KR101676124B1 - Thermoplastic resin composition having exellent chemical resistantce and molded article prepared therefrom - Google Patents

Abstract

(상기 R₁ 내지 R₄는 탄소수 10 내지 25 개의 알킬기이다)로 표시되는 화합물을 포함하는 열가소성 수지 조성물 및 이로부터 제조된 성형품에 관한 것이다.
본 기재에 따르면, 충격강도, 유동성 및 내열성이 우수하면서도 신너에 대한 내화학성이 우수한 열가소성 수지 조성물을 제공하는 효과가 있다. The present invention relates to a thermoplastic resin composition having excellent chemical resistance and a molded article produced therefrom, and more particularly, to an acrylonitrile-butadiene-styrene graft copolymer and an acrylonitrile-
[Chemical Formula 1]

(Wherein R ₁ to R ₄ are alkyl groups having 10 to 25 carbon atoms) and a molded article produced from the same.
According to the present invention, there is provided an effect of providing a thermoplastic resin composition excellent in impact strength, fluidity and heat resistance, and excellent in chemical resistance to thinner.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having excellent chemical resistance and a molded article made therefrom. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a thermoplastic resin composition having excellent chemical resistance and a molded article produced therefrom. More particularly, the present invention relates to a thermoplastic resin composition having excellent impact strength, fluidity, and heat resistance and excellent chemical resistance against a thinner, To a molded article.

When painting the ABS resin, a thinner is used. At this time, the thinner component chemically attacks the ABS resin, causing a problem such as cracking.

Conventionally, in order to strengthen the chemical resistance of the thinner, methods of increasing the rubber content, increasing the rubber size, increasing the acrylonitrile content, and increasing the molecular weight have been used. However, in the case of injection molding of a large- There were many restrictions.

U.S. Patent No. 3,010,936

In order to solve the problems of the prior art as described above, the present invention aims to provide a thermoplastic resin composition excellent in impact strength, fluidity and heat resistance, and excellent in chemical resistance to thinner, and a molded article produced therefrom.

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

In order to achieve the above object, the present invention relates to an acrylonitrile-butadiene-styrene graft copolymer and an acrylonitrile-

[Chemical Formula 1]

(Wherein R &_lt; ₁ > to R &_lt; ₄ > are alkyl groups having 10 to 25 carbon atoms) and a molded article produced from the same.

The present invention also relates to a thermoplastic resin composition comprising an acrylonitrile-butadiene-styrene-based graft copolymer (B) having a heat resistance enhanced by adding at least one of an alphamethylstyrene (AMS) heat resistant resin and a phenyl maleimide (Hereinafter referred to as 'ABS resin'), and a molded article produced from the thermoplastic resin composition.

According to the present invention, there is provided an effect of providing a thermoplastic resin composition excellent in impact strength, fluidity and heat resistance, and excellent in chemical resistance to thinner, and a molded article produced therefrom.

The thermoplastic resin composition of the present invention comprises an ABS resin,

[Chemical Formula 1]

(Wherein R ₁ to R ₄ are alkyl groups having 10 to 25 carbon atoms).

R ₁ to R ₄ may be, for example, an alkyl group having from 15 to 20 carbon atoms or from 16 to 18 carbon atoms. Within this range, there is an effect of excellent balance of physical properties and chemical resistance to thinner.

The compound represented by Formula 1 may be used in an amount of 0.3 to 35 parts by weight, 1 to 25 parts by weight, or 1.5 to 17 parts by weight based on 100 parts by weight of the total amount of ABS resin, and the balance of physical properties, It has excellent chemical resistance.

As another example, the thermoplastic resin composition of the present invention comprises 100 parts by weight of a base resin comprising 10 to 50% by weight of an ABS resin, 10 to 90% by weight of a heat-resistant resin and 0 to 80% by weight of an aromatic vinyl compound-vinyl cyanide copolymer , The following formula 1

[Chemical Formula 1]

And 0.1 to 10 parts by weight of a compound represented by the general formula ( ₁₎ : wherein R ₁ to R ₄ are alkyl groups having 10 to 25 carbon atoms.

As another example, the base resin may include 10 to 50% by weight of an ABS resin, 20 to 90% by weight of a heat-resistant resin, and 0 to 65% by weight of an aromatic vinyl compound-vinyl cyanide copolymer.

The compound represented by the formula (1) is, for example, 0.2 to 8 parts by weight or 0.5 to 5 parts by weight based on 100 parts by weight of the base resin. Within this range, the effect of excellent chemical resistance to fluidity and thinner is obtained have.

For example, the thermoplastic resin composition may have an MI of 2.5 to 15 g / 10 min, or 3.0 to 10 g / 10 min, and has an excellent balance of physical properties within this range.

For example, the thermoplastic resin composition may have an HDT of 90 to 115 캜 or 95 to 115 캜, and an excellent balance of physical properties within this range.

The thermoplastic resin composition has a chemical resistance (1.0% strain curvature jig, 200 * 12.7 * 3.2 mm, thinner 1 cc) of 25 seconds or more, 30 seconds or more, 50 seconds or 50 to 300 seconds, It can be applied to an article which is excellent in heat resistance, chemical resistance and physical property balance, and in which heat resistance is particularly required.

The thermoplastic resin composition can be applied to injection-molded products, for example. In this case, the thermoplastic resin composition is excellent in chemical resistance to thinner and has an effect of preventing cracks.

The injection molded article of the present invention is characterized by being produced from the thermoplastic resin composition of the present invention.

Hereinafter, the present invention will be described in detail for each component.

First, the substrate is that the chemical resistance of a molded article manufactured from superior thermoplastic resin compositions, and which, more particularly, by adding a heat-resistant resin to the ABS resin which enhance the heat resistance Formula ₁ (R 1 to R ₄ has a carbon number of 10 To 25 alkyl groups) to improve heat resistance and chemical resistance, and a molded article obtained by molding the thermoplastic resin composition.

Acrylonitrile-butadiene-styrene (ABS) resin "and" heat-resistant acrylonitrile-butadiene-styrene (ABS) resin " Refers to both a copolymer obtained by substituting a part of the graft copolymer with a heat resistant monomer or a resin obtained by adding a heat resistant copolymer or a heat resistant resin to an acrylonitrile-butadiene-styrene (ABS) graft copolymer.

[Chemical Formula 1]

Ⅰ. Thermoplastic resin composition

1. ABS resin

The ABS resin of the present invention is a copolymer obtained by grafting an aromatic vinyl compound and a vinyl cyanide compound onto a rubbery polymer.

The rubbery polymer is not limited in its constitution, but may be a diene rubber such as polybutadiene, polystyrene-butadiene or polyacrylonitrile-butadiene, a saturated rubber in which hydrogen is added to the diene rubber, a poly Acrylic rubbers such as isoprene rubber, chloroprene rubber, ethylene-propylene (EPM) rubber, and ethylene-propylene-diene monomers (e.g., polybutylene terephthalate, Ethylene-propylene-diene (EPDM) rubber, and polybutadiene rubber among diene rubbers is preferably used.

The content of the rubbery polymer is not limited in the present invention, but is preferably 30 to 75% by weight based on the total weight of the graft copolymer resin. Not only the graft ratio is high within the above range, but also the impact strength and chemical resistance of the final molded product are excellent.

The aromatic vinyl compound grafted to the rubber polymer is not limited in its kind but may be selected from the group consisting of styrene, alpha-methylstyrene, beta-methylstyrene, p-methylstyrene, ethyl And is selected from the group consisting of styrene, ethylstyrene, hydroxystyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, and vinylnaphthalene. One or more of them may be used, and styrene is preferably used.

The content of the aromatic vinyl compound is not limited in the present invention, but is preferably 20 to 65% by weight based on the total weight of the graft copolymer resin, and it is possible to efficiently increase the graft ratio with the rubbery polymer in the above range.

The composition of the vinyl cyanide grafted onto the rubbery polymer is not limited in its constitution, but it may be a saturated nitrile type such as acrylonitrile, an unsaturated nitrile such as methacrylonitrile and ethacrylonitrile, , And acrylonitrile (acrylonitrile) is preferably used.

The content of the vinyl cyanide compound is not limited in the present invention, but is preferably 5 to 30% by weight based on the total weight of the graft copolymer resin, and it is possible to efficiently increase the graft ratio with the rubber polymer in the above range.

The ABS resin is most preferably an acrylonitrile-butadiene-styrene graft copolymer in which acrylonitrile and styrene are grafted to a butadiene rubber polymer exhibiting excellent physical properties such as impact resistance and heat resistance.

The ABS resin used in one embodiment of the present invention is a styrene-acrylonitrile (SAN) grafted on butadiene rubber as shown in the following formula (2). However, the term 'ABS resin' is not necessarily limited to acrylonitrile-butadiene-styrene copolymer resin, but may be a resin composed of a copolymer of a vinyl cyanide compound-rubber polymer-aromatic vinyl compound It is also possible to extend the interpretation to

(2)

2. Heat-resistant resin (heat-resistant reinforcement matrix )

As a general method of imparting heat resistance to the ABS resin, a method of adding alpha-methylstyrene or maleimide monomers excellent in heat resistance in the ABS polymerization process and a method of adding heat- There is a method of mixing the resin with the ABS resin.

The heat-resistant resin is usually prepared by copolymerizing an α-methylstyrene or maleimide monomer with an aromatic vinyl compound monomer such as vinyl cyan compound such as acrylonitrile and / or styrene, 3-membered copolymer.

A method of producing a heat-resistant ABS resin by kneading a heat-resistant resin with the ABS resin has been proposed. The method of producing such a heat-resistant ABS resin is a method of producing a heat-resistant ABS resin by replacing a part or the entire amount of styrene used for producing a heat-resistant copolymer for kneading with alpha-methylstyrene having excellent heat resistance (U.S. Patent Nos. 3,010,936 and 4,659,790) and a maleimide compound to prepare a heat resistant ABS resin (JP-A-58-206657, JP-A-63-162708, JP-A-63-235350 And U.S. Patent No. 4,757,109), a method of kneading with a polycarbonate resin, and a method of filling an inorganic material.

The heat-resistant resin of the present invention is produced by copolymerizing an aromatic vinyl compound with a polymer monomer having heat-resistant properties within a certain temperature range, or is further produced by copolymerizing a vinyl cyan compound.

Examples of the heat-resistant polymeric monomer include alpha-methylstyrene, N-phenyl maleimide, N-phenyl maleic acid and styrene maleic anhydride. At least one selected from the group consisting of

The heat-resistant resin according to the present invention may further include, for example, a copolymer containing alpha-methylstyrene (N-phenylmaleimide), based on a copolymer containing alpha-methylstyrene.

I) alpha-methylstyrene polymers (hereinafter referred to as AMS resins)

As the heat resistant resin of the present invention, the AMS polymer is a copolymer of alpha methyl styrene (hereinafter referred to as 'AMS') and acrylonitrile (AN) such as the following chemical formula 3 or a copolymer of AMS, acrylonitrile (AN) Styrene), generally 50 to 80 parts by weight of an AMS monomer, 20 to 50 parts by weight of acrylonitrile (AN) and 0 to 10 parts by weight of styrene are copolymerized at a predetermined ratio. When the content of the AMS monomer is less than 50 parts by weight, there may be a problem that the heat resistance is lowered and discolored to yellow when heated. When the content of the AMS monomer exceeds 80 parts by weight, AMS is continuously added to the resulting heat- There may be a problem that the combined structure ([AMS] - [AMS] - [AMS]: pyrolysis structure) is rapidly generated and easily decomposed into heat. When the content of acrylonitrile (AN) is less than 20 parts by weight, conversion and molecular weight may be deteriorated. When the amount of acrylonitrile (AN) is more than 50 parts by weight, a large amount of acrylonitrile (AN) And the gel polymer is very weak to heat and may act as a foreign matter of red or black color upon heating, thereby damaging the appearance of the product. If the content of styrene is more than 10 parts by weight, the heat resistance may be lowered.

(3)

For example, the present invention is desirably composed of 15 to 40% by weight of an ABS resin, 20 to 85% by weight of an AMS heat-resistant resin, and 0 to 65% by weight of a general SAN resin. When the content of the AMS resin is less than 20% by weight, sufficient heat resistance can not be obtained. When the content of the AMS resin exceeds 85% by weight, there is a problem that the impact strength is lowered due to the relative shortage of the ABS resin.

Ii) N-Phenyl Maleimide polymer (hereinafter referred to as PMI-based resin)

As the heat-resistant resin of the present invention, the PMI-based resin may be a copolymer of an N- (substituted) maleimide, a vinyl-based monomer and an unsaturated dicarboxylic acid. Typically, the PMI-based resin refers to a ternary copolymer of N-phenylmaleimide-styrene-maleic anhydride as represented by the following chemical formula (4), for example PMI 45 to 55 wt% It is preferable that it is composed of 40 to 50 wt% of styrene and 1 to 10 wt% of maleic anhydride, and most preferably 50 wt% of PMI, 45 wt% of styrene and 5 wt% of maleic anhydride, The present invention is not limited thereto.

[Chemical Formula 4]

The PMI-based resin of the present invention can be used alone or in combination with the AMS-based resin. Specific examples thereof include 15 to 40% by weight of ABS resin, 5 to 40% by weight of PMI-based heat resistant resin, and 20 to 80% Or 15 to 40% by weight of an ABS resin, 20 to 80% by weight of an AMS-based heat-resistant resin, 5 to 40% by weight of a PMI-based heat-resistant resin and 0 to 60% by weight of a SAN resin. In the above range, excellent heat resistance and impact resistance are exhibited.

3. SAN Resin (General Matrix)

Typically, the matrix of the ABS resin is a copolymer of an aromatic vinyl compound and a vinyl cyanide compound.

The cyanide vinyl compound and the aromatic vinyl compound have been described above in the 'graft copolymer', and thus will not be described.

The matrix copolymer of the present invention may be, for example, a styrene-acrylonitrile (hereinafter referred to as " SAN ") copolymer obtained by copolymerizing styrene and acrylonitrile as aromatic vinyl compounds, Quot;). In this specification, the term "SAN resin" is not necessarily limited to styrene-acrylonitrile (SAN) copolymer resin, and may be a copolymer of vinyl cyan compound and aromatic vinyl compound Explain that it is also possible to perform an extended analysis with a constructed resin.

[Chemical Formula 5]

The present invention relates to a heat resistant ABS resin which is applied as a matrix by applying an AMS and / or PMI heat resistant resin to an ABS resin or a general SAN resin having a weight average molecular weight (Mw) of 100,000 to 180,000 g / Resin is used.

4. Chemical resistance improver

The chemical resistance improver of the present invention is a compound represented by the following formula (1) wherein R ₁ to R ₄ are alkyl groups having 10 to 25 carbon atoms.

[Chemical Formula 1]

The compound represented by Formula 1 is 0.1 to 10 parts by weight based on 100 parts by weight of the ABS resin. Within this range, the compound has an excellent balance of physical properties, fluidity, and chemical resistance to thinner.

Hereinafter, possible production methods for producing the thermoplastic resin composition of the present invention will be described.

Ⅱ. Manufacturing method

Known methods for producing the copolymer resin include emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, suspension polymerization and bulk polymerization, and emulsion polymerization and bulk polymerization.

As is well known from the above methods, emulsion polymerization and suspension polymerization are advantageous in that the reaction temperature is relatively easy to release due to the relatively easy release of reaction heat, and thus the polymer is less deformed due to heat. On the other hand, emulsifier, viscosity enhancer or coagulant And the added materials are not removed at the final stage, so that they remain as impurities in the final product, thereby deteriorating various physical properties. Further, after completion of the polymerization, additional processes such as dehydration, coagulation or drying to remove water as a reaction medium must be performed, and the removed water must be subjected to a wastewater treatment process. Therefore, it is economically more costly This process has the disadvantage of being a process.

On the other hand, it is difficult to control the reaction heat or the viscosity of the reaction solution by solution polymerization or bulk polymerization. However, since there is no additive used separately for the polymerization, residual impurities in the final product are so small that the physical properties are excellent, And unreacted monomers are recovered and used again. Therefore, unlike emulsion polymerization or suspension polymerization, production cost is very low.

Although the present invention is not limited to any one of the above production methods, it is common to produce by emulsion polymerization or bulk polymerization at the production site.

In addition, the ABS resin used in the examples of the present invention was prepared by emulsion polymerization, and the AMS heat-resistant resin and the PMI heat-resistant resin were produced by bulk polymerization.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention within the scope and spirit of the following claims, Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

1. Preparation and preparation of composition

A. ABS Graft Copolymer: DP270 (manufactured by LG Chemical Co., Ltd.), which was prepared by emulsion polymerization, was used. The butadiene content of the resin was 60% by weight and the volume average rubber particle size was 0.3 占 퐉.

B. Heat resistant reinforcement SAN matrix

(B-1) AMS heat-resistant resin: 100 UH (manufactured by LIG Chemical Co., Ltd.), which was prepared by bulk polymerization of α-methylstyrene (AMS) and acrylonitrile (AN)

(B-2) PM-series heat-resistant resin: MS-NB (manufactured by Denka) composed of N-phenyl maleimide (PMI), styrene and maleic anhydride was used .

C. SAN resin: A product name 92HR (manufactured by LG Chemical Co., Ltd.) manufactured by bulk polymerization was used. The resin had an acrylonitrile (AN) content of 27% by weight and a weight average molecular weight (Mw) of 130,000 g / mol.

D. Chemical resistance improver: Pentaerythritol tetrastearate (PETS, manufactured by FACI) was used as the compound represented by the formula (1).

Examples 1 to 7 and Comparative Examples 1 to 5

The components shown in Table 1 were kneaded at 240 ° C using a twin-screw extruder according to the proportions thereof, and thermoplastic resin composition specimens were prepared through injection at 240 ° C.

division Example Comparative Example One 2 3 4 5 6 7 One 2 3 4 5 A 25 25 25 25 30 30 30 25 25 30 30 30 B-1 60 75 75 75 50 0 0 60 75 50 0 0 B-2 0 0 0 0 20 35 0 0 0 20 35 0 C 15 0 0 0 0 35 70 15 0 0 35 70 D 2 0.5 2 5 2 2 2 0 0 0 0 0

[Test Example]

The properties of the thermoplastic resin compositions (specimens) prepared in Examples 1 to 6 and Comparative Examples 1 to 4 were measured by the following methods, and the results are shown in Table 2 below.

(1) Impact Strength: A 3.2 mm thick sample having a notch formed according to ASTM D256 was measured using an Izod impact strength meter (TINIUS OLSEN).

(2) Flowability (MI): Measured under the conditions of 220 캜 and 10 kgf / cm ² according to ASTM D1238.

(3) Heat distortion temperature (HDT): The heat distortion temperature of the specimen having a thickness of 6.35 mm was measured at a rate of 18.6 kgf / cm 2 at 120 ° C / hr according to ASTM D648.

(4) Chemical resistance: The time for cracks to occur on the specimen after applying a cushion of 200 * 12.7 * 3.2 mm to a curvature jig having 1.0% strain and applying 1 cc of thinner (T-803 manufactured by Norubi Chemical Co., Ltd.) Were measured.

division Example Comparative Example One 2 3 4 5 6 7 One 2 3 4 5 Impact strength (kgfcm / cm) 20.7 18.1 18.8 20.2 18.9 14.1 33.1 18.5 17.9 18.1 13.3 32.4 Flowability (g / 10 min) 9.1 7.0 7.1 7.0 3.5 3.0 20.3 9.0 7.0 3.5 3.0 20.5 HDT (° C) 98 102 102 102 107 112 88 98 102 107 112 88 Chemical resistance (seconds) 57 25 51 92 52 55 63 23 14 27 19 51

As shown in Table 2, the thermoplastic resin compositions (Examples 1 to 7) of the present invention corresponded to the thermoplastic resin compositions not containing PETS (Comparative Examples 1 to 5) in fluidity and heat resistance , The impact strength slightly increased, and the chemical resistance was excellent.

Claims (17)

delete delete delete To 100 parts by weight of a base resin consisting of 10 to 50% by weight of an acrylonitrile-butadiene-styrene graft copolymer, 35 to 75% by weight of a heat resistant resin and 0 to 35% by weight of a SAN resin,
[Chemical Formula 1]

(Wherein R1 to R4 are alkyl groups having 10 to 25 carbon atoms), and 2 to 5 parts by weight of a compound represented by the formula
Thermoplastic resin composition. 5. The method of claim 4,
Wherein the heat-resistant resin is an AMS resin, a PMI resin, or a mixture thereof
Thermoplastic resin composition. 6. The method of claim 5,
Wherein the AMS-based heat-resistant resin is an? -Methylstyrene copolymer
Thermoplastic resin composition. 6. The method of claim 5,
The PMI-based heat-resistant resin is characterized by being an N-phenylmaleimide copolymer
Thermoplastic resin composition. 5. The method of claim 4,
Wherein the SAN resin has a weight average molecular weight of 100,000 to 180,000 g / mol
Thermoplastic resin composition. 5. The method of claim 4,
Wherein the base resin comprises 15 to 40% by weight of an acrylonitrile-butadiene-styrene graft copolymer, 50 to 75% by weight of an AMS-based heat-resistant resin, and 0 to 35% by weight of a SAN resin
Thermoplastic resin composition. 5. The method of claim 4,
Wherein the base resin comprises 25 to 40% by weight of an acrylonitrile-butadiene-styrene graft copolymer, 35 to 40% by weight of a PMI-based heat resistant resin, and 20 to 35% by weight of a SAN resin
Thermoplastic resin composition. 5. The method of claim 4,
Wherein the base resin comprises 25 to 40% by weight of an acrylonitrile-butadiene-styrene graft copolymer, 20 to 50% by weight of an AMS heat resistant resin, 15 to 25% by weight of a PMI heat resistant resin and 0 to 35% Characterized by comprising
Thermoplastic resin composition. delete 5. The method of claim 4,
Wherein the thermoplastic resin composition has an MI of 2.5 to 15 g / 10 min
Thermoplastic resin composition. 5. The method of claim 4,
Wherein the thermoplastic resin composition has an HDT of 90 to 115 캜
Thermoplastic resin composition. 5. The method of claim 4,
The thermoplastic resin composition is characterized in that the chemical resistance (1.0% strain curvature jig, 200 * 12.7 * 3.2 mm, thinner 1 cc) is 25 seconds or more
Thermoplastic resin composition. 5. The method of claim 4,
The thermoplastic resin composition is characterized by being applied to an injection-painted product
Thermoplastic resin composition. An injection-molded article produced from the thermoplastic resin composition of any one of claims 4 to 11 and 13 to 16.