KR20080064566A - Thermoplastic resin composition comprising ethylene-acrylate copolymer and article therefrom - Google Patents

Abstract

A thermoplastic resin composition is provided to realize excellent mechanical properties, weather resistance, surface gloss, scratch resistance, transparency, coatability, printability and adhesion in molded products, sheets and films. A thermoplastic resin composition comprises: (a) 5-55 wt% of an ethylene-acrylate copolymer comprising 10-50 mol% of ethylene and 50-90 mol% of acrylate; (b) 10-80 wt% of a polyolefin resin; and (c) 10-80 wt% of a polyacrylate resin. The ethylene-acrylate copolymer has a weight average molecular weight of 10,000 g/mol or higher.

Description

Thermoplastic resin composition comprising an ethylene-acrylate copolymer, and an article made therefrom {THERMOPLASTIC RESIN COMPOSITION COMPRISING ETHYLENE-ACRYLATE COPOLYMER AND ARTICLE THEREFROM}

The present invention relates to a thermoplastic resin composition, and to an article made therefrom, and more particularly, to a thermoplastic resin comprising an ethylene-acrylate copolymer composed of 10 to 50 mol% ethylene and 50 to 90 mol% acrylate. A composition, and an article made therefrom.

In general, polyolefin resins such as polyethylene (PE) and polypropylene (PP) are widely used in various applications due to their excellent moldability, mechanical properties, chemical resistance, etc., and low cost. However, when the polyolefin-based resin is applied as a molded article, there is a problem that the surface hardness is low and scratches easily occur. Moreover, since it is nonpolar resin, there exists a problem that physical properties, such as paintability and printability, are inferior.

As a method for improving the surface properties of such a polyolefin resin, there is a method of increasing the surface hardness of the resin using an organic-inorganic filler, a method of performing a plasma treatment, corona treatment, etc. on the surface of the resin in order to improve the paintability Etc. However, the above methods have a problem in that the cost is increased due to the secondary treatment process.

On the other hand, polyacrylate resins are excellent in scratch resistance and excellent in appearance characteristics of molded articles, and are widely used in various display materials. Moreover, since it is a polar resin which has a polar group, it is excellent in coating property. However, there is a limit that physical properties such as impact resistance and chemical resistance do not reach the polyolefin resin.

As described above, in order to overcome the problem that the polyolefin-based resin is easily scratched and to impart paintability, to impart physical properties such as impact resistance and chemical resistance to the polyacrylate-based resin, polyolefin-based resin and polyacrylate Techniques for blending resins are known. However, a simple compounding method does not have good compatibility between the two resins, and may cause a problem in that the disadvantages of the resins are highlighted. Therefore, in preparing such a mixed resin, it is a major technical problem to select a suitable compatibilizer.

Japanese Patent Application Laid-Open No. 2-215849 (published on Aug. 28, 1990) discloses a method of improving the compatibility between two resins by adding a propylene-methacryl block copolymer as a compatibilizer to polypropylene and methacryl-based resins. Japanese Laid-Open Patent Publication No. 2001-247723 (published on September 11, 2001) discloses a method of mixing an olefin-vinyl copolymer, a vinyl acrylic copolymer and a vinyl acrylic copolymer. These prior arts are to prepare a resin composition by activating the terminal of the olefin resin through a plurality of post reactions to the polyolefin resin to be blended, and then introducing an acrylic monomer thereto. However, since such a post reaction is a reaction using a polymer, it is necessary to consider reactivity or conversion, and there is a problem that the reaction time is long. Therefore, in the present invention, a resin composition may be more easily prepared by first preparing a copolymer of an olefin monomer and an acrylic monomer to be used, rather than a post reaction of the polymer as in the prior art.

In order to solve the problems of the prior art as described above, the present invention is an advantage of the polyolefin resin and polyacrylate resin, mechanical properties, weather resistance, surface gloss, scratch resistance, molding, transparency, paintability, printability, and adhesion It aims at providing the thermoplastic resin composition which is excellent in this and is applicable to a molded article, a sheet | seat, a film, etc.

Moreover, an object of this invention is to provide the article manufactured from the thermoplastic resin composition of this invention.

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

As a result of intensive studies to achieve the above object, the present inventors have succeeded in producing a thermoplastic resin composition including an ethylene-acrylate copolymer having a new component composition, and completed the present invention based on this.

The present invention provides a thermoplastic resin composition comprising (a) an ethylene-acrylate copolymer, (b) a polyolefin resin, and (c) a polyacrylate resin.

The thermoplastic resin composition may comprise (a) 5 to 50% by weight of an ethylene-acrylate copolymer consisting of 10 to 50 mol% of ethylene and 50 to 90 mol% of acrylate; (b) 10 to 80% by weight of polyolefin resin, and (c) 10 to 80% by weight of polyacrylate resin.

Moreover, this invention provides the article manufactured from the thermoplastic resin composition of this invention.

As used herein, "copolymer" refers to a polymer made of two or more comonomers, and "comonomer" refers to monomers that make up the copolymer. In addition, in this specification, "acrylate" in "ethylene-acrylate copolymer" means an acrylic acid compound including an acrylic acid ester, an acrylic acid salt, and the like.

As described above, in the prior art, a technique of blending a polyolefin resin and a polyacrylate resin to improve physical properties has been proposed, but in this case, there is a technical limitation that compatibility between resins and difficulty in selecting an appropriate compatibilizer are difficult. there was. However, the ethylene-acrylate copolymer used as a component of the thermoplastic resin composition according to the present invention is a random copolymer of ethylene and a polar monomer, has a high content of polar groups, and can be prepared by freely adjusting the content of the polar groups. have. In addition, when used in combination with a polyolefin resin and a polyacrylate resin, since the compatibility is excellent, there is no problem of compatibility or selection of a compatibilizer, causing the advantages of the polyolefin resin and polyacrylate resin, It is excellent in mechanical properties, weather resistance, surface gloss, scratch resistance, molding, transparency, paintability, printability, and adhesion, and can be applied to various industrial fields requiring such physical properties.

Hereinafter, the present invention will be described in detail.

(a) Ethylene-acrylate copolymer

The first component of the thermoplastic resin composition according to the invention is an ethylene-acrylate copolymer.

The ethylene-acrylate copolymer is preferably included in 5 to 50% by weight in the thermoplastic resin composition of the present invention. If the content is less than 5% by weight, there is a problem that the compatibility is lowered, and when the content exceeds 50% by weight, the phenomenon that the physical properties of the copolymer are outstanding rather than the physical properties of the polyolefin resin and the polyacrylate resin are highlighted. There is a problem.

The ethylene-acrylate copolymer is preferably composed of 10 to 50 mol% of ethylene and 50 to 90 mol% of acrylate, more preferably composed of 10 to 40 mol% of ethylene and 60 to 90 mol% of acrylate. The ethylene content in the ethylene-acrylate copolymer is an important factor in improving mechanical properties such as flexibility and stretchability, and the acrylate content is an important factor in determining transparency when applied to molded articles, sheets, and films. Therefore, by appropriately adjusting the content between the monomers in the ethylene-acrylate copolymer, it is possible to have an effect excellent in transparency and mechanical properties at the same time. If the content of ethylene is less than 10 mol%, it is disadvantageous in terms of flexibility and stretchability, so it is not suitable for applications such as films. If the content of ethylene exceeds 50 mol%, the mechanical strength is excellent. Since the transparency is lowered and the ethylene reactivity is significantly lower than the acrylate reactivity, technical implementation is impossible from the viewpoint of polymerization.

In addition, the ethylene-acrylate copolymer applied in the present invention is characterized by changing the composition ratio of ethylene and acrylate in accordance with the composition ratio of polyolefin resin and polyacrylate resin. That is, when the content of the polyolefin resin in the resin composition is increased and the content of the polyacrylate resin is decreased, even if the copolymer having a higher ethylene content is used less than the copolymer having a low ethylene content, The compatibility between resins can be greatly improved.

The ethylene-acrylate copolymer preferably has a mass average molecular weight of 10,000 g / mol or more, more preferably 70,000 g / mol. When the mass average molecular weight is less than 10,000 g / mol, the mechanical strength of the thermoplastic resin composition, molded articles, sheets, and films produced therefrom is lowered. On the other hand, when the mass average molecular weight is 70,000 g / mol or more, mechanical strength such as tensile strength is further improved. Since the higher the average molecular weight, the upper limit is not necessary.

The ethylene-acrylate copolymer is preferably a copolymer of ethylene with at least one acrylate comonomer selected from the group consisting of alkyl acrylates and alkyl methacrylates.

Examples of the acrylate comonomer include acrylic acid and methacrylic esters of alcohols having 1 to 12 carbon atoms in straight or branched chain, preferably acrylic acid and methacrylic esters of alcohols having 1 to 8 carbon atoms in straight or branched chain. . Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth ) Acrylates, 2-ethylbutyl (meth) acrylates, and acrylic acid esters of 2-ethylhexyl (meth) acrylates and neo-isomers of alcohols having 5 to 12 carbon atoms, and especially n-alkyl methacrylates. desirable.

The alkyl acrylate or alkyl methacrylate monomer is a vinyl ester such as vinyl acetate as a third monomer in addition to ethylene, an alkyl acrylate or alkyl methacrylate monomer, partial esters of acrylic acid, methacrylic acid or maleic acid, And monomers such as carbon monoxide.

(b) polyolefin resin

The second component of the thermoplastic resin composition according to the invention is a polyolefin resin.

The polyolefin resin is preferably contained in 10 to 80% by weight in the thermoplastic resin composition of the present invention. If the content is less than 10% by weight, there is a problem that impact resistance, chemical resistance is lowered, when the content exceeds 80% by weight there is a problem that scratch resistance, paintability is lowered.

The polyolefin resin is preferably at least one selected from the group consisting of polypropylene, propylene-alpha olefin copolymers, polyethylene, ethylene-alpha olefin copolymers, and ethylene-propylene-diene terpolymers. Wherein the propylene-alphaolefin copolymer comprises at least one alphaolefin comonomer selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene; It is a copolymer of propylene, and an ethylene-alpha olefin copolymer is a copolymer of the said alpha olefin comonomer and ethylene. In addition, the ethylene-propylene-diene terpolymer is at least one diene monomer selected from the group consisting of 1,4-hexadiene, 1,6-octadiene, and 2-methyl-1,5-hexadiene, propylene, ethylene Terpolymer.

(c) polyacrylate resin

The third component of the thermoplastic resin composition according to the invention is a polyacrylate resin.

The polyacrylate resin is preferably contained in 10 to 80% by weight in the thermoplastic resin composition of the present invention. If the content is less than 10% by weight, there is a problem that the scratch resistance, paintability is lowered, when the content exceeds 80% by weight there is a problem that the impact resistance, chemical resistance is lowered.

As polyacrylate resin, alkyl acrylate or alkyl methacrylate type resin is preferable. Specific examples include poly methyl methacrylate, poly ethyl acrylate, poly n-butyl acrylate, poly iso-butyl acrylate, poly t-butyl acrylate, poly n-hexyl acrylate, and poly 2-ethylbutyl acrylic At least 1 sort (s) chosen from the group which consists of a rate is preferable. In addition, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate and the like can also be used.

The thermoplastic resin composition of the present invention may be prepared by molding the above components by dry blending or melt blending, and then mixing them with an extruder. At this time, in the case of dry mixing, it can be carried out using equipment such as a tumbler mixer, and in the case of melt mixing, a brabender mixer, a single-srew extruder or a twin-screw extruder srew extruder). In addition, the composition of the present invention can be processed using a processing machine such as blow, cast extrusion molding.

The thermoplastic resin composition of the present invention may be processed in the same manner as described above to produce an article such as a multilayer film, a sheet or a container having a single or various structures.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

EXAMPLE

Example 1

20 g of polyethylene-methylmethacrylate (PEMMA) copolymer having an ethylene content of 30% by weight and a methylmethacrylate content of 70% by weight, polyethylene (PE) resin (manufactured by LG Chemical, trade name: BE0350, flow index (MI) ) = 0.25) 20 g and 60 g of polymethyl methacrylate (PMMA) (manufactured by LGMMA, P) were melt-blended in a batch using a Hakke mixer to obtain a resin composition.

Example 2

Example 1, except that 40 g of polyethylene resin (manufactured by LG Chemical, trade name: BE0350, flow index (MI) = 0.25), and 40 g of polymethyl methacrylate (manufactured by LGMMA, P) were used. It was carried out in the same manner as.

Example 3

Example 1, except that 60 g of polyethylene resin (manufactured by LG Chemical, trade name: BE0350, flow index (MI) = 0.25), and 20 g of polymethyl methacrylate (manufactured by LGMMA, P) were used. It was carried out in the same manner as.

Comparative Example 1

20 g of polyethylene-methylmethacrylate copolymer having an ethylene content of 5% by weight and a methylmethacrylate content of 95% by weight, polyethylene resin (manufactured by LG Chemical, trade name: BE0350, flow index (MI) = 0.25) 60 g , 20 g of polymethyl methacrylate (manufactured by LGMMA, P) was melt-blended in a batch using a Hakke mixer to obtain a resin composition.

Comparative Example 2

50 g of polyethylene resin (manufactured by LG Chemical, trade name: BE0350, flow index (MI) = 0.25) without using a polyethylene-methyl methacrylate copolymer in Comparative Example 1, polymethyl methacrylate (manufactured by LGMMA, P) ) Was carried out in the same manner as in Comparative Example 1, except that 50 g was used.

[Test Example]

The physical properties of the resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were measured by the following methods, and the results are shown in Table 1 below.

* Hardness: measured according to ASTM D2240 method.

* Izod impact strength was measured according to ASTM D256 method.

* Tensile test: measured according to ASTM D638 method.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Resin composition (% by weight) PEMMA 20 20 20 20 0 PE 20 40 60 60 50 PMMA 60 40 20 20 50 Hardness 115 110 90 63 57 Impact strength (kgcm / cm) 33 38 41 18 8 Tensile Strength (kgf / ㎠) 650 640 595 410 430

As shown in Table 1, the resin composition of Examples 1 to 3 comprising an ethylene-acrylate copolymer composed of 10 to 50 mol% ethylene, and 50 to 90 mol% acrylate according to the present invention, Compared to Comparative Example 1 comprising an ethylene-acrylate copolymer whose component content is outside the scope of the present invention, and Comparative Example 2 containing no ethylene-acrylate copolymer, hardness, impact strength, and tensile strength It was confirmed that the mechanical properties are very excellent.

As described above, according to the present invention, by including (a) an ethylene-acrylate copolymer, (b) a polyolefin resin, and (c) a polyacrylate resin, mechanical properties that are advantages of the polyolefin resin and the polyacrylate resin There is an effect of providing a thermoplastic resin composition excellent in weather resistance, surface gloss, scratch resistance, molding, transparency, paintability, printability, and adhesion.

In addition, there is an effect of providing a sheet, a film, a container, and the like, which are produced from the thermoplastic resin composition of the present invention and used for the surface of a home appliance, a housing material, a mechanical device, and the like.

Claims (15)

(a) 5 to 55% by weight of an ethylene-acrylate copolymer consisting of 10 to 50 mol% ethylene and 50 to 90 mol% acrylate; (b) 10 to 80% by weight of polyolefin resin, and (c) 10 to 80% by weight of a polyacrylate resin Thermoplastic resin composition. The method of claim 1, The ethylene-acrylate copolymer is composed of 10 to 40 mol% ethylene and 60 to 90 mol% acrylate Thermoplastic resin composition. The method of claim 1, The mass average molecular weight of the ethylene-acrylate copolymer is 10,000 g / mol or more Thermoplastic resin composition. The method of claim 3, wherein The mass average molecular weight is 70,000 g / mol or more, characterized in that Thermoplastic resin composition. The method of claim 1, The ethylene-acrylate copolymer is a copolymer of ethylene and at least one acrylate comonomer selected from the group consisting of alkyl acrylates and alkyl methacrylates. Thermoplastic resin composition. The method of claim 5, The said acrylate comonomer is 1 or more types chosen from the group which consists of acrylic acid and methacrylic acid ester of a C1-C12 alcohol of a linear or branched chain, It is characterized by the above-mentioned. Thermoplastic resin composition. The method of claim 6, The said acrylate comonomer is methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, n- At least one member selected from the group consisting of hexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and neo-isomer acrylic acid esters of alcohol having 5 to 12 carbon atoms Characterized by Thermoplastic resin composition. The method of claim 1, The polyolefin resin is at least one member selected from the group consisting of polypropylene, propylene-alpha olefin copolymers, polyethylene, ethylene-alpha olefin copolymers, and ethylene-propylene-diene terpolymers. Thermoplastic resin composition. The method of claim 8, The propylene-alphaolefin copolymer is at least one alpha olefin fin comonomer selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene. And a copolymer of propylene Thermoplastic resin composition. The method of claim 8, The ethylene-alpha olefin copolymer may include at least one alpha olefin comonomer selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene; Characterized in that the copolymer of ethylene Thermoplastic resin composition. The method of claim 8, The ethylene-propylene-diene terpolymer is at least one diene monomer selected from the group consisting of 1,4-hexadiene, 1,6-octadiene, and 2-methyl-1,5-hexadiene, propylene, ethylene It is characterized in that the terpolymer of Thermoplastic resin composition. The method of claim 1, The polyacrylate resin is an alkyl acrylate or alkyl methacrylate resin, characterized in that Thermoplastic resin composition. The film comprising the thermoplastic resin composition of any one of claims 1 to 12. A sheet comprising the thermoplastic resin composition of any one of claims 1 to 12. 13. A container comprising the thermoplastic resin composition of any one of claims 1-12.