KR20160129171A - Thermoplastic resin composition and molded article using thereof - Google Patents
Thermoplastic resin composition and molded article using thereof Download PDFInfo
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- KR20160129171A KR20160129171A KR1020150060603A KR20150060603A KR20160129171A KR 20160129171 A KR20160129171 A KR 20160129171A KR 1020150060603 A KR1020150060603 A KR 1020150060603A KR 20150060603 A KR20150060603 A KR 20150060603A KR 20160129171 A KR20160129171 A KR 20160129171A
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- South Korea
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- silicone
- thermoplastic resin
- resin composition
- impact modifier
- molded article
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/62—Mechanical aspects
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to a thermoplastic resin composition and a molded article using the same, wherein the thermoplastic resin composition comprises (A) a methyl methacrylate-based polymer; And (B) a silicone-based impact modifier. The silicone impact modifier (B) has an average particle diameter in the range of 50 to 200 nm, and can provide excellent weather resistance, scratch resistance and coloring property while reinforcing impact resistance.
Description
The present invention relates to a thermoplastic resin composition and a molded article using the thermoplastic resin composition. More particularly, the present invention relates to a thermoplastic resin composition capable of simultaneously realizing excellent impact resistance, weather resistance, scratch resistance and coloring property, and a molded article using the same.
Recently, there has been a continuing demand for unpainted materials due to manufacturing cost and environmental problems in automobile interior and exterior materials, housing of electronic products and the like.
The polymethylmethacrylate resin used as the unpainted material is excellent in weatherability and scratch resistance, and is transparent and easy to color. However, it has a problem that the impact resistance is weak and the gloss is limited.
As disclosed in Korean Patent No. 0725940, a technique of reinforcing a weak impact resistance of a polymethyl methacrylate resin by adding an impact modifier to a polymethyl methacrylate resin has been disclosed. However, in addition to impact resistance, weatherability and colorability can be simultaneously realized There is no limit.
Therefore, by developing the weather resistance, scratch resistance and coloring property simultaneously while reinforcing the impact resistance of the polymethyl methacrylate resin, it is possible to develop a technology for a thermoplastic resin applicable to automobile interior and exterior materials and housings of electronic products without painting .
The present invention provides a thermoplastic resin composition capable of realizing excellent weather resistance, scratch resistance and coloring property while reinforcing impact resistance by adding a silicone impact modifier to the methyl methacrylate polymer at an optimum ratio, and a molded article using the thermoplastic resin composition .
It is also intended to provide a thermoplastic resin composition and a molded article using the same that can improve the impact resistance, scratch resistance and coloring property by optimizing the constituent components of the silicone impact modifier and the ratio of the particle size and the content thereof.
In order to accomplish the above object, the present invention provides a thermoplastic resin composition comprising: (A) a methyl methacrylate polymer; And (B) a silicone-based impact modifier, wherein the silicone-based impact modifier (B) may have an average particle diameter of 50 to 200 nm.
The silicone-based impact modifier (B) comprises a core (B-1) comprising a silicone rubber and an alkyl acrylate polymer; And a shell (B-2) graft-polymerized from a monomer mixture comprising at least one monomer selected from the group consisting of alkyl acrylates, alkyl methacrylates, styrene and acrylonitrile in the core Lt; / RTI >
The core (B-1) may contain 20 to 80% by weight of the silicone rubber and 20 to 80% by weight of the alkyl acrylate polymer. The core (B-1) May comprise a butyl acrylate polymer.
The silicone rubber of the core (B-1) may comprise polydimethylsiloxane, and the methyl methacrylate polymer (A) may be selected from the group consisting of methyl methacrylate, methyl acrylate, styrene and acrylonitrile And copolymerizing at least one monomer with methyl methacrylate.
Also, the thermoplastic resin composition may include 60 to 90% by weight of the methyl methacrylate polymer (A) and 10 to 40% by weight of the silicone impact modifier (B).
Next, the molded article using the thermoplastic resin composition of the present invention includes the thermoplastic resin composition of the present invention, and the molded article may have a pencil hardness of H class or higher as measured according to ASTM D3363 after 1 hour from the occurrence of scratch.
The molded article may have a notched Izod impact strength of 4 kgf · cm / cm or more measured at 23 ° C. in accordance with ASTM D256.
The molded article may have a brightness value L measured by ASTM E308 of a specularly reflected light removing method (SCE) of less than 4.0, and a color change value (ΔE) after evaluation of 2,000 hours of exposure under SAE J 1960 conditions may be less than 2.0.
According to the present invention, by adding the silicone-based impact modifier to the methyl methacrylate-based polymer at an optimum ratio, excellent weather resistance, scratch resistance and coloring property can be realized while reinforcing impact strength.
Further, by optimizing the constituent components of the silicone impact modifier, and the ratio of the particle size and the content thereof, the impact resistance, scratch resistance and coloring property can be improved.
Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described in detail below. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.
Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, commonly used predefined terms are not ideally or excessively interpreted unless explicitly defined otherwise.
The present invention relates to a thermoplastic resin composition and a molded article using the same.
First, the thermoplastic resin composition of the present invention comprises (A) a methyl methacrylate polymer; And (B) a silicone-based impact modifier. Each of these components is described in detail below.
(A) a methyl methacrylate-based polymer
The methyl methacrylate-based polymer (A) used in the present invention may be a polymer of a monomer containing methyl methacrylate.
Preferably, methyl methacrylate is copolymerized with at least one monomer selected from the group consisting of methyl methacrylate, methyl acrylate, styrene, and acrylonitrile.
The content ratio of the monomer to the methyl methacrylate may be from 1: 1.5 to 1: 4.0, and preferably from 1: 2.0 to 1: 4.0. Within this range, weatherability and scratch resistance are maximized, and compatibility with the silicone impact modifier (B) is also excellent.
(B) a silicone impact modifier
The silicone-based impact modifier (B) used in the present invention contains a silicone rubber component and can enhance the scratch resistance not only by the impact reinforcing effect but also by the unique restoring force.
The silicone-based impact modifier (B) may be in the form of a core-shell, preferably a core (B-1) comprising a silicone rubber and an alkyl acrylate polymer; And a graft polymerized shell (B-2) from a monomer mixture comprising at least one monomer selected from the group consisting of alkyl acrylates, alkyl methacrylates, styrenic aromatic compounds, and acrylonitrile in the core have.
The core (B-1) may comprise 20 to 80% by weight of the silicone rubber and 20 to 80% by weight of the alkyl acrylate polymer. Preferably 40 to 60% by weight of the silicone rubber and 40 to 60% by weight of the alkyl acrylate polymer. Within this range, the effect of improving impact resistance and scratch resistance can be maximized.
The silicone rubber of the core (B-1) may be any rubber surface including a silicone component, but may preferably include polydimethylsiloxane.
The alkyl acrylate-based polymer of the core (B-1) may be any of monomers containing an alkyl acrylate component such as ethyl acrylate, butyl acrylate, propyl acrylate, pentyl acrylate, hexyl acrylate, However, it is preferable to include butyl acrylate as the monomer. The butyl acrylate polymer polymerized from the monomer containing butyl acrylate has excellent polymerization reactivity at the time of polymerization and has excellent impact resistance due to a relatively low glass transition temperature (Tg).
The average particle diameter of the silicone impact modifier (B) may be 50 to 200 nm. Preferably 100 to 200 nm, and more preferably 130 to 160 nm. When the average particle diameter is less than 50 nm, the impact reinforcing effect is insignificant, and when the average particle diameter is more than 200 nm, the coloring property is significantly deteriorated.
Here, the particle size of the silicone impact modifier (B) can be expressed numerically by a measurement method to represent the average size of the population. However, as a general purpose, the mode diameter indicating the maximum value of the distribution and the median value of the integral distribution curve (Average number average, length average, area average, mass average, volume average, etc.). In the present invention, unless otherwise specified, the average particle diameter is a number average particle diameter, and D50 % Of the particle size).
The thermoplastic resin composition of the present invention may contain 60 to 90% by weight of the methyl methacrylate polymer (A) and 10 to 40% by weight of the silicone impact modifier (B).
A thermoplastic resin composition having excellent impact resistance, scratch resistance, weather resistance and coloring property within the above content ratio range can be realized.
Next, the present invention can provide a molded article comprising the thermoplastic resin composition. For example, the thermoplastic resin composition can be applied to an automobile exterior part, particularly an automobile exterior part which can be unpainted, and particularly, a molded article which can be applied to a pillar or a side mirror housing can do.
According to ASTM D3363, the molded article may have a pencil hardness of H class or higher as measured 1 hour after the occurrence of scratches. Due to the excellent restoring force of the silicone impact modifier contained in the thermoplastic resin composition, unlike the conventional art, excellent pencil hardness of H grade or more can be maintained even after 1 hour from the occurrence of scratch.
In addition, the molded product may have a brightness value (L) measured by ASTM E308 of a regular reflection light removing method (SCE) of less than 4.0, preferably 0.1 to 3.5. The color value of the thermoplastic resin composition molding specimen prepared by adding the same amount of carbon black to the brightness value L was measured using a specular component excluded SCE (Konica Minolta CM-3600d color difference The values measured using the system. Here, the lower the brightness value, the better the blackness (coloring property). As shown in the experimental data below, the molded article produced from the present invention exhibits a lightness value (L) of less than 4.0 and is excellent in coloring property.
Further, the molded article may have a hue change value (ΔE) of less than 2.0, preferably 0.3 to 1.8 after evaluation of 2,000 hours exposure under SAE J 1960 conditions. Here, the color change value? E is an index indicating the color difference in the International CIE Lab color indicator. The equation for calculating? E is shown in the following equation 1.
[Equation 1]
In the CIE Lab color indicator, the lightness is indicated by L, and the chromaticity indicating the color and saturation is indicated by a and b. The larger the value of a, the closer to red, and the smaller the value of a, the closer to green. The larger the b value, the closer to yellow, and the smaller the b value, the closer to blue.
The smaller the ΔE value, the less the color change and the better the weather resistance.
The molded article may have a notched Izod impact strength of 4 kgf · cm / cm or more measured at 23 ° C. according to ASTM D256, preferably 5 to 16 kgf · cm / cm Lt; / RTI >
The physical properties of such a molded article are determined through several experiments to confirm the critical significance of simultaneously realizing excellent impact resistance, weather resistance and coloring property in the thermoplastic resin composition within the range.
The following are experimental results to demonstrate the superiority of the thermoplastic resin composition of the present invention.
The specifications of the methyl methacrylate polymer (a) and the silicone impact modifier (b) used in Examples and Comparative Examples of the present invention are as follows.
(a) a methyl methacrylate-based polymer
IH830, a polymethyl methacrylate resin manufactured by LG Chemical Co., Ltd., was used.
(b) impact modifier
(b-1) a silicone-based impact modifier
A styrene-acrylonitrile copolymer was grafted to a core containing an average particle size of about 150 nm and containing 50% by weight of polydimethylsiloxane and 50% by weight of a butyl acrylate polymer to form a core-shell structure silicone impact modifier Respectively.
(b-2) a butadiene impact modifier
A butadiene-based impact modifier having a core-shell structure in which a styrene-acrylonitrile copolymer was grafted to a polybutadiene rubber core and had an average particle size of about 260 nm was used.
(b-3) acrylate-based impact modifier
An acrylate-based impact modifier having a core-shell structure in which a styrene-acrylonitrile copolymer was grafted on a butylacrylate rubber core with an average particle size of about 170 nm was used.
(b-4) Silicone-based impact modifier
A styrene-acrylonitrile copolymer was grafted onto a core containing an average particle size of about 350 nm and containing 50% by weight of polydimethylsiloxane and 50% by weight of a butyl acrylate polymer to use a silicone-based impact modifier having a shell- Respectively.
(c) carbon black
Orion's HI-BLACK 50L product was used.
(d) UV stabilizer
A TINUVIN 329 product from BASF was used.
Each component was added in accordance with the contents of Table 1 below and melt kneaded in a twin-screw extruder heated to 250 캜 to prepare a thermoplastic resin composition in the form of a pellet. The thus-obtained pellets were dried at a temperature of 80 DEG C for 2 hours or more, and then a test piece for measuring the physical properties was prepared using a 6O oz injection molding machine under conditions set at a cylinder temperature of 250 DEG C and a mold temperature of 60 DEG C.
The properties of the specimens obtained from the composition of the components shown in Table 1 were evaluated in the following manner. The results are shown in Table 2 below.
Property evaluation method
(1) Impact resistance: The Izod impact strength was measured at a temperature of 23 ° C in accordance with ASTM D256 for 1/8 "notched Izod impact strength specimens.
(2) Scratch resistance: 152.4 × 152.4 × 3.2 mm The specimen was subjected to scratching with a pencil hardness measuring instrument equipped with a weight of 500 g on the surface of the specimen according to ASTM D3363, and after 1 hour, the surface was observed to determine the pencil hardness grade Were measured.
(3) Coloring property: Brightness value (L) was measured according to ASTM E308 using a CM-3600d colorimeter of Konica Minolta as a specular reflection removing method (SCE) for a 3.2 mm thick specimen.
(4) Weatherability: The color change value (ΔE) was measured for a thickness of 3.2 mm after evaluation of exposure for 2,000 hours in SAE J1960 condition.
(kgf · cm / cm)
As shown in Table 2, the thermoplastic resin compositions of Examples 1 to 4 according to the present invention have excellent impact resistance, scratch resistance, coloring property and weather resistance.
On the other hand, in Comparative Example 1 in which no impact modifier (b) was added at all, it was confirmed that the impact resistance was significantly lowered.
Further, it was confirmed that in Comparative Example 2 in which the content ratio between the methyl methacrylate polymer (a) and the silicone impact modifier (b-1) was out of the range of the present invention, the weather resistance was lowered than in Examples 1 to 4.
Comparative Example 3 using a butadiene-based impact modifier (b-2) instead of the silicone-based impact modifier (b-1) of the present invention was remarkably poor in scratch resistance and weather resistance and was comparable to that of the acrylate impact modifier (b-3) Example 4 confirmed that scratch resistance and colorability were poor.
It was also confirmed that Comparative Example 5 using a silicone impact modifier (b-4) having an average particle diameter larger than that of the silicone impact modifier (b-1) of the present invention significantly decreased coloring property as compared with Examples 1 to 4.
Therefore, through the above experiments, the properties of the present invention exhibited remarkably excellent properties in the combination of the constituent components and the content ratio between the constituents, and the critical significance thereof was proved.
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 exemplary embodiments. It is clear that the present invention can be suitably modified and applied in the same manner. Therefore, the above description does not limit the scope of the present invention, which is defined by the limitations of the following claims.
Claims (11)
Wherein the average particle diameter of the silicone impact modifier (B) is 50 to 200 nm.
The silicone-based impact modifier (B) comprises a core (B-1) comprising a silicone rubber and an alkyl acrylate polymer; And a shell (B-2) graft-polymerized from a monomer mixture comprising at least one monomer selected from the group consisting of alkyl acrylates, alkyl methacrylates, styrene and acrylonitrile in the core Wherein the thermoplastic resin composition is a thermoplastic resin composition.
The core (B-1) comprises 20 to 80% by weight of the silicone rubber and 20 to 80% by weight of the alkyl acrylate-based polymer.
Wherein the alkyl acrylate-based polymer of the core (B-1) comprises a butyl acrylate polymer.
Wherein the silicone rubber of the core (B-1) comprises polydimethylsiloxane.
Wherein the methyl methacrylate polymer (A) is obtained by copolymerizing methyl methacrylate with at least one monomer selected from the group consisting of methyl methacrylate, methyl acrylate, styrene and acrylonitrile.
The thermoplastic resin composition contains 60 to 90% by weight of the methyl methacrylate polymer (A) and 10 to 40% by weight of the silicone impact modifier (B).
The molded article has a pencil hardness of H class or higher as measured according to ASTM D3363 1 hour after the occurrence of scratches.
Wherein the molded article has a lightness value (L) measured by ASTM E308 of not more than 4.0 and a color change value (DELTA E) of less than 2.0 after evaluation by exposure to 2,000 hours in SAE J 1960 condition.
Said molded article having a 1/8 "notched Izod impact strength of at least 4 kgf · cm / cm measured at a temperature of 23 ° C. in accordance with ASTM D256.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020150060603A KR20160129171A (en) | 2015-04-29 | 2015-04-29 | Thermoplastic resin composition and molded article using thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020150060603A KR20160129171A (en) | 2015-04-29 | 2015-04-29 | Thermoplastic resin composition and molded article using thereof |
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| KR20160129171A true KR20160129171A (en) | 2016-11-09 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170141109A (en) * | 2016-06-14 | 2017-12-22 | 주식회사 엘지화학 | Acrylic processing aid and vinyl chloride resin composition comprising the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100725940B1 (en) | 2005-12-06 | 2007-06-11 | 엘지엠엠에이 주식회사 | Polymethyl methacrylate resin composition |
-
2015
- 2015-04-29 KR KR1020150060603A patent/KR20160129171A/en not_active Application Discontinuation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100725940B1 (en) | 2005-12-06 | 2007-06-11 | 엘지엠엠에이 주식회사 | Polymethyl methacrylate resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170141109A (en) * | 2016-06-14 | 2017-12-22 | 주식회사 엘지화학 | Acrylic processing aid and vinyl chloride resin composition comprising the same |
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