chemical Co., Ltd., product name MA201) was added instead of the ABS graft copolymer. Except that was carried out in the same manner as in Example 2.

[Test Example]

The physical properties of the thermoplastic resin composition specimens obtained in Examples 1 to 7 and Comparative Examples 1 to 6 were measured by the following method, and the results are shown in Table 1 below.

How to measure

* Average particle size: The Nicomp 370HPL instrument of Nicomp, USA was measured by the dynamic laser light scattering method.

Weight average molecular weight (Mw, g / mol): Relative values for standard polystyrene (PS) samples were determined by gel chromatography (GPC).

* Notched Izod Impact Strength (kgfcm / cm): A specimen of 6.4 mm thickness was measured according to the standard measurement ASTM D256.

* Melt Index (Melt Index, g / 10 min): Measured according to the standard measurement ASTM D1238 (220 ℃, 10 kg conditions) using the specimen.

* Plating adhesion (N / cm): 100 mm long, 100 mm wide, 3 mm thick plated specimens with 10 mm width scratches and vertically pushed with a push-pull gage The average value for the measured value was shown while peeling off 80 mm in the direction.

* Appearance quality evaluation after the cold-resistant heat circulation test: First, the heating and cooling were repeated in the chamber using the specimen under the conditions of the following ① to ⑤.

① Maintain chamber temperature at -40 ℃ for 60 minutes

② The temperature in the chamber is raised to 80 ° C. within 1 minute.

③ Keep the temperature in the chamber at 80 ℃ for 60 minutes

④ Cool down the chamber temperature to -40 ℃ within 1 minute

⑤ Repeat the process of ① to ④ four times

The degree of plating crack generation was visually checked for the specimens after the above-described cold-heat cycle test, and when cracks and plating swelling did not occur at all, and cracks and plating swelling occurred in part, they were shown by dividing by ×.

* Discoloration evaluation: The appearance of the specimens was visually evaluated, and there were almost no discoloration.

division Example Comparative example One 2 3 4 5 6 7 One 2 3 4 5 6 (a-1) 10 10 10 5 15 10 10 10 10 10 30 10 10 (a-2) 20 20 20 20 20 15 30 20 20 20 20 5 - (a-3) - - - - - - - - - - - - 20 (b) 70 70 70 75 65 75 60 70 70 70 50 85 70 (c) 0.1 One 2 One One One One - 3 0.05 One One One Melt index 21 22 22 24 17 27 13 22 23 22 5 30 14 Impact strength 25 24 24 20 28 18 32 24 24 23 35 11 31 Plating adhesion 8.4 9.1 9.3 8.6 9.4 8.4 9.3 7.2 9.2 7.2 9.4 6.3 6.9 Appearance quality ○ ○ ○ ○ ○ ○ ○ × ○ × ○ × × discoloration ○ ○ ○ ○ ○ ○ ○ ○ × ○ ○ ○ ○

As shown in Table 1, in Examples 1 to 7, manufactured according to the present invention, having a melt index and impact strength of equal or more, excellent in color and plating adhesion, and various external environmental changes according to the cold and heat cycling test It was confirmed that the appearance quality was maintained.

On the other hand, in the case of Comparative Example 1 containing no metal activity inhibitor, Comparative Example 3 containing a trace amount and Comparative Example 6 including the (a-3) graft copolymer having an average particle diameter exceeding the scope of the present invention, the adhesion of plating was Low and accordingly, cracks and plating swelling occurred in the cooling and heat cycle tests, and in Comparative Example 2 including an excessive amount of the metal activity inhibitor, it was confirmed that discoloration was very severe due to the metal activity inhibitor.

In addition, in the case of Comparative Example 4 containing an excess of the (a-1) graft copolymer having a small average particle diameter of the rubber, it was confirmed that the melt index is very poor, and the (a-2) graft copolymer having a large average particle diameter of the rubber In the case of Comparative Example 5 containing a small amount of impact strength was significantly reduced, it was confirmed that cracks and plating swelling occurred during the cold-heat cycle test.

In conclusion, the present inventors, when preparing a thermoplastic resin composition, when using a graft copolymer of a different rubber size, and when containing a metal active inhibitor in a certain amount, the present inventors have more than equivalent mechanical properties, discoloration and appearance quality It was confirmed that the thermoplastic resin composition having excellent plating adhesion and a molded article including the same may be implemented without deterioration.

Claims

(a-1) 1 to 25% by weight of a graft copolymer in which an aromatic vinyl compound and a vinyl cyan compound are grafted to a conjugated diene rubber polymer having an average particle diameter of rubber of 0.03 to less than 0.2 µm, (a-2) rubber 10 to 45 wt% of a graft copolymer grafted with an aromatic vinyl compound and a vinyl cyan compound to a conjugated diene rubber polymer having an average particle diameter of 0.2 to 0.5 µm and (b) an aromatic vinyl compound-vinyl cyan compound copolymer 50 to 100 parts by weight of the base resin including 80% by weight; And (c) 0.1 to 2.5 parts by weight of a metal activity inhibitor,
A thermoplastic resin composition having a melt index (220 ° C., 10 kg) of 10 to 30 g / 10 min, a plating adhesion of 8.0 to 9.2 N / cm, and a material for plating.

The method of claim 1,
The conjugated diene rubber polymers of (a-1) and (a-2) are each composed of butadiene polymer, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene copolymer and derived polymers thereof. The thermoplastic resin composition, characterized in that at least one member selected from the group.

The method of claim 1,
The aromatic vinyl compounds of (a-1), (a-2) and (b) are styrene, α-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, vinyltoluene and derivatives thereof, respectively. Thermoplastic resin composition, characterized in that at least one member selected from the group consisting of.

The method of claim 1,
The vinyl cyan compounds of (a-1), (a-2) and (b) are each one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and derivatives thereof Thermoplastic resin composition.

The method of claim 1,
The (b) aromatic vinyl compound-vinyl cyan compound copolymer is a thermoplastic resin composition, characterized in that prepared by bulk polymerization.

The method of claim 1,
(B) the aromatic vinyl compound-vinyl cyan compound copolymer comprises a vinyl cyan compound in an amount of 10 to 40% by weight.

The method of claim 1,
(B) the aromatic vinyl compound-vinyl cyan compound copolymer has a weight average molecular weight of 50,000 to 200,000 g / mol thermoplastic resin composition.

The method of claim 1,
Wherein (c) the metal activity inhibitor is a thermoplastic resin composition, characterized in that the phenolic compound represented by the formula (1).
[Formula 1]

(W is an integer of 1 to 50, x and y are each an integer of 1 to 20, and z is an integer of 1 to 100)

The method of claim 8,
(C) the metal activity inhibitor is 1-N ', 12-N'-bis (2-hydroxybenzoyl) dodecanedihydrazide (1-N', 12-N'-bis (2-hydroxybenzoyl) dodecanedihydrazide), 3- (salicyloylamino) -1,2,4-triazole and 1,2-bis (3,5-di-t-butyl-4 -Hydroxyhydrocinnamoyl) hydrazine (1,2-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamoly) hydrazine) is at least one member selected from the group consisting of thermoplastic resins.

delete

A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 9.