KR101072120B1 - Abs resin composition with excellent chemical resistance and toughness - Google Patents

Abstract

The present invention relates to an acrylonitrile-butadiene-styrene resin composition having excellent chemical resistance (ESCR) and toughness, and more particularly to an acrylonitrile-butadiene-styrene copolymer acrylate-styrene-acrylonitrile air. The present invention relates to an acrylonitrile-butadiene-styrene resin composition comprising a super-polymerized acrylonitrile-butadiene-styrene copolymer and a styrene-acrylonitrile copolymer.

According to the present invention, there is an effect of providing an acrylonitrile-butadiene-styrene resin composition excellent in chemical resistance, toughness and impact strength to the blowing agent used in the urethane insulation layer on the refrigerator inner.

Chemical resistance, impact strength, acrylonitrile-butadiene-styrene, acrylate-styrene-acrylonitrile, styrene-acrylonitrile, bulk polymerization

Description

Acrylonitrile-butadiene-styrene resin composition excellent in chemical resistance and toughness {ABS RESIN COMPOSITION WITH EXCELLENT CHEMICAL RESISTANCE AND TOUGHNESS}

The present invention relates to an acrylonitrile-butadiene-styrene resin composition, and more particularly, to an acrylonitrile-butadiene-styrene resin composition having excellent chemical resistance, toughness and impact strength to a urethane blowing agent in the manufacture of a refrigerator bed.

Acrylonitrile-butadiene-styrene resin or rubber-modified styrene (HIPS) is mainly used as the inner resin of the refrigerator, and is manufactured by vacuum forming a thin sheet-like sheet. The urethane liquid is injected between the manufactured refrigerator inner material and the outer steel plate frame to undergo foaming and solidification. The urethane liquid includes a foaming agent, and a foaming agent is mainly a freon-based compound (CFC-11, HCFC-141b, HFC-245fa, etc.) and cyclopentane are used, and the blowing agent compounds are applied to chemical cracks in areas where internal stresses are concentrated in contact with the inner parts of the resin during the refrigerator manufacturing process or the manufacturing process. Therefore, the inner lining of the refrigerator should be resistant to such urethane blowing agents.

In order to improve the resistance to the above-mentioned blowing agent, that is, chemical resistance, ongoing research is being conducted, but there are not many techniques for simultaneously increasing the chemical resistance and simultaneously improving the toughness and impact strength, which are essential physical properties of the refrigerator wound material.

Conventional techniques for increasing chemical resistance include a method of increasing the content of vinyl cyanide compound in the ABS resin of Japanese Patent Application Laid-Open No. 2-284906 and a method using a high molecular weight styrene-acrylonitrile resin having a molecular weight of 800,000 or more of EP19728. Is disclosed. However, an increase in the content of the vinyl cyanide compound or the introduction of a high molecular weight SAN resin has problems such as yellowing during the resin processing and a decrease in fluidity.

In addition, a method using the ASA resin of Japanese Patent Laid-Open No. 4-170460 is disclosed. However, when the ASA resin is used, the impact resistance is reduced at low temperatures and room temperature because the acrylic rubber component has a higher glass transition temperature than the diene rubber component. A problem arises.

In addition, there is a method of introducing PE into ABS resin by using the PE-g-SAN compatibilizer of Korean Patent No. 10-0572282, but when PE or PP is applied together with the compatibilizer, peeling occurs during the processing of the resin and a significant decrease in physical properties. There is a problem.

In order to solve the problems of the prior art as described above, the present invention provides an acrylonitrile-butadiene-styrene resin composition which is particularly excellent in chemical resistance while maintaining good impact resistance and toughness. The purpose is to provide.

In order to achieve the above object, the present invention (A) 20 to 50 parts by weight of acrylonitrile-butadiene-styrene copolymer containing a rubbery polymer having an average particle size of 0.1 to 0.5 ㎛; (B) 5 to 20 parts by weight of an acrylate-styrene-acrylonitrile copolymer containing an acrylate rubber having an average particle size of 0.1 to 0.5 mu m; (C) 5 to 20 parts by weight of the super-diameter bulk acrylonitrile-butadiene-styrene copolymer having a rubber average particle size of 5 to 10 m; (D) 40 to 80 parts by weight of the styrene-acrylonitrile copolymer; provides an acrylonitrile-butadiene-styrene resin composition comprising a.

Hereinafter, the content of the present invention will be described in detail.

(A) Acrylonitrile-butadiene-styrene copolymer (hereinafter '(A) ABS copolymer')

The (A) ABS copolymer according to the present invention contains a rubbery polymer (rubber latex) having an average particle size of 0.1 to 0.5 µm, and an aromatic vinyl compound such as styrene and an acrylonitrile in the rubbery polymer (rubber latex) The monomer mixture of the vinyl cyanide compound may be prepared by graft polymerization.

The aromatic vinyl compound may be selected from the group consisting of substituted styrenes of styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, and t-butylstyrene, and the amount thereof may be 30 to 60 parts by weight based on the entire ABS copolymer. More specifically, it is preferable to use 30 to 60 parts by weight based on 100 parts by weight of the total (A) ABS copolymer.

The vinyl cyanide compound may be selected from one or more selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, of which acrylonitrile is preferred, and the amount of the vinyl cyanide compound is 10 to 20 based on the entire ABS copolymer. It may be part by weight, and more specifically, it is preferable to use 10 to 20 parts by weight based on 100 parts by weight of the total (A) ABS copolymer. If the content is less than 10, the chemical resistance and rigidity is lowered, and if it is more than 20, there may be a problem of the fluidity decrease.

The rubber polymer (rubber latex) may be selected from the group consisting of polybutadiene, styrene-butadiene copolymer, polyisoprene and butadiene-isoprene copolymer, the average particle diameter of the rubber latex is preferably 0.1 to 0.5㎛ Do. If the average particle diameter is less than 0.1 ㎛ the gloss of the final product is improved, but the impact strength is lowered, if the average particle diameter is more than 0.5 ㎛ may be significantly reduced gloss and fluidity of the final product.

The rubber polymer (rubber latex) may be used in an amount of 20 to 60 parts by weight based on the entire ABS copolymer, and more preferably, 20 to 60 parts by weight based on 100 parts by weight of the total (A) ABS copolymer. . If the content is 20 parts by weight or less, it is difficult to implement the impact strength required in the present invention, when there is more than 60 may have a problem that the fluidity is lowered.

(B) Acrylate Styrene Acrylonitrile  Copolymer (hereinafter '(B) ASA  Copolymer ')

(B) The ASA copolymer contains an acrylate rubber having an average particle size of 0.1 to 0.5 µm, and may be prepared by graft polymerization of a vinyl cyanide compound and an aromatic vinyl compound on the acrylate rubber.

The acrylate rubber may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, the amount of which may be 20 to 60 parts by weight based on the entire ASA copolymer, more limited Therefore, it is preferable to use 20 to 60 parts by weight based on 100 parts by weight of the entire ASA copolymer. The average particle diameter of the acrylate-based rubber particles is preferably 0.1 to 0.5㎛. If the average particle diameter is less than 0.1㎛ improves the gloss of the final product but the impact strength is lowered, if the average particle diameter exceeds 0.5㎛ the gloss and fluidity of the final product Can be significantly lowered.

The aromatic compound may be at least one selected from the group consisting of styrene, alpha-methyl styrene, para-methyl styrene, vinyl toluene, and t-butyl styrene, the amount of which is 30 to 60 parts by weight based on the entire ASA copolymer. More preferably, it is preferable to use 30 to 60 parts by weight based on 100 parts by weight of the entire (B) ASA copolymer.

The vinyl cyanide compound may be selected from one or more selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile, and the amount of the vinyl cyanide compound may be 10 to 20 parts by weight based on the entire ASA copolymer, and more specifically, It is preferable to use 10-20 weight part based on 100 weight part of said whole (B) ASA copolymers, It is also possible to graft copolymerize a (meth) acrylic acid ester compound and a functional monomer as needed.

The (B) ASA copolymer improves the chemical resistance of the final ABS resin composition with respect to the urethane foaming compound, but the acrylate has a higher glass transition temperature than the diene rubber component, so that the tensile strength of the final ABS resin composition is low and normal temperature. It can reduce the strength and impact strength.

The reduction of tensile strength and impact strength can be compensated by further including the following (C) ABS copolymer, the final ABS resin composition comprising the (B) ASA copolymer and (C) ABS copolymer is tensile There is no decrease in strength and impact strength, and the chemical resistance is also improved by the (B) ASA copolymer.

(C) large diameter Acrylonitrile Butadiene-styrene copolymer (hereinafter '(C) super-diameter ABS  Copolymer ')

The (C) super-diameter ABS copolymer resin is a continuous or batch dose bulk polymerization method, butadiene-based rubber and styrene in a mixed solution in which aromatic vinyl compounds such as styrene and vinyl cyanide compounds such as acrylonitrile are dissolved in a reaction solvent. -It can superpose | polymerize by adding 1 or more types chosen from the group which consists of butadiene type rubbers.

The butadiene-based or styrene-butadiene-based rubber may be used in an amount of 5 to 20 parts by weight based on the total amount of the super-diameter ABS copolymer, and more specifically, 5 to 20 parts by weight based on 100 parts by weight of the total super-diameter ABS copolymer. It is preferable that it is included by 20 weight part, and it is preferable that average particle diameter is 5-10 micrometers. If the average particle diameter is less than 5 μm, it is difficult to expect the desired level of chemical resistance, tensile strength and impact resistance improvement. If the average particle diameter is more than 10 μm, the chemical resistance, tensile strength and impact resistance are increased, but the gloss of the final product is sharply decreased. Therefore, a problem arises that it is difficult to use the refrigerator inner material.

The aromatic vinyl compound may be used by selecting one or more from the group consisting of substituted styrenes of styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, and t-butylstyrene, of which styrene is preferable. . The aromatic vinyl compound may be 60 to 80 parts by weight based on the total amount of the super-diameter ABS copolymer, and more specifically, 60 to 80 parts by weight based on 100 parts by weight of the total super-diameter ABS copolymer when the graft copolymer is prepared. .

The vinyl cyanide compound may be used by selecting one or more from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, and in particular, it is preferable to use acrylonitrile, and the content of the super-diameter ABS copolymer as a whole It may be 15 to 30 parts by weight, and more preferably 15 to 30 parts by weight based on 100 parts by weight of the total ultra-diameter ABS copolymer when manufacturing graft copolymer.

(D) styrene-acrylonitrile copolymer (hereinafter '(D) SAN copolymer')

The (D) SAN copolymer may be prepared by bulk polymerization or suspension polymerization of monomers of an aromatic vinyl compound and a vinyl cyanide compound, and a weight average molecular weight is preferably 100,000 to 200,000. When the weight average molecular weight is less than 100,000, The chemical resistance, tensile strength and impact strength is lowered, and when it exceeds 200,000, the workability and fluidity of the resin is lowered.

As the aromatic vinyl compound, if one or more selected from the group consisting of styrene, alpha-methyl styrene, para-methyl styrene, vinyl toluene and t-butyl styrene can be used, the amount thereof is 60 to the whole SAN copolymer. It may be 70 parts by weight, it is more preferably used 60 to 70 parts by weight based on 100 parts by weight of the total SAN copolymer. If the content of the aromatic vinyl compound is less than 60 parts by weight, there is a problem of lowering the rigidity or processability, and if it exceeds 70 parts by weight, there is a problem of lowering the chemical resistance due to the relative decrease of the acrylonitrile content.

As the vinyl cyanide compound, at least one selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile may be used, and the amount of the vinyl cyanide compound is 30 to 40 weight based on the total amount of the (D) SAN copolymer resin. It may be part, more preferably 30 to 40 parts by weight based on 100 parts by weight of the total SAN copolymer resin. When the content of the vinyl cyanide compound is less than 30 parts by weight, the chemical resistance is lowered. When the content of the vinyl cyanide compound is more than 40 parts by weight, the flowability is decreased, resulting in poor workability and adversely affect the color of the final product.

The final ABS resin composition of the present invention having the composition as described above may be prepared by a conventional melt kneading process, antioxidants, heat stabilizers, lubricants, ultraviolet stabilizers, lubricants as needed within the scope of the present invention without departing from the object Additives such as release agents, flame retardants, antistatic agents, antidrip agents, inorganic fillers, impact modifiers and the like may be used.

When the extrusion sheet for refrigerator internals including the final ABS resin composition is manufactured, the final ABS resin composition having excellent toughness and impact strength as well as chemical resistance to a foaming agent can be prepared as compared with a conventional ABS resin composition.

In addition, the final ABS resin composition is excellent in chemical resistance to compounds used as polyurethane foaming agents, such as freon-based and cyclopentane, as well as in the refrigerator inner phase, can be used for the chemical resistance against the resin using the foaming agent. .

Hereinafter, preferred examples will be described in order to help the understanding of the present invention.

[Example]

Example 1

(A) Acrylonitrile-butadiene-styrene copolymer resin

60 parts by weight of a rubbery polymer having a rubbery average particle size of 0.3 μm, 30 parts by weight of styrene, and 10 parts by weight of acrylonitrile were used.

(B) acrylate-styrene-acrylonitrile copolymer resin

LG Chemical Co., Ltd. ASA SA927 was used, which includes 50 parts by weight of an acrylate rubbery polymer having a rubbery average particle size of 0.3 μm, 38 parts by weight of styrene, and 12 parts by weight of acrylonitrile.

(C) Extra large diameter ABS resin (C1)

LG ABS MA210, a large diameter ABS resin manufactured by continuous bulk polymerization method, comprising 9 parts by weight of a rubbery polymer having an average particle size of 9.4 μm, 68 parts by weight of styrene, and 23 parts by weight of acrylonitrile. Used.

(D) Styrene-acrylonitrile (SAN) copolymer resin

LG Chem SAN 96HC Co., Ltd., comprising 67 parts by weight of styrene and 33 parts by weight of acrylonitrile, having a weight average molecular weight of 170,000, was used.

(A), (B), (C) and (D) prepared above were mixed with (A) 23 parts by weight, (B) 10 parts by weight, (C1) 10 parts by weight and (D) 57 parts by weight, respectively. , ABS resin composition was prepared.

[Example 2]

In Example 1, the contents of (A), (B), (C) and (D), respectively, (A) 21 parts by weight, (B) 10 parts by weight, (C1) 20 parts by weight and (D) 49 parts by weight It carried out similarly to Example 1 except the part used.

Comparative Example 1

Except for using only (A) and (D) in Example 1, except that 33 parts by weight (A) and 67 parts by weight of (D) was carried out in the same manner as in Example 1.

Comparative Example 2

In Example 1, only (A), (C) and (D) were used, and (A) 33 parts by weight, (C2) 10 parts by weight and (D) 57 parts by weight were used, and (C) was (C1). LG Chemical Co., Ltd., which is a large-diameter ABS resin manufactured by a continuous bulk polymerization method, comprising 13 parts by weight of a rubbery polymer having an average particle size of 1.3 μm, 69 parts by weight of styrene, and 18 parts by weight of acrylonitrile. It carried out similarly to Example 1 except having used ABS MA201 (C2).

Comparative Example 3

In Example 1, except that only (A), (B) and (D), and (A) 24 parts by weight, (B) 10 parts by weight and (D) 66 parts by weight is the same as in Example 1 It was carried out.

[Comparative Example 4]

In Example 1, only (A), (B) and (C) were used, and (A) 23 parts by weight, (B) 10 parts by weight, (C) 10 parts by weight and (D) 57 parts by weight were used. Wherein (C) instead of (C1), the rubbery average particle size is 1.3 ㎛ ㎛ rubber polymer 13 parts by weight, styrene 69 parts by weight and acrylonitrile 18 parts by weight, a large diameter ABS resin produced by a continuous bulk polymerization method LG Chemicals, Inc. MA ABS MA201 (C2) was used in the same manner as in Example 1 except that.

[Comparative Example 5]

In Example 1, only (A), (C) and (D), and the same as in Example 1 except that (A) 33 parts by weight, (C1) 10 parts by weight and (D) 57 parts by weight It was carried out.

For accurate experimental results, the rubber contents of the compositions of Examples and Comparative Examples prepared above were the same, and the physical properties of the specimens prepared above were measured in the following manner. Molding conditions and physical property evaluation conditions used in the present invention are as follows.

(1) HCFC-141b chemical resistance test

Tensile specimens of 195 mm x 19 mm x 3 mm were prepared by injection molding, and then measured using JIG fabricated directly for chemical resistance evaluation. The molded specimens were fixed to JIG for each strain, and then placed in a desiccator, injected with 350 ml of HCFC-141b, covered with a lid, and left for 18 hours at -20 ° C and 4 hours at room temperature. After that, the specimens were taken out and left for 30 minutes, and the JIG values of the strains which were not bent at 180 ^{° and} cracks were measured. The cyclopentane chemical resistance test was measured using the same injection specimens and JIG as described above. Each strain was fixed in JIG, immersed in cyclopentane for 2 minutes, then taken out and maintained for 2 minutes, and then bent 180 ^° to measure the strain of JIG without cracking.

(2) toughness

The energy to withstand until fracture was measured by the area consisting of stress-strain curves by the ASTM D638 method.

(3) Izod impact strength

Based on ASTM D256 (1/4 ", 23 ℃) was measured at room temperature (23 ℃) and low temperature (-20 ℃).

In addition to the above Examples and Comparative Examples, the results of measuring the chemical resistance, tensile strength and Izod impact strength in each Example and Comparative Example are shown in Table 1 (unit: parts by weight).

※ ↑ ↓: The chemical resistance which can be measured by the chemical resistance measuring machine used in this experiment is 0.3 to 2.0, wherein ↑ is more than 2.0, and ↓ is less than 0.3.

(A): ABS resin containing the rubbery polymer of an average particle diameter of 0.3 micrometer

(B): ASA resin containing the acrylate-based rubbery polymer having an average particle diameter of 0.3 µm

(C1): ABS resin produced by continuous bulk polymerization with an average particle diameter of 9.4 탆

(C2): ABS resin produced by continuous bulk polymerization having an average particle diameter of 1.3 μm

(D): SAN resin with a weight average molecular weight of 170,000

From the results of the above [Table 1], [Example 1] and [Example 2] of the present invention is an ABS resin composition prepared by containing acrylate-based ASA rubber copolymer resin and super-diameter continuous bulk polymerization ABS, It shows excellent chemical resistance, toughness and impact strength. In addition, even when the ASA rubber polymer having a relatively higher glass transition temperature than the ABS rubber polymer was introduced, it was found that the impact strength was reinforced by producing an ABS resin composition including the super-diameter bulk polymerized ABS.

[Comparative Example 1] is an ABS resin composition containing (A) and (D), which is not excellent in impact strength, toughness and chemical resistance, and [Comparative Example 2] is (A), (C2) and (D) As an ABS resin composition containing, it was found that the chemical resistance and toughness is not excellent. In addition, Comparative Example 3 is an ABS resin composition containing (A), (B) and (D), it was found that the toughness and impact strength at low temperatures are not excellent.

[Comparative Example 5] is an ABS resin composition containing (A), (C1) and (D), and it was found that chemical resistance and toughness of HCFC-141b are lowered by not including component (B). .

[Comparative Example 2] and [Comparative Example 4] includes a continuous bulk polymerized ABS resin composition (C2) having an average rubber particle diameter of 1.3 μm instead of (C1), it is not excellent in chemical resistance, toughness and impact strength, This can be seen that the effect of the chemical resistance and toughness when the average particle size of the rubber is more than 4 ㎛ the critical point.

As described above, the present invention provides an acrylonitrile-butadiene-styrene copolymer by introducing an acrylate-styrene-acrylonitrile copolymer and a super-diameter bulk polymerization acrylonitrile-butadiene-styrene copolymer, Not only is it excellent in chemical resistance against urethane foaming agents, but also has an effect of providing an ABS resin composition for a refrigerator internal wound having excellent physical properties such as toughness and impact strength.

While the invention has been described in detail with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the spirit of the invention, and such modifications and variations belong to the appended claims. will be.

Claims (9)

(A) 20 to 50 parts by weight of acrylonitrile-butadiene-styrene copolymer containing a rubbery polymer having an average particle size of 0.1 to 0.5 mu m;  (B) 5 to 20 parts by weight of an acrylate-styrene-acrylonitrile copolymer containing an acrylate rubber having an average particle size of 0.1 to 0.5 mu m; (C) 5 to 20 parts by weight of the super-diameter bulk acrylonitrile-butadiene-styrene copolymer having an average particle size of the rubbery polymer of 5 to 10 m; And (D) 40 to 80 parts by weight of styrene-acrylonitrile copolymer; The copolymer (A) has an acrylonitrile content of 10 to 20 parts by weight of the acrylonitrile-butadiene-styrene copolymer grafted to the rubbery polymer, The copolymer (B) has an acrylonitrile content of 10 to 20 parts by weight of the acrylate-styrene-acrylonitrile copolymer grafted to the acrylate rubbery, The copolymer (C) has an acrylonitrile content of 15 to 30 parts by weight of the acrylonitrile-butadiene-styrene copolymer grafted to the rubbery polymer, The acrylonitrile-butadiene-styrene resin composition of (D) the styrene-acrylonitrile copolymer has an acrylonitrile content of 30 to 40 parts by weight. The method of claim 1, The acrylonitrile-butadiene-styrene copolymer of the above (A) 30 to 60 parts by weight of an aromatic vinyl compound selected from the group consisting of substituted styrenes of styrene, α-methylstyrene, p-methylstyrene, vinyltoluene and t-butylstyrene; 10 to 20 parts by weight of a vinyl cyanide compound selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile; And Acrylonitrile-butadiene-styrene resin comprising: 20 to 60 parts by weight of a rubbery polymer selected from the group consisting of polybutadiene, styrene-butadiene copolymer, polyisoprene and butadiene-isoprene copolymer Composition. delete delete The method of claim 1, The (C) acrylonitrile-butadiene-styrene copolymer 60 to 80 parts by weight of an aromatic vinyl compound selected from the group consisting of substituted styrenes of styrene, α-methylstyrene, p-methylstyrene, vinyltoluene and t-butylstyrene; 15 to 30 parts by weight of a vinyl cyanide compound selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile; 5 to 20 parts by weight of at least one rubber selected from the group consisting of polybutadiene, styrene-butadiene copolymer, polyisoprene and butadiene-isoprene copolymer; Ronitrile-butadiene-styrene resin composition. The method of claim 1, The (D) styrene-acrylonitrile copolymer 60 to 70 parts by weight of an aromatic vinyl compound selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, vinyltoluene and t-butylstyrene; 30 to 40 parts by weight of a vinyl cyanide compound selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile; Acrylonitrile-butadiene-styrene resin composition comprising a. The method of claim 1, The weight average molecular weight of the (D) styrene-acrylonitrile copolymer is 100,000 to 200,000 acrylonitrile-butadiene-styrene resin composition. Claims 1, 2, 5 to 7, characterized in that the refrigerator sheet for extrusion interior prepared by containing the acrylonitrile-butadiene-styrene resin composition according to any one of claims. The method of claim 1, An acrylonitrile-butadiene-styrene resin composition, which is used for chemically resistant resins for urethane blowing agents.