KR20160104522A - High melt flow polymethylmethacrtylate resin composition and articles thereof - Google Patents
High melt flow polymethylmethacrtylate resin composition and articles thereof Download PDFInfo
- Publication number
- KR20160104522A KR20160104522A KR1020150083847A KR20150083847A KR20160104522A KR 20160104522 A KR20160104522 A KR 20160104522A KR 1020150083847 A KR1020150083847 A KR 1020150083847A KR 20150083847 A KR20150083847 A KR 20150083847A KR 20160104522 A KR20160104522 A KR 20160104522A
- Authority
- KR
- South Korea
- Prior art keywords
- methyl methacrylate
- acrylate
- resin composition
- impact modifier
- flow
- Prior art date
Links
Classifications
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
Description
The present invention relates to a high-flow poly (methyl methacrylate) resin composition and a molded article made therefrom, and more particularly, to a high-flow poly (methyl methacrylate) resin composition which can improve fluidity and impact resistance without deteriorating optical properties, A methyl methacrylate resin composition and a molded article made therefrom.
Polymethyl methacrylate (PMMA) is a typical transparent resin which is used in various fields requiring excellent transparency and weather resistance and excellent mechanical properties. With the recent growth of the display industry, the demand for such transparent materials has been greatly increased, attracting great interest. In particular, in the case of a light guide plate, which is an important material of an LCD display backlight, polymethylmethacrylate has excellent optical transmittance, is small in birefringence and excellent in light resistance, and thus is used as a main material of optical components.
Such a polymethyl methacrylate resin is prepared by polymerizing only methyl methacrylate or copolymerizing a small amount of another acrylate monomer by bulk polymerization, suspension polymerization, solution polymerization or the like, but the impact strength is weaker than other plastic materials It is easily broken by an external impact. Therefore, techniques for impact resistance reinforcement using an impact modifier have been studied.
Conventionally, the impact resistant polymethyl methacrylate resin can be obtained by adding an impact modifier in powder or flake form obtained in the step of agglomerating, dehydrating and drying an elastomer latex to a polymethyl methacrylate resin and melt extruding at a high temperature. However, when the latex prepared by emulsion polymerization is obtained in the form of powder, there is a disadvantage in that it is economically disadvantageous in terms of energy and energy saving aspect, and the high temperature melting method has a problem that the dispersion of the impact modifier falls in the matrix. In order to achieve the desired impact strength, a large amount of impact modifier has to be used.
Conventionally, such impact resistant polymethylmethacrylate resin has been mainly used as a part requiring a small area or a small size transparency such as a vessel of a TV, but recently, a large area material such as an air conditioner front cover, The trend is expanding.
In order to solve these problems, there is an increasing demand for a polymethyl methacrylate resin having excellent flow properties while maintaining transparency and impact resistance.
When such a resin is to be produced, the molecular weight of the polymethyl methacrylate resin can be lowered or copolymerized with a monomer having a low glass transition temperature (Tg) during the production of the resin. However, when the molecular weight of the polymethyl methacrylate resin is low, the impact resistance is lowered. When a large amount of monomers having a low glass transition temperature (Tg) is copolymerized, the heat resistance of the impact resistant polymethyl methacrylate resin is reduced .
Korean Patent Laid-Open No. 10-2011-0069269 (Patent Document 1) discloses a method for improving fluidity and impact resistance by simultaneously introducing a suspension, an impact modifier and an aggregating agent into a suspension polymerization of methyl methacrylate and at least one comonomer Discloses polymethyl methacrylate resins. However, although fluidity and impact resistance are partially improved, optical properties such as transparency and haze are deteriorated, and thus, there is a problem that it is difficult to use as an exterior material of an electric appliance requiring transparency.
In order to solve the above problems, it is an object of the present invention to provide a shockproof polymethyl methacrylate resin having improved flowability. More specifically, it is intended to provide a high-flowable polymethyl methacrylate resin composition capable of improving fluidity and impact resistance without deteriorating optical properties by including a specific impact modifier and flow improver.
The present invention also provides a high-flowable polymethyl methacrylate resin composition which can increase the compatibility of a methyl methacrylate resin with an impact modifier and improve fluidity and impact resistance more effectively even when a small amount of flow improver is contained .
Another object of the present invention is to provide a polymethylmethacrylate molded body formed from the high-flow poly (methyl methacrylate) resin composition and having improved flowability and impact resistance without deteriorating optical properties such as transparency and haze.
In order to accomplish the above object, the present invention provides a process for producing a high-molecular poly (methylmethacrylate), which comprises (a) a methyl methacrylate resin, (b) an acrylic impact modifier having a core- And a methacrylate resin composition.
[Chemical Formula 1]
Wherein R 1 and R 2 are each independently straight-chain or branched (C 1 -C 20) alkyl and R 3 is hydrogen or (C 1 -C 20) alkyl.
According to an embodiment of the present invention, 100 parts by weight of a mixture comprising (a) 50 to 90% by weight of a methyl methacrylate resin and (b) 10 to 50% by weight of an acrylic impact modifier having a core- And 0.1 to 5 parts by weight of the flow improver (c).
According to one embodiment of the present invention, the methyl methacrylate resin is a copolymer of polymethyl methacrylate alone or methyl methacrylate and alkyl acrylate, and the alkyl acrylate is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, iso Propyl acrylate, n-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, and hydroxyethyl acrylate.
According to one embodiment of the present invention, the acrylic impact modifier (b) of the core-shell structure (b) is prepared by adding an acrylic acid alkyl ester monomer or a methacrylic acid alkyl ester monomer, an unsaturated nitrile monomer, and an aromatic vinyl The acrylic impact modifier may include, but is not limited to, a shell formed by graft polymerization of a monomer, and the acrylic impact modifier may have an average particle size of 150 to 300 nm.
According to an embodiment of the present invention, the shell may include an inner shell and an outer shell, and the outer shell may be formed by polymerizing an acrylic acid alkyl ester monomer or a methacrylic acid alkyl ester monomer, The shell may be formed by polymerizing the unsaturated nitrile-based monomer and the aromatic vinyl-based monomer.
According to one embodiment of the present invention, the flow improver may be selected from one or more of the following formulas (2) to (4), but is not limited thereto.
(2)
(3)
[Chemical Formula 4]
According to one embodiment of the present invention, the high-flow poly (methyl methacrylate) resin composition is one of the antioxidant, plasticizer, mold releasing agent, heat stabilizer, antistatic agent, nucleating agent, flame retardant, flame retardant, lubricant, impact modifier, Or two or more kinds of additives.
In order to accomplish the above object, the present invention relates to a molded article produced from the above-described high-kinematic poly (methyl methacrylate) resin composition.
According to one embodiment of the present invention, the molded article may have a 1/4 "Izod impact strength of 2.2 to 5.0 kgfcm / cm measured according to ASTM D256 and a 3.0 mm transmittance measured according to ASTM D1003 of greater than or equal to 90% have.
INDUSTRIAL APPLICABILITY According to the high fluidity polymethylmethacrylate resin composition of the present invention and the molded article produced therefrom, it is possible to improve the flowability and impact resistance without deteriorating the optical properties such as transparency and haze by including specific impact modifiers and flow improvers There are advantages. The compatibility of the methyl methacrylate resin and the impact modifier is greatly increased even if a small amount of a specific flow improver is contained therein, thereby remarkably improving the fluidity and impact resistance.
In particular, it is possible to reduce the appearance defects of various types and to significantly improve the manufacturing defect rate. Therefore, it is possible to apply not only materials for household electrical appliances which require transparency, but also various materials such as an air conditioner front cover and a transparent window of a washing machine.
Further, due to the combination of the impact modifier and the flow improver, the fluidity is remarkably improved, so that it is possible to form a structure with a complicated structure, and a large-size injection molding is possible.
Hereinafter, preferred embodiments and physical properties measuring methods of the high-dynamic-modified polymethyl methacrylate resin composition and the molded article produced therefrom will be described in detail. The present invention may be better understood by the following examples, which are for the purpose of illustrating the present invention and are not intended to limit the scope of protection defined by the appended claims.
The present invention relates to an acrylic impact modifier having a core-shell structure and a specific flow improver incorporated into a methyl methacrylate resin and compounding the acrylic impact modifier, thereby significantly improving fluidity and impact resistance without deteriorating optical properties such as transparency and haze, Methacrylate resin can be produced, and thus the present invention has been completed.
Hereinafter, one embodiment of the present invention will be described in more detail.
The high-performance polymethylmethacrylate resin composition according to an embodiment of the present invention may include (a) a methyl methacrylate resin, (b) an acrylic impact modifier having a core-shell structure, and (c) a flow modifier.
The methyl methacrylate resin (a) according to one embodiment of the present invention is not limited as long as it is a methyl methacrylate resin well known in the art, and examples thereof include methyl methacrylate homopolymer, Lt; RTI ID = 0.0 > alkyl acrylate. ≪ / RTI > When the alkyl acrylate is copolymerized, the workability can be further improved, which is effective.
More specifically, the methyl methacrylic resin (a) may be a copolymer prepared from 70 to 99.9% by weight of methyl methacrylate and 0.1 to 30% by weight of alkyl acrylate, but is not limited thereto.
The alkyl acrylate according to one embodiment of the present invention is not limited as long as it is a compound well known in the art. For example, the alkyl of the alkyl acrylate can be (C1-C10) alkyl or (C3-C10) cycloalkyl and the alkyl or cycloalkyl is optionally substituted with C3-C7) cycloalkyl, halogen, nitro, cyano, hydroxy, amino, but is not limited thereto.
The alkyl acrylate is more preferably selected from the group consisting of methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate and hydroxyethyl acrylate Or two or more species may be selected, but are not limited thereto.
The content of the methyl methacrylate resin according to one embodiment of the present invention is not limited, but it may include 50 to 90% by weight of the mixture containing the methyl methacrylate resin and the acrylic impact modifier having the core-shell structure. By being included in the above range, the impact resistance can be effectively improved without deteriorating the optical properties such as transparency and haze, and is effective.
The acrylic impact modifier (b) of the core-shell structure according to one embodiment of the present invention is not limited as long as it is a compound known to those skilled in the art to be added in order to improve impact resistance in combination with a methyl methacrylic resin Do not. Further, even when only a small amount of the flow improver (c) is contained due to the combination with the specific flow improver (c), the compatibility of the methyl methacrylate resin and the impact modifier is increased and the flowability and impact resistance are significantly improved There are advantages to be able to.
More specifically, it may include a shell formed by graft-polymerizing an acrylic acid alkyl ester monomer, a methacrylic acid alkyl ester monomer, an unsaturated nitrile monomer, and an aromatic vinyl monomer on the surface of a core formed of a rubbery polymer.
The rubbery polymer may be, for example, butadiene rubber, acrylic rubber, ethylene-propylene copolymer rubber, butadiene-styrene copolymer rubber, isoprene rubber, ethylene-propylene-diene terpolymer rubber, polyorganosiloxane- ) Acrylate rubber composites, and mixtures thereof, but is not limited thereto.
As the rubbery polymer, a butadiene rubber or a butadiene-styrene copolymer rubber may preferably be used.
According to one embodiment of the present invention, the shell may include an inner shell and an outer shell. The outer shell may be formed by polymerizing an acrylic acid alkyl ester monomer or a methacrylic acid alkyl ester monomer, and the inner shell may be formed by polymerizing the unsaturated nitrile monomer and the aromatic vinyl monomer, It is not.
The specific kind of the acrylic acid alkyl ester monomer or methacrylic acid alkyl ester monomer constituting the outer shell is not particularly limited. But are not limited to, for example, (C1-C10) alkyl acrylate, (C1-C10) alkyl methacrylate, and mixtures thereof.
More specifically, it is possible to use acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, t-butyl acrylate, n-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, One or two kinds of monomers selected from among ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, n-butyl methacrylate, n-octyl methacrylate and 2- Or more, and more preferably methyl methacrylate can be used.
According to one embodiment of the present invention, the unsaturated nitrile-based monomer constituting the inner shell is a compound having an unsaturated hydrocarbon capable of radical polymerization and a cyanation group, and is not limited as long as it is a compound well known in the art.
For example, acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like, which may be used alone or in a mixture. Preferably acrylonitrile can be used.
According to an embodiment of the present invention, the aromatic vinyl-based monomer constituting the inner shell is not particularly limited, but styrene, (C1-C10) alkyl substituted styrene substituted with hydrogen of a vinyl group, (C1-C10) alkyl-substituted styrene, halogen-substituted styrene in which the hydrogen of the vinyl group is substituted, halogen-substituted styrene in which the hydrogen of the benzene group is substituted, and vinylnaphthalene.
More specifically, the aromatic vinyl-based monomer is at least one selected from the group consisting of styrene,? -Methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, monochlorostyrene, dichlorostyrene, trichlorostyrene, Naphthalene, 2-vinylnaphthalene, and mixtures thereof, and it is more effective to use styrene or? -Methylstyrene.
For example, the inner shell may be formed by polymerizing the unsaturated nitrile-based monomer and the aromatic vinyl monomer, and the outer shell may be formed of the acrylic acid alkyl ester Based monomer, a methacrylic acid alkyl ester-based monomer, or a mixture thereof, but is not limited thereto.
More specifically, the inner shell may be a styrene-acrylonitrile copolymer (SAN) and the outer shell may be polymethyl methacrylate (PMMA).
The acrylic impact modifier of the core-shell structure according to an embodiment of the present invention may have an average particle diameter of 150 to 300 nm, more preferably 200 to 250 nm, but is not limited thereto. When the average particle diameter is within the above range, the mechanical properties such as impact resistance and scratch resistance can be remarkably improved while maintaining the optical properties such as transparency and haze of the high-dynamic polymethyl methacrylate resin composition.
The content of the acrylic impact modifier of the core-shell structure according to an embodiment of the present invention is not limited, but may be 10 to 50 wt% of the mixture containing the methyl methacrylic resin and the acrylic impact modifier of the core-shell structure have. By being included in the above range, flowability and impact resistance can be effectively improved without deterioration of optical properties such as transparency and haze in combination with a flow improver, which is effective.
When the content of the acrylic impact modifier is less than 10% by weight, the impact resistance improving effect may be insignificant. When the content is more than 50% by weight, optical properties such as transparency and haze may be deteriorated.
The flow improver (c) according to one embodiment of the present invention improves the flowability of the composition by reducing the frictional force between the compounds during compounding of the methyl methacrylate resin and the acrylic impact modifier having the core-shell structure, And to improve the appearance characteristics of the molded article. In particular, it is possible to remarkably improve the flowability and impact resistance by increasing the compatibility of the methyl methacrylate resin and the impact modifier by adding a remarkably small amount compared to conventional flow improvers such as waxes and lubricants, Or large-area injection machining.
The flow improver according to an embodiment of the present invention is not limited, but is preferably a compound represented by the following formula (1).
[Chemical Formula 1]
Wherein R 1 and R 2 are each independently straight-chain or branched (C 1 -C 20) alkyl and R 3 is hydrogen or (C 1 -C 20) alkyl.
Typically, hydrocarbon waxes such as paraffin and polyethylene wax are used to improve the fluidity of the thermoplastic resin; Fatty acid lubricants such as stearic acid and lauric acid; Fatty acid amide-based lubricants such as stearic acid amide, palmitic acid amide, ethylene bis-stearamide and the like; Alcohol-based lubricants such as cetyl alcohol and stearyl alcohol; And metal salt-based lubricants such as calcium stearate and barium stearate. However, in order to secure sufficient fluidity, it is necessary to use an excess amount of the lubricant. When the lubricant is used in excess, the transparency is rapidly lowered, and the glass transition temperature of the resin is lowered, resulting in a decrease in heat resistance.
In order to solve the above problems, the present invention includes a compound represented by the general formula (1) as a flow modifier, so that it is used together with a methyl methacrylate resin and an acrylic impact modifier having a core-shell structure, And that the optical properties such as transparency and haze are not deteriorated and the fluidity can be effectively increased.
More specifically, the flow improver according to an embodiment of the present invention may be one or more selected from the following formulas (2) to (4).
(2)
(3)
[Chemical Formula 4]
The content of the flow improver according to an embodiment of the present invention is not limited, but may be 0.1 to 5 parts by weight based on 100 parts by weight of the mixture comprising the methyl methacrylate resin and the acrylic impact modifier having a core-shell structure . More preferably 1 to 3 parts by weight. By including the flow improver in the above range, the fluidity of the composition can be remarkably improved during injection molding without deteriorating the optical properties such as transparency and haze, and the appearance property can be improved to improve the defective rate in the structure injection and the large- There is an advantage that it can be greatly reduced.
According to an embodiment of the present invention, the flow modifier may be used alone, or a mixture of the compound represented by the formula (2) and the compound represented by the formula (3) or (4) But is not limited thereto.
The high-performance polymethylmethacrylate resin composition according to an embodiment of the present invention may contain one or two of an antioxidant, a plasticizer, a releasing agent, a heat stabilizer, an antistatic agent, a nucleating agent, a flame retardant, a flame retardant, a lubricant, And may further include additives selected above the species.
The content of the additive may be appropriately included within a range that does not impair the physical properties of the high-performance poly (methyl methacrylate) resin composition of the present invention. For example, 0.01 to 100 parts by weight based on 100 parts by weight of the high-flow poly (methyl methacrylate) resin composition, but the present invention is not limited thereto.
According to another embodiment of the present invention, there can be provided a molded article produced from the high-kinematic polymethylmethacrylate resin composition.
The molded article according to an embodiment of the present invention may have a 1/4 "Izod impact strength of 2.2 to 5.0 kgfcm / cm measured according to ASTM D256 and a 3.0 mm transmittance measured according to ASTM D1003 of at least 90% .
Therefore, it can be applied not only to materials for home appliances, such as air conditioner front cover and transparent window of washing machine, but also to various materials, and it is possible to mold structures with complicated structure as the fluidity remarkably improves, There is an advantage that utilization can be increased for various purposes as much as possible.
BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments and physical properties measuring methods of the high-dynamic-concavity polymethyl methacrylate resin composition of the present invention and molded articles produced therefrom will be described in detail.
Property measurement
1. Impact strength
Measured in a notched condition for 1/4 "thick specimens according to ASTM D256 specifications.
2. Melt Flow Index (MI)
The melt flow index (MI) was measured at 230 캜 and 3.8 kg in accordance with ASTM D1238.
3. Pencil Hardness
The pencil hardness at a load of 1 kg was measured according to ASTM D3363 standard.
4. Liquidity synergies
The high purity polymethyl methacrylate resin composition pellets according to the present invention were injected into a helical flow mold having a mold clamping force of 170 tons and a thickness of 2 mm and a width of 15 mm and then injection molding at a mold temperature of 60 DEG C and an injection pressure of 700 kg / Cm < 2 > at 250 < [deg.] ≫ C to measure the length of the injection mold filled in the helical flow mold. Compared with the methyl methacrylic resin alone (Comparative Example 5), the relative increase in the length of the methyl methacrylic resin when the flow improver was contained (Comparative Example 6) was comparatively compared with that of the methyl methacrylic resin alone, Relative synergistic effect was shown based on Comparative Example 7 containing a reinforcing agent.
5. Measurement of transmittance and haze
The transmittance and haze of 3.0 mm injection specimens were measured in HM-150 (Murakami Color Research Laboratory) equipment according to ASTM D1003.
[Example 1]
As shown in the following Table 1, 85 weight parts of methyl methacrylate having a weight average molecular weight of 89,000 g / mol and 85 weight parts of 15 weight percent copolymer of methyl acrylate, a flow improver (Sigma Aldrich) (M210, Kaneka, average particle diameter: 220 nm) and 0.1 part by weight of an antioxidant (Irgnox 1010, manufactured by BASF) in 10 parts by weight of 10 parts by weight of a 10% by weight aqueous solution of an acrylic impact reinforcing agent having a core- (L / D = 36, SM PLATEK) at a cylinder temperature of 230 DEG C and pelletized by a twin-screw extruder (32 L / D = 36, SM PLATEK) Specimens were prepared. After the specimen was prepared, the specimen was allowed to stand at room temperature for 24 hours and the physical properties thereof were measured. The results are shown in Table 2 below.
[Example 2]
As shown in the following Table 1, the same procedure as in Example 1 was carried out except that the content of the flow improver represented by the general formula (2) was changed. After the specimen was prepared, the properties were measured after staying at room temperature for 24 hours. Respectively.
[Example 3-4]
(Sigma Aldrich) represented by the general formula (2) and the general formula (3) was used instead of the flow improver represented by the general formula (2) as shown in the following Table 1, And the physical properties were measured. The results are shown in Table 2 below.
[Example 5]
As shown in the following Table 1, except that the content of the methyl methacrylate resin and the impact modifier was changed, the same procedure as in Example 1 was carried out. After the specimen was prepared, the properties were measured after staying at room temperature for 24 hours. Table 2 shows the results.
[Comparative Example 1]
Except that PBA (ADP-1200, manufactured by BASF) was used instead of the flow modifier represented by the general formula (2) as shown in the following Table 1. The properties were measured after standing the sample at room temperature for 24 hours The results are shown in Table 2 below.
[Comparative Example 2]
Except that PBA (poly (butylacrylate), ADP-1200, manufactured by BASF) was used instead of the flow modifier represented by the general formula (2) as shown in the following Table 1. After preparing the specimen, The properties were measured after standing, and the results are shown in Table 2 below.
[Comparative Example 3]
Except that EBS (ethylene bis (stearamide), HI-LUBE 500P, Shinwon Chemical Co., Ltd.) was used instead of the flow modifier represented by the formula (2) as shown in Table 1 below. And the physical properties were measured. The results are shown in Table 2 below.
[Comparative Example 4]
As shown in the following Table 1, the same procedure as in Example 1 was carried out except that the content of the flow improver represented by the general formula (2) was changed. After the specimen was prepared, the properties were measured after staying at room temperature for 24 hours. Respectively.
[Comparative Example 5]
As shown in the following Table 1, except that an impact modifier and a flow improver were not used, 100 parts by weight of a methyl methacrylate resin was used, and the same procedure as in Example 1 was conducted. And the results are shown in Table 2 below.
[Comparative Example 6]
As shown in the following Table 1, except that an impact modifier was not used, 100 parts by weight of a methyl methacrylate resin was used. The sample was prepared in the same manner as in Example 1, and the properties were measured after staying at room temperature for 24 hours , And the results are shown in Table 2 below.
[Comparative Example 7]
As shown in the following Table 1, the same procedure as in Example 1 was carried out except that the flow improver represented by the general formula (2) was not used. After the specimen was prepared, the properties were measured after staying at room temperature for 24 hours. Respectively.
[Comparative Example 8]
As shown in the following Table 1, except that the content of the methyl methacrylate resin and the impact modifier was changed, the same procedure as in Example 1 was carried out. After the specimen was prepared, the properties were measured after staying at room temperature for 24 hours. Table 2 shows the results.
[Table 1]
[Table 2]
As shown in Table 2, in Comparative Examples 1 to 3 using conventional lubricants without using the flow improver of the present invention, it was found that the optical properties of transmittance and haze were decreased, and Comparative Example 4 , The fluidity increased sharply, scratch resistance was lowered, and haze was increased, indicating that it was not suitable as a transparent home appliance exterior material.
Comparative Example 5, which did not use an impact modifier and a flow improver, showed an excellent pencil strength and transmittance but a sharp decrease in impact strength. In Comparative Example 6 including a flow improver, fluidity But the impact strength was still low, indicating that it was not suitable as a high-flow molded product.
In addition, in Comparative Example 7 in which no flow improver was used, the impact strength was improved as compared with Comparative Example 5 and Comparative Example 6, but it was found that the fluidity was insufficient and thus it was not suitable for producing a large-area molded article.
It was found that the fluidity improving effect was remarkably exhibited in Examples 1 to 5 as compared with Comparative Examples 6 to 7 in which only the flow improver or the impact modifier was included because the flow improver and the impact modifier were simultaneously adopted, But the mechanical properties such as impact strength and the like were also excellent without decreasing the transmittance and the haze.
Therefore, according to the present invention, by including a small amount of a methyl methacrylate resin, an acrylic impact modifier having a core-shell structure, and a specific flow improver, the impact strength and scratch resistance And the optical properties of the haze are not reduced, it is possible to provide a high-flowability polymethyl methacrylate resin composition which is easily processed and is suitable for large-area injection molding or the like.
While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention. Accordingly, the above description should not be construed as limiting the scope of the present invention defined by the limits of the following claims.
Claims (9)
[Chemical Formula 1]
Wherein R 1 and R 2 are each independently straight-chain or branched (C 1 -C 20) alkyl and R 3 is hydrogen or (C 1 -C 20) alkyl.
Based on 100 parts by weight of a composition comprising (a) 50 to 90% by weight of a methyl methacrylate resin and (b) 10 to 50% by weight of an acrylic impact modifier having a core-
And 0.1 to 5 parts by weight of the flow improver (c).
The methyl methacrylate resin is a copolymer of polymethyl methacrylate alone or methyl methacrylate and alkyl acrylate,
Wherein the alkyl acrylate is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate and hydroxyethyl acrylate Or two kinds of high-polydimethylsiloxane resins.
The acrylic impact modifier of the core-shell structure (b) is obtained by graft polymerization of an acrylic acid alkyl ester monomer, a methacrylic acid alkyl ester monomer, an unsaturated nitrile monomer and an aromatic vinyl monomer on the surface of a core of a rubber- / RTI >
Wherein the acrylic impact modifier has an average particle size of 150 to 300 nm.
Wherein the shell comprises an inner shell and an outer shell, the outer shell being formed by polymerizing an acrylic acid alkyl ester monomer or a methacrylic acid alkyl ester monomer,
Wherein the inner shell is formed by polymerizing the unsaturated nitrile-based monomer and the aromatic vinyl-based monomer.
Wherein the flow modifier is at least one selected from the following formulas (2) to (4).
(2)
(3)
[Chemical Formula 4]
The high-flow poly (methyl methacrylate) resin composition may further include one or more additives selected from an antioxidant, a plasticizer, a releasing agent, a heat stabilizer, an antistatic agent, a nucleating agent, a flame retardant, a flame retardant, a lubricant, Wherein the poly (methyl methacrylate) resin composition is a poly (methyl methacrylate) resin composition.
Wherein the molded article has a 1/4 "Izod impact strength of 2.2 to 5.0 kgfcm / cm measured according to ASTM D256, and a 3.0 mm transmittance measured according to ASTM D1003 of 90% or more.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20150027037 | 2015-02-26 | ||
| KR1020150027037 | 2015-02-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20160104522A true KR20160104522A (en) | 2016-09-05 |
| KR101676023B1 KR101676023B1 (en) | 2016-11-15 |
Family
ID=56938931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150083847A KR101676023B1 (en) | 2015-02-26 | 2015-06-15 | High melt flow polymethylmethacrtylate resin composition and articles thereof |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101676023B1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002138116A (en) * | 2000-10-31 | 2002-05-14 | Nippon Zeon Co Ltd | (meth)acrylate polymer mixture, method of producing the same and molded article thereof |
| KR20070108008A (en) * | 2006-05-04 | 2007-11-08 | 제일모직주식회사 | Resin composition having good scratch resistance |
| US20080057317A1 (en) * | 2006-08-30 | 2008-03-06 | Eastman Chemical Company | Sealant compositions having a novel plasticizer |
| KR20110069269A (en) | 2009-12-17 | 2011-06-23 | 엘지엠엠에이 주식회사 | Method for high flow impact modified pmma resin |
-
2015
- 2015-06-15 KR KR1020150083847A patent/KR101676023B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002138116A (en) * | 2000-10-31 | 2002-05-14 | Nippon Zeon Co Ltd | (meth)acrylate polymer mixture, method of producing the same and molded article thereof |
| KR20070108008A (en) * | 2006-05-04 | 2007-11-08 | 제일모직주식회사 | Resin composition having good scratch resistance |
| US20080057317A1 (en) * | 2006-08-30 | 2008-03-06 | Eastman Chemical Company | Sealant compositions having a novel plasticizer |
| KR20110069269A (en) | 2009-12-17 | 2011-06-23 | 엘지엠엠에이 주식회사 | Method for high flow impact modified pmma resin |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101676023B1 (en) | 2016-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5756496B2 (en) | Methacrylic resin and method for producing the same | |
| KR101874160B1 (en) | Transparent thermoplastic resin composition and article produced therefrom | |
| KR101332432B1 (en) | Styrenic thermoplastic resin composition | |
| CN102443256B (en) | High-heat-resistance polycarbonate (PC)/acrylonitrile styrene acrylate copolymer (ASA) alloy material and preparation method thereof | |
| EP2027207A1 (en) | Resin composition having good scratch resistance | |
| JP6359080B2 (en) | Impact-processed PMMA with improved optical properties | |
| US10358552B2 (en) | Impact-resistant molding material having an improved characteristics profile | |
| CN102532737B (en) | Transparent high-hardness impact-resistant acrylonitrile butadiene styrene (ABS) plastic alloy composition | |
| JP5674325B2 (en) | Molded product obtained using methacrylic resin composition | |
| KR101464250B1 (en) | Thermoplastic Resin Composition With Improved White Turbidity Phenomenon at Low Temperature | |
| CN110655710B (en) | Scratch-resistant impact-resistant polypropylene material and preparation method thereof | |
| KR100983872B1 (en) | Transparent Thermoplastic Resin with High Gloss and Hardness | |
| KR20110076753A (en) | Thermoplastic resin composition and molded product using the same | |
| KR20150001991A (en) | Thermoplastic resin composition and molded article using the same | |
| KR20150137558A (en) | Thermoplastic resin composition having improved heat and scratch resistance | |
| KR101676023B1 (en) | High melt flow polymethylmethacrtylate resin composition and articles thereof | |
| KR101688684B1 (en) | Transparent Thermoplastic Resin Composition with Excellent Chemical Resistance | |
| KR20170074647A (en) | Thermoplastic resin composition and molded article comprising the same | |
| JP2007145882A (en) | Multistage-polymerized methacrylic resin polymer | |
| KR101633156B1 (en) | Methacrylate copolymer having good heat resistance property and pencil hardness property, method of preparing the same and resin composition comprising copolymer | |
| KR101435241B1 (en) | Low temperature stress whitening resistant and scratch resistant thermoplastic resin composition | |
| KR20170051619A (en) | Thermoplastic resin composition and article produced therefrom | |
| JPH07286086A (en) | Heat-resistant thermoplastic resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| A302 | Request for accelerated examination | ||
| E902 | Notification of reason for refusal | ||
| E90F | Notification of reason for final refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20191107 Year of fee payment: 4 |