KR101796345B1 - Vinyl Copolymer Having High Heat Resistant and Low-gloss Transparent and Thermoplastic Resin Composition Therefrom - Google Patents

Abstract

The present invention relates to a vinyl copolymer produced by copolymerizing (A) an aromatic vinyl monomer, (B) a vinyl cyanide monomer and (C) a maleimide monomer, and a thermoplastic resin composition containing the copolymer.

Description

(Vinyl Copolymer Having High Heat Resistant and Low-gloss Transparent and Thermoplastic Resin Composition Therefrom), which is excellent in heat resistance and low-glossiness,

The present invention relates to a vinyl copolymer and a thermoplastic resin composition containing the vinyl copolymer. More particularly, the present invention relates to a vinyl copolymer excellent in heat resistance and low gloss, which is produced by including (A) an aromatic vinyl monomer, (B) a vinyl cyanide monomer and (C) a maleimide monomer, and a thermoplastic resin composition containing the same .

The acrylonitrile-butadiene-styrene (ABS) resin based on styrene is excellent in moldability as well as physical properties such as impact resistance, mechanical rigidity, heat distortion property and gloss, Housings, and general goods.

Recently, there is an increasing demand for a resin capable of expressing a low gloss and a smooth texture at the same time as an interest in an emulsion of a resin which is out of a cold feeling plastic increases. Particularly, there is a tendency that the demand for automobile interior materials and exterior materials of electronic products which have to be looked at for a long time by human touch. In addition, as the environmental regulations are strengthened, the application range of the low-gloss resin which can directly form the coating while omitting the coating process is gradually expanding.

Among these materials, materials such as automobile interior materials, building materials, and interior are characterized in that they are required to realize low light properties and heat resistance characteristics at the same time. The general-purpose products, which simultaneously demand low gloss and heat resistance, are becoming more sophisticated and increasing in size.

One of the most widely used methods for producing such a low-gloss heat-resistant resin, particularly a low-gloss heat-resistant ABS resin, is to add a part of the components constituting the ABS resin to a styrene monomer having excellent heat resistance, And a matting agent (quencher) is applied in place of the heat-resistant copolymer.

For example, a heat resistant resin such as an alpha methyl styrene-styrene-acrylonitrile (AMS-SAN) copolymer or an N-phenylmaleimide-styrene-acrylonitrile (PMI-SAN) An acrylic filler, an acrylic filler, an acrylic filler, or a cross-linked styrene resin, and melt-extruding the same with another ABS resin raw material. Another method is to prepare a heat-resistant ABS resin by using the above-mentioned heat-resistant copolymer, and then remove the gloss in the post-processing step.

As another method, there is a method of forming a microscale rough surface by regulating the size of rubber particles, which is a dispersed phase of the resin, when the heat resistant ABS is produced by using the heat resistant copolymer as described above. The surface thus formed scatters the incident light and lowers the gloss.

As a method for improving the heat resistance of heat-resistant ABS resin, a heat-resistant copolymer resin is made by using alpha-methylstyrene (AMS), or heat-resistant copolymerization is performed using N-phenyl maleimide (PMI) There is a method of melt-extruding the heat-resistant copolymer resin together with a heat-resistant copolymer resin matrix and a graft rubber and other additives prepared so as to improve the compatibility with the matrix.

Such methods are described in many articles and US Pat. No. 4,659,790, US Pat. No. 4,757,109, or the like. However, in order to simultaneously realize low light properties and heat resistance improvement, such a melt extrusion method should use an additive capable of realizing a low light property together with a heat resistant copolymer resin. Implementing the low light effect using the additive is convenient in various aspects, but the uniformity of the gloss is unstable depending on the dispersed state of the additive, so that the quality is limited. In addition, since the specific gravity of the additive generally used is high, not only the specific gravity of the final product is increased but also the manufacturing cost is increased by using an expensive quencher. In addition, there is a method of using an injection mold or a casting process through a corrosion mold without using an additive. However, when a corrosion mold is used, the introduction of an additional process increases the manufacturing cost and may cause pollution, which is also disadvantageous from the environmental viewpoint.

U. S. Patent No. 4,659, 790 (Apr. 21, 1987) U.S. Patent No. 4,757,109 (July 7, 1988)

SUMMARY OF THE INVENTION The present invention has been made to overcome the above problems, and it is an object of the present invention to provide a vinyl copolymer excellent in heat resistance and low gloss and a thermoplastic resin composition containing the vinyl copolymer.

It is another object of the present invention to provide a molded article excellent in heat resistance and light extinguishing property, which is produced from the thermoplastic resin composition.

In order to achieve the above object, the present invention provides a vinyl copolymer comprising (A) an aromatic vinyl monomer, (B) a vinyl cyanide monomer and (C) a maleimide monomer.

In the thermoplastic resin composition according to one embodiment of the present invention, the vinyl copolymer includes 60 to 80% by weight of an aromatic vinyl monomer (A), 20 to 40% by weight of a vinyl cyanide monomer (B) Based monomer and 1 to 20% by weight of a mid-based monomer.

In the thermoplastic resin composition according to one embodiment of the present invention, the vinyl copolymer may further contain (D) 1 to 5% by weight of a silicone compound having two or more unsaturated reactive groups.

In the thermoplastic resin composition according to one embodiment of the present invention, the vinyl-based copolymer may have a glass transition temperature of 105 to 130 캜.

Another aspect of the present invention relates to a thermoplastic resin composition comprising an aromatic vinyl-cyanide vinyl copolymer and a graft rubber copolymer in the vinyl copolymer, wherein the thermoplastic resin composition comprises 10 to 40% by weight of a vinyl copolymer, 20 to 85% by weight of an aromatic vinyl-cyanide vinyl copolymer, and 5 to 40% by weight of a graft rubber copolymer.

The thermoplastic resin composition is characterized by having a flow index (MI) of 5 to 25, a degree of 60 DEG gloss of 5 to 80% and a softening point (VST) of 100 to 120 DEG C at 220 DEG C / 10 kg .

Another aspect of the present invention relates to a molded article excellent in heat resistance and low gloss including the thermoplastic resin composition.

The thermoplastic resin composition according to the present invention can realize excellent extinction properties and high heat resistance properties by restricting the structure of the cross-linking agent used in copolymerization. Accordingly, the present invention has the advantage that low gloss and high heat resistance can be simultaneously realized in a resin and a molded article using the same, even if a small amount of quencher is contained therein, and excellent molding processability can be obtained.

Hereinafter, the vinyl copolymer excellent in heat resistance and low glossiness according to the present invention and the thermoplastic resin composition containing the vinyl copolymer will be described in detail. The following embodiments are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. It will be apparent to those skilled in the art that, unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, And a description of the known function and configuration will be omitted.

&Quot; (meth) acrylate "means" acrylate "and" methacrylate ", unless otherwise specified in the present specification, Acrylate ester " and "methacrylic acid alkyl ester ", and the term" (meth) acrylic acid ester "may mean" acrylic acid ester "and" methacrylic acid ester ".

The inventors of the present invention have found that when a conventional crosslinking agent, that is, a silicone compound having two or more unsaturated reactive groups, is included, uniformity of low gloss and appearance can be achieved at the same time, but the same glass transition temperature as a general aromatic vinyl- In order to improve heat resistance and to further improve the need for mixing with a copolymer having a high heat resistance. As a result, when the structure of the cross-linking agent used in the silicone compound having two or more unsaturated groups is limited, And exhibits a high quenching effect while satisfying heat resistance, thereby completing the present invention.

Hereinafter, each component of the thermoplastic resin composition according to the present invention will be described in detail.

The vinyl copolymer of the present invention is produced by copolymerizing (A) an aromatic vinyl monomer, (B) a vinyl cyanide monomer and (C) a maleimide monomer. (A) an aromatic vinyl monomer

The aromatic vinyl monomer may be selected from the group consisting of styrene, C ₁ to C ₁₀ alkyl substituted styrene, (o, m, p) -halogen substituted styrene, (o, m, p) -vinyltoluene, Styrene, vinyl naphthalene, and combinations thereof, but is not limited thereto. The alkyl-substituted styrene may include, but is not limited to, one selected from? -Methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and combinations thereof.

(B) a vinyl cyanide monomer

The vinyl cyanide monomer may be selected from acrylonitrile, methacrylic acid, methacrylonitrile, ethacrylonitrile, and combinations thereof, and acrylonitrile is preferably used. They may be applied alone or in a mixture of two or more.

(C) maleimide monomer

In the present invention, the maleimide-based monomer may be a monomer having a structure represented by the following formula (1).

[Chemical Formula 1]

Wherein R ₁ , R ₂ , R ₄ and R ₅ are each independently selected from the group consisting of hydrogen, (C ₁ -C ₂₀ ) alkyl, (C ₃ -C ₂₀ ) cycloalkyl or (C ₆ -C ₂₀ ) aryl R ₃ is a (C ₁ -C ₂₀ ) alkylene group or a (C ₆ -C ₂₀ ) arylene group, and when R ₃ is phenylene, the substituted position of the imide group is ortho, meta or para.

The maleimide-based monomer according to the present invention is not limited to the type having the structure of Formula 1, but preferably phenylenebismaleimide may exhibit excellent heat resistance while exhibiting a high extinction effect.

In the present invention, the vinyl copolymer includes (A) 60 to 80% by weight of an aromatic vinyl monomer, (B) 20 to 40% by weight of a vinyl cyanide monomer and (C) 1 to 20% by weight of a maleimide monomer But is not limited thereto.

The vinyl-based copolymer according to the present invention may further contain (D) 1 to 5% by weight of a silicone compound having two or more unsaturated reactive groups.

The silicone compound (D) having two or more unsaturated reactive groups may contain one or two or more compounds represented by the following formula (2).

(2)

In Formula 2, l , m and n are each an integer of 0 to 100 (but not simultaneously 0), and R ₁ to R ₈ are each independently hydrogen, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group , A substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, a substituted or unsubstituted C ₂ to C ₃₀ alkynyl group, a substituted or unsubstituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, a substituted or unsubstituted C ₁ to C ₃₀ heteroaryl group, a hydroxyl group, an alkoxy group, an amino group, an epoxy group, a carboxyl group, a halogen group, an ester group, an isocyanate group of the, or a mercapto group, the R At least two of R ₁ to R ₈ include a polymerizable unsaturated reactive group, and the compound may have a linear or cyclic structure.

More specifically, the silicone compound having two or more unsaturated reactive groups (D) may contain one or two or more compounds represented by the following formula (3).

(3)

In the above formula (3), R ₉ to R ₁₄ independently represent a substituted or unsubstituted C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C ₂ to C ₂₀ An alkenyl group and a substituted or unsubstituted C ₆ to C ₂₀ And R ₁₅ to R ₁₇ are each independently hydrogen or a substituted or unsubstituted C ₁ to C ₆ alkyl group, and p is an integer of 1 to 6.

The silicone compound having two or more unsaturated reactive groups according to the present invention may be 1,3,5-trimethyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetramethyl- 5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, 1,3,5-triethyl- 1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetraethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-penta Ethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, and mixtures thereof.

In the present invention, the vinyl-based copolymer may have a glass transition temperature of 105 to 130 ° C.

The present invention can provide a thermoplastic resin composition containing the vinyl-based copolymer.

In the present invention, the thermoplastic resin composition may include an aromatic vinyl-cyanide vinyl copolymer and a graft rubber copolymer in the vinyl copolymer.

The aromatic vinyl-cyanide vinyl copolymer is obtained by polymerizing an aromatic vinyl compound with a vinyl cyanide compound, wherein the aromatic vinyl compound is at least one selected from the group consisting of aromatic vinyl monomers (A), that is, styrene, C ₁ to C ₁₀ alkyl- (o, m, p) -halogen substituted styrene, (o, m, p) -vinyltoluene, (o, m, p) -methoxystyrene, vinylnaphthalene and combinations thereof. , The alkyl-substituted styrene may also include one selected from a-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and combinations thereof, but the present invention is not limited thereto

The vinyl cyanide compound may also be selected from among the vinyl cyanide monomers (B), that is, acrylonitrile, methacrylic acid, methacrylonitrile, ethacrylonitrile, and combinations thereof. Preferably, acrylonitrile It is good to use. They may be used alone or as a mixture of two or more thereof, but the present invention is not limited thereto.

In the present invention, the aromatic vinyl-cyanide vinyl copolymer may contain aromatic vinyl: vinyl cyanide in an amount of 20 to 80% by weight: 40 to 60% by weight.

In the present invention, the graft rubber copolymer may be prepared by grafting an aromatic vinyl compound and a vinyl cyanide compound onto a conjugated diene rubber latex.

As the conjugated diene rubber latex, general butadiene rubber latex or styrene-butadiene copolymer latex can be used, but the present invention is not limited thereto. The conjugated diene rubber latex may have an average particle size of preferably 0.1 to 5.0 mu m. The conjugated diene rubber latex may be 5 to 70% by weight of the total weight of the graft copolymer.

The aromatic vinyl compound may include but is not limited to one selected from styrene, C ₁ to C ₁₀ alkyl-substituted styrene, halogen-substituted styrene, vinyl toluene, vinyl naphthalene, and combinations thereof. The alkyl-substituted styrene may include, but is not limited to, one selected from? -Methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and combinations thereof.

The vinyl cyanide compound may be acrylonitrile, methacrylonitrile or ethacrylonitrile, and it is preferable to use acrylonitrile.

The graft copolymer using the above component can be produced by any of the conventional methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization. The polymerization initiator can be used in the presence of the above components Emulsion polymerization or bulk polymerization can be carried out.

In the present invention, the graft rubber copolymer may have a rubber content of 5 to 40% by weight.

In the present invention, the thermoplastic resin composition may comprise 1 to 20% by weight of a vinyl copolymer, 20 to 85% by weight of an aromatic vinyl-cyanide vinyl copolymer and 5 to 40% by weight of a graft rubber copolymer.

The thermoplastic resin composition of the present invention may contain additives such as a dye, a pigment, a flame retardant, a filler, a stabilizer, a lubricant, an antibacterial agent, a releasing agent, an antistatic agent and an antioxidant to further impart moldability and physical properties. These additives may be used alone or in combination of two or more, but are not necessarily limited thereto.

The thermoplastic resin composition prepared according to the embodiment of the present invention has a flow index (MI) of 5 to 25, a degree of 60 DEG gloss of 5 to 80% at 220 DEG C / 10 kg, a softening point (VST) 120 < 0 > C.

The present invention provides a molded article produced from the thermoplastic resin composition. The molded article exhibits low heat resistance and high heat resistance, and exhibits mechanical properties similar to conventional molded articles, and thus can be applied to various materials such as electronic products and housings.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples.

The specifications and physical properties of each component used in the following Examples and Comparative Examples are as follows.

The components used in the present invention are shown in Table 1 below.

[Table 1]

delete

(Property evaluation)

(1) Weight average molecular weight (unit: g / mol)

The powder sample was dissolved in tetrahydrofuran (THF), and then measured using Gel Permeation Chromatography (GPC; lient Technologies 1200 series). At this time, Shodex LF-804 (8.0.1.D. × 300 mm) was used as a column and polystyrene (Shodex) was used as a standard sample.

(2) Glass transition temperature (unit: ° C)

The temperature was first raised to 160 ° C at a rate of 20 ° C / min using Q Instrument, Inc. of TA Instrument, and the temperature was gradually increased to 160 ° C at a rate of 10 ° C / minute after being cooled to 50 ° C. The inflection point of the endothermic transition curve was determined as the glass transition temperature.

(3) Surface gloss (unit:%)

The degree of gloss was measured at an angle of 60 degrees using the BYK-Gardner Gloss Meter of BYK Co., Ltd. according to the evaluation method defined in ASTM D523.

(4) Izod impact strength (unit: kgf · cm / cm)

Lt; / RTI > were measured by notched conditions on 1/8 "thick specimens by the evaluation method specified in ASTM D256.

(5) The melt-flow index (MI)

Measured in accordance with ASTM D1238 at 220 캜 / 10 kg, and the unit is g / 10 min.

(6) Vicat Softening Temperature (VST) (unit: ° C)

1/4 "thick specimens were measured under the conditions of 5 kgf and 50 ° C / hour according to ISO 306B50.

(Examples 1 to 3 and Comparative Examples 1 and 2)

The thermoplastic resin compositions of each of the examples and comparative examples were prepared by the compositions shown in the following Table 2, and then extruded to prepare thermoplastic resins in the form of pellets. At this time, a twin-screw extruder having an L / D of 29 and a diameter of 45 mm was used, and the barrel temperature was set at 230 ° C. The prepared pellets were dried at 80 DEG C for 2 hours, and then a cylinder temperature of 240 DEG C and a mold temperature of 60 DEG C were set using a 6 oz injection molding machine to prepare test specimens having a size of 9 cm x 5 cm x 0.2 cm. The physical properties of the prepared specimens were measured and are shown in Table 3.

[Table 2]

[Table 3]

The vinyl-based copolymers according to Examples 1 to 3 of the present invention were insoluble due to crosslinking and could not measure the weight average molecular weight, and the glass transition temperature reached a maximum of 119.5 ° C. The physical properties of the specimens were compared with those of the aromatic vinyl-cyanide vinyl copolymer (SAN) and the grafted rubber copolymer (g-ABS). As a result, while the impact strength was maintained, the non-cured softening point reached a maximum of 106.1 ° C, Respectively. In addition, it was confirmed that excellent melt flowability and extinction characteristics are realized.

On the other hand, in Comparative Examples 1 and 2, the glass transition temperature of the vinyl-based copolymer was low because it did not contain the maleimide-based monomer unlike the examples, and the compounded sample did not exhibit the extinction characteristic, The index was too low to be inferior in moldability, and the heat resistance characteristics were remarkably lowered in all Comparative Examples.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Various modifications and variations are possible in light of the above teachings.

Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .

Claims (9)

(A) an aromatic vinyl monomer, (B) a vinyl cyanide monomer, and (C) a maleimide monomer,
Wherein the maleimide-based monomer is a vinyl-based copolymer comprising a structure represented by the following formula
[Chemical Formula 1]

Wherein R ₁ , R ₂ , R ₄ and R ₅ are each independently selected from the group consisting of hydrogen, (C ₁ -C ₂₀ ) alkyl, (C ₃ -C ₂₀ ) cycloalkyl or (C ₆ -C ₂₀ ) aryl R ₃ is a (C ₁ -C ₂₀ ) alkylene group or a (C ₆ -C ₂₀ ) arylene group, and when R ₃ is phenylene, the substituted position of the imide group is ortho, meta or para. .
The method according to claim 1,
The vinyl copolymer is a vinyl-based copolymer comprising (A) 60 to 79% by weight of an aromatic vinyl monomer, (B) 20 to 39% by weight of a vinyl cyanide monomer, and (C) 1 to 20% by weight of a maleimide monomer. coalescence.
delete The method according to claim 1,
The vinyl-based copolymer further comprises (D) 1 to 5% by weight of a silicone compound having two or more unsaturated reactive groups.
The method according to claim 1,
Wherein the vinyl-based copolymer has a glass transition temperature of 105 to 130 占 폚.
A thermoplastic resin composition comprising a vinyl copolymer, an aromatic vinyl-cyanide vinyl copolymer and a graft rubber copolymer according to any one of claims 1 to 2 and 4 to 5.
The method according to claim 6,
Wherein the thermoplastic resin composition comprises 10 to 40% by weight of a vinyl copolymer, 20 to 85% by weight of an aromatic vinyl-cyanide vinyl copolymer, and 5 to 40% by weight of a graft rubber copolymer.
A molded article comprising the thermoplastic resin composition of claim 6.
9. The method of claim 8,
The molded article has a degree of gloss of 5 to 80% measured at an angle of 60 ° according to the evaluation method defined in ASTM D523 and a heat resistance measured at a load of 5 kg at 50 ° C / hr by the evaluation method specified in ISO 306B50 VST) of 100 to 120 < 0 > C.