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NL2002910A - Environmentally-friendly polylactic acid resin composition. - Google Patents

Environmentally-friendly polylactic acid resin composition. Download PDF

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NL2002910A
NL2002910A NL2002910A NL2002910A NL2002910A NL 2002910 A NL2002910 A NL 2002910A NL 2002910 A NL2002910 A NL 2002910A NL 2002910 A NL2002910 A NL 2002910A NL 2002910 A NL2002910 A NL 2002910A
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polylactic acid
acid resin
resin
resin composition
polycarbonate
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NL2002910A
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NL2002910C2 (en
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Young-Mi Chung
Chang-Do Jung
Young-Jun Lee
Ji-Won Pack
Young-Chul Kwon
Hyung-Tak Lee
Jin-Kyung Cho
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Cheil Ind Inc
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Priority to NL2002910A priority Critical patent/NL2002910C2/en
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Description

Environmentally-friendly polylactic acid resin composition
The present invention relates to an environmentally-friendly polylactic acid resin composition. More particularly, the present invention relates to an environmentally-friendly polylactic acid resin composition having excellent heat resistance and appearance and improved welding impact strength.
There has been much research on development of strong polymer materials for special purposes, and on safety thereof. However, as a discarded polymer has been socially recognized as a severe environmental problem all over the world, development of an environmentally-friendly polymer material has been required.
Environmentally-friendly polymers can be mainly classified into photodegradable and biodegradable polymers. The biodegradable polymer has a functional group that can be decomposed by microorganisms.
Among these polymers, an aliphatic polyester polymer has gained the most attention, since it has excellent porosity and an easily-adjustable decomposition characteristic. In particular, polylactic acid (PLA) has a market share of 150,000 tons in the world and expansively covers the field where common plastic is used, for example food packing materials and containers, cases for electronics, and the like. At present, a polylactic acid resin is mainly used for disposable products such as food containers, wraps, films, and the like due to the biodegradable characteristic. This polylactic acid resin is manufactured in American NatureWorks LLC., Japanese Toyota Motors Inc., and the like.
However, since a conventional polylactic acid resin lacks formability, mechanical strength, and heat resistance, a thin film made therefrom can be easily destroyed. Since it has low resistance against high temperature, a molded product made therefrom can be distorted at 60°C or higher.
In order to overcome these problems, trial have occurred for blending a polylactic acid resin and a petroleum-based thermoplastic plastic, for example a polycarbonate resin, a polyamide resin, an acrylonitrile-butadiene-styrene (ABS) resin, a polyacetal resin, and the like, with the polylactic acid resin.
Japanese Patent Laid-Open Publication No. 1999— 279380 discloses a polylactic acid resin and an acrylonitrile styrene resin composition, and Japanese Patent Laid-Open Publication No. 2006-70224 discloses a polylactic acid resin and an acrylonitrile-butadiene-styrene resin composition to improve heat resistance. Japanese Patent Laid-Open Publication No. 2006-143772 and U.S. Patent No. 5,272,221 disclose a method of enhancing biomass by using a polylactic acid-polyamide resin composition. In addition, Japanese Patent Laid-Open Publication No. 2003-147180 and No. 2003-138119 disclose a method of increasing heat resistance by using a polyoxymethylene-polylactic acid resin composition.
Japanese Patent Laid-Open Publication No. 2005— 048067 and No. 2006-199743 disclose a method of improving heat resistance by using a polylactic acid-polycarbonate resin composition. However, since the polylactic acid resin and polycarbonate resin have low compatibility, they have a limit to property improvement, and a problem of a flow mark or welding line degrading the appearance of products.
Macromolecules 20,904 (1987) and 26, 6918 (1993) disclose crystalline improvement by fusing L-isomeric polylactic acid and D-isomeric polylactic acid. Furthermore,
Japanese Patent Laid-Open Publication No. 2007-023083 and No. 2006-241607 disclose inducement of high crystallinity and improvement of thermal stability and mechanical strength by using a stereo-complex polylactic acid.
An exemplary embodiment of the present invention provides an environmentally-friendly polylactic acid resin composition having excellent heat resistance and appearance, and improved welding impact strength.
Another embodiment of the present invention provides an environmentally-friendly polylactic acid resin composition, which is suitable for various molded products requiring heat resistance and mechanical strength, for example for vehicles, machine parts, electronic parts, office machines, miscellaneous goods, and the like.
The embodiments of the present invention are not limited to the above technical purposes, and a person of ordinary skill in the art can understand other technical purposes .
According to one embodiment of the present invention, an environmentally-friendly polylactic acid resin composition is provided that includes (A) a mixed resin including (al) a polylactic acid (PLA) resin and (a2) a polycarbonate resin, and (B) a compatibilizer being capable of forming a stereo-complex with the polylactic acid resin.
The compatibilizer may be a copolymer of a polylactic acid resin that is an optical isomer of the polylactic acid resin, and polycarbonate. When the polylactic acid resin of the mixed resin is mostly an L-isomer, the compatibilizer is a D-isomeric polylactic acid. When the polylactic acid resin of the mixed resin is mostly a D-isomer, the compatibilizer is an L-isomeric polylactic acid. The former combination is more preferable according to one embodiment in terms of economic aspects.
According to another embodiment of the present invention, provided is a molded product made from the environmentally-friendly polylactic acid resin composition.
Hereinafter, further embodiments of the present invention will be described in detail.
The environmentally-friendly polylactic acid resin composition of the present invention has excellent appearance and improved mechanical strength and heat resistance as well as welding impact strength, and can thereby be usefully used to manufacture various molded products requiring heat resistance and mechanical strength, for example for vehicles, machine parts, electronic parts, miscellaneous machines, and the like.
Exemplary embodiments of the present invention will hereinafter be described in detail. However, these embodiments are only exemplary, and the present invention is not limited thereto.
As used herein, the term "(meth)acrylonitrile" refers to acrylonitrile or methacrylonitrile and the term "(meth)acrylate" refers to acrylate or methacrylate.
One embodiment of the present invention is drawn to an environmentally-friendly polylactic acid resin composition having improved compatibility between a polylactic acid resin and a polycarbonate resin by using a compatibilizer therebetween.
The environmentally-friendly polylactic acid resin composition according to one embodiment of the present invention includes (A) a mixed resin including (al) a polylactic acid (PLA) resin and (a2) a polycarbonate resin, and (B) a compatibilizer being capable of forming a stereocomplex with the polylactic acid resin.
Exemplary components included in the environmentally-friendly polylactic acid resin composition according to embodiments of the present invention will hereinafter be described in detail. However, these embodiments are only exemplary, and the present invention is not limited thereto.
(A) Mixed resin (al) Polylactic acid (PLA) resin
In general, a polylactic acid resin is a commercially-available polyester-based resin made by using lactic acid acquired by decomposing corn starch as a monomer .
The polylactic acid resin consists of an L-isomeric lactic acid, a D-isomeric lactic acid, or an L,D-isomeric lactic acid. They can be used singularly or in combination. The polylactic acid resin may include an L-isomer in an amount of 95 wt% or more in terms of balance among heat resistance, formability, and economic efficiency. It may include the L-isomer in an amount of 95 to 100 wt% and the D-isomer in an amount of 0 to 5 wt% considering hydrolysis resistance.
In addition, the polylactic acid resin has no particular limit of molecular weight or molecular weight distribution as long as it can be molded. However, when it has a weight average molecular weight of more than 80,000, it can provide a molding product with balanced mechanical strength and heat resistance. In another embodiment, a polylactic acid resin may preferably have a weight average molecular weight ranging from 90,000 to 500,000.
The polylactic acid resin may be included in an amount of 25 to 80 wt% in a mixed resin, which is included in an environmentally-friendly polylactic acid resin composition according to one embodiment of the present invention. In another embodiment, it may be included in an amount of 40 to 80 wt%. When the polylactic acid resin is included within the range, it may contribute to balance between formability and heat resistance.
(a2) Polycarbonate resin
The polycarbonate resin may be prepared by reacting diphenols of the following Chemical Formula 1 with a compound of phosgene, halogen formate, carbonate, or a combination thereof.
[Chemical Formula 1]
Figure NL2002910AD00071
In the above Chemical Formula 1, A is a single bond, a substituted or unsubstituted Cl to C5 alkylene, a substituted or unsubstituted Cl to C5 alkylidene, a substituted or unsubstituted C3 to C6 cycloalkylene, a substituted or unsubstituted C5 to C6 cycloalkylidene, CO, S, or SO2, and
Rn and 1½ are each independently a substituted or unsubstituted Cl to C30 alkyl, or a substituted or unsubstituted C6 to C30 aryl, and nn and ni2 are each independently integers ranging from 0 to 4.
As used herein, when a specific definition is not provided, the term "substituted" refers to one substituted with at least a substituent selected from the group consisting of a halogen, a Cl to C30 alkyl, a Cl to C30 haloalkyl, a C6 to C30 aryl, a Cl to C20 alkoxy, and combinations thereof.
The diphenols represented by the above Chemical Formula 1 may be used in combinations to constitute repeating units of the polycarbonate resin. The diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2.2- bis- (4-hydroxyphenyl)-propane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, 2.2- bis-(3,5-dichloro-4-hydroxyphenyl)-propane, and the like .
In one embodiment, 2,2-bis-(4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl)-propane, or 1,1-bis- (4-hydroxyphenyl)-cyclohexane of the diphenols may be preferable, and in another embodiment, 2,2-bis-(4-hydroxyphenyl)-propane may be more preferable.
In one embodiment, the polycarbonate resin has a weight average molecular weight ranging from 10,000 to 200,000, and in another embodiment, it has a weight average molecular weight ranging from 15,000 to 80,000, but is not limited thereto.
The polycarbonate resin may be mixtures of polycarbonate resins obtained using two or more diphenols that are different from each other. The polycarbonate resin may be a linear polycarbonate resin, a branched polycarbonate resin, a polyester carbonate copolymer, and the like.
The linear polycarbonate resin may include a bisphenol-A based polycarbonate resin. The branched polycarbonate resin may include one produced by reacting a multi-functional aromatic compound such as trimellitic anhydride, trimellitic acid, and so on with diphenols and carbonate. The multi-functional aromatic compound may be included in an amount of 0.05 to 2 mol% based on the total amount of the branched polycarbonate resin. The polyester carbonate copolymer resin may include one produced by reacting a difunctional carboxylic acid with diphenols and carbonate. The carbonate r may include a diaryl carbonate such as diphenyl carbonate, and ethylene carbonate.
The polycarbonate resin may be included in an amount of 20 to 75 wt% in the mixed resin of an environmentally-friendly polylactic acid resin composition. In another embodiment, it may be included in an amount of 20 to 60 wt%. When the polycarbonate resin is included within the range, it can maintain appropriate biomass and secure balance between formability and heat resistance.
(B) Compatibilizer
In the present invention, the compatibilizer may include a copolymer including a polylactic acid that can form a stereo-complex with the the polylactic acid resin (al) of the mixed resin (A).
The copolymer may be a copolymer of an optical isomer of polylactic acid (al) of the mixed resin (A), and polycarbonate. In other words, when a polylactic acid resin (al) of the mixed resin (A) is an L-isomer, the polylactic acid including the compatibilizer is a D-isomer. When the polylactic acid resin (al) of the mixed resin (A) is a D-isomer, the polylactic acid of the compatibilizer is an L-isomer.
When a copolymer of polylactic acid of the D-isomer and the polycarbonate is used, it may be more economically advantageous than when used singularly.
Since a polylactic acid resin as a mixed resin and a polycarbonate resin have poor compatibility with each other, they may easily leave a flow mark on the surface of extruded products and a severe welding line, deteriorating welding impact strength.
According to the embodiment of the present invention, since a copolymer of olylactic acid resin of a mixed resin, preferably polylactic acid resin of an L-isomer, and polylactic acid of an optical isomer that can form a stereo-complex, preferably polylactic acid of a D-isomer, and polycarbonate is used as a compatibilizer, it forms a polylactic acid stereo-complex on the interface of the polylactic acid resin and the polycarbonate resin and resultantly maximizes crystallinity of the polylactic acid on the interface and compatibility between the resins.
The polylactic acid of the D-isomer is the same as that aforementioned in a mixed resin, and the polylactic acid of the L-isomer is the same as that aforementioned in a mixed resin. The polycarbonate may include any polycarbonate resin used in a mixed resin, and is not further explained in detail. However, the polycarbonate resin as a compatibilizer may have a lower weight average molecular weight than a polycarbonate resin used in a mixed resin. For example, it may have a weight average molecular weight ranging from 1000 to 100,000.
Furthermore, the polylactic acid of the D-isomer may have a weight average molecular weight (Mw) ranging from 1000 to 200,000. When the compatibilizer has an appropriate molecular weight, it can be effectively disposed on the interface of two polymers of the polylactic acid resin and the polycarbonate resin and have good effects on compatibility. When it has a lower molecular weight, it may have low miscibility and reactivity with each polymer. On the contrary, when it has a higher molecular weight, it may deteriorate fluidity and thereby may not move onto the interface of two polymers, or may be phase-separated.
In addition, when a copolymer includes an optical isomer of polylactic acid constituting a mixed resin, preferably D-polylactic acid, and polycarbonate in a weight ratio of 5:95 to 95:5, it can have a good influence on property balances among welding impact strength, heat resistance, and appearance. In another embodiment, it may include them in a weight ratio of 30:70 to 70:30.
According to the embodiment of the present invention, a copolymer as a compatibilizer may include a polylactic acid-polycarbonate copolymer including polylactic acid with a weight average molecular weight (Mw) ranging from 1000 to 200,000 by ring-opening polymerization of a D,D-lactide monomer and using bisphenol-A polycarbonate with a weight average molecular weight (Mw) ranging from 1000 to 100,000 as an initiator.
The compatibilizer may be included in an amount of 0.01 to 30 parts by weight in an environmentally-friendly polylactic acid resin composition of the present invention based on 100 parts by weight of a mixed resin. In another embodiment, it may be included in an amount of 2 to 10 parts by weight. When the compatibilizer is used within the range, it can improve property balance among heat resistance, appearance, and welding line.
(C) Impact modifier
The environmentally-friendly polylactic acid resin composition of the present invention can include an impact modifier to improve impact strength.
The impact modifier improves affinity with the polylactic acid resin, and includes a core-shell type copolymer, a chain-shaped modifier, or a combination thereof.
The core-shell type copolymer has a core-shell structure where unsaturated monomers are grafted into a rubber core to form a hard shell. The unsaturated monomers include styrene, alkyl- or halogen-substituted styrene, (meth)acrylonitrile, methacrylic acid alkyl ester series, acrylic acid alkyl esters, anhydride, and alkyl- or phenyl-N-substituted maleimide. The rubber core includes a rubber polymer obtained by polymerizing a diene-based rubber monomer, an acrylate-based rubber monomer, and a silicone-based rubber monomer .
The rubber may be prepared by polymerizing one or more rubber monomers selected from the group consisting of monomers of a diene-based rubber with 4 to 6 carbons, an acrylate-based rubber, and a silicone-based rubber.
The diene-based rubber includes a butadiene rubber, an acryl rubber, an ethylene/propylene rubber, a styrene/butadiene rubber, an acrylonitrile/butadiene rubber, an isoprene rubber, an ethylene-propylene-diene (EPDM) terpolymer, and the like.
The acrylate-based rubber includes an acrylate monomer such as methylacrylate, ethylacrylate, n-propylacrylate, n-butylacrylate, 2-ethylhexylacrylate, hexylmethacrylate, or 2-ethylhexyl(meth)acrylate, and the like. Curing agents such as ethyleneglycoldi(meth)acrylate, propyleneglycoldi(meth)acrylate, 1,3-butyleneglycoldi(meth)acrylate or 1,4-butyleneglycoldi(meth)acrylate, allyl(meth)acrylate, triallylcyanurate, and the like may be used along with the acrylate monomers.
The silicone-based rubber is obtained from cyclosiloxane. Examples of the cyclosiloxane include dimethylsiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethyIcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetrapheny1cyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like. These cyclosiloxanes may be used for preparation of the silicone-based rubber. Curing agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and the like may be used along with the cyclosiloxanes.
In one embodiment, the silicone-based rubber or a mixture of the silicone-based rubber and acrylate-based rubber may be preferable due to structural stability of the silicone-based rubber. The rubber has an average particle diameter ranging from 0.4 to lpm in terms of balance between impact resistance and coloring properties.
In addition, the unsaturated monomer that can be grafted into a rubber may include more than one unsaturated compound selected from the group consisting of styrene, an alkyl or halogen substituted styrene, (meth)acrylonitrile, methacrylic acid ester series, methacrylic acid alkyl ester series, acrylic acid ester series, anhydride, and alkyl- or phenyl-N-substituted maleimide.
Each methacrylic acid alkyl ester series or acrylic acid alkyl ester series is an alkyl ester of acrylic acid or methacrylic acid. For example, a Ci to C8 alkyl ester that is obtained from a reaction of acrylic acid and Ci to C8 monohydryl alcohols may be used. Specific examples include methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid propyl ester, and the like. In one embodiment, methacrylic acid methyl ester is preferable.
The anhydride includes acid anhydride. More specifically, the anhydride may be a carboxylic acid anhydride such as maleic anhydride, itaconic anhydride, and so on.
In the core-shell type copolymer, the core material of rubber and an unsaturated monomer for grafting are mixed in a weight ratio ranging from 50 to 90 : 5 to 30.
When the core-shell type copolymer includes the core material of rubber and an unsaturated monomer for grafting within the range, it has excellent compatibility with a resin. As a result, it can have excellent impact reinforcement effects.
In addition, a chain-type ester-based or olefin-based copolymer includes a thermoplastic polyester or polyolefin-based main chain to which an epoxy or anhydride functional group is grafted.
For example, the olefin-based copolymer can be prepared by selecting at least one from olefin-based monomers such as ethylene, propylene, isopropylene, butylenes, and isobutylene. The olefin-based copolymer can be prepared by using a Ziegler-Natta catalyst, which is an olefin polymerization catalyst, or a methallocene-based catalyst for a more selective structure. In addition, a functional group such as anhydrous maleic acid, glycidylmethacrylate, oxazoline, and the like can be grafted into an olefin-based copolymer in order to improve dispersion.
The method of grafting the functional group into an olefin-based copolymer can be easily understood by those who have common knowledge in a related art of the present invention.
The impact modifier may be included in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of a mixed resin including (A) (al) an L-isomeric polylactic acid resin and (a2) a polycarbonate resin. When the impact modifier is included within the range, it can contribute to impact reinforcing effects and improve mechanical strength such as tensile strength, flexural strength, flexural modulus, and the like.
(D) Other Additive
According to the embodiments of the present invention, an environmentally-friendly polylactic acid resin composition may further include an additive selected from the group consisting of an antioxidant, a weather-resistance agent, a release agent, a colorant, an ultraviolet (UV) blocker, a filler, a nucleus-forming agent, a plasticizer, an auxiliary agent for adhesion, an adhesive, and a combination thereof, unless it interferes with the purpose of the present invention.
The antioxidant may include an antioxidant of phenols, phosphides, thioethers, or amines. The weather-resistant agent may include benzophenones or amines.
The release agent may include fluorine-included polymer, silicone oil, metal stearate, metal montanate, montanic acid ester wax, or polyethylene wax. The colorant may include a dye or a pigment.
The ultraviolet (UV) blocker may include titanium oxide or carbon black, the filler may include silica, clay, calcium carbonate, calcium sulfate, or glass bead, and the nucleus-forming agent may include talc or clay.
The environmentally-friendly polylactic acid resin composition can be prepared in a method of preparing a common resin composition. For example, it can be prepared into pellets by simultaneously mixing the components and other additives and fusing and extruding them. In the extruding process, the polylactic acid of the mixed resin and the compatibilizer form a stereo-complex.
The environmentally-friendly polylactic acid resin composition can be used to mold various products, in particular, a product simultaneously requiring excellent heat resistance and mechanical strength. For example, it can be molded into vehicle parts, machine parts, electronic parts, parts for office machines such as computers, miscellaneous goods, and the like. In particular, it can be used for housings for electronics such as a television, a computer, a printer, a washing machine, a cassette player, audio equipment, a mobile phone, and the like.
According to another embodiment of the present invention, provided is a product molded from the environmentally-friendly polylactic acid resin composition.
Hereinafter, the present invention is illustrated in more detail with reference to examples. However, they are exemplary embodiments of the present invention and are not limiting.
Examples
According to examples and comparative examples, (A) (al) an L-isomer of a polylactic acid resin and (a2) a polycarbonate resin, (B) a compatibilizer, and (C) an impact modifier are as follows.
(A) Mixed Resin (al) L-isomer of a polylactic acid (PLA) resin 4032D including 97.5 wt% of an L-isomer, which is made by USA NatureWorks LLC, was used.
(a2) Polycarbonate Resin A PANLITE L-1250WP resin made by Japanese Teijin Ltd. was used.
(B) Compatibilizer A compatibilizer was prepared in the following process .
(bl) PC-PDLA-1: Bisphenol-A was mixed with diphenyl carbonate in a weight ratio of 1.04 : 1. The mixture was reacted with 10-7 to 10”° mol% catalyst (potassium hydroxide, KOH) in a batch-type reactor. Herein, the reaction temperature was gradually raised from 180°C to 300°C according to a viscosity increase of the reaction medium. In addition, a reflux column and a vacuum pump were connected to the reactor to remove a reaction product, phenol, under 1 torr or less of vacuum. Herein, the phenol was only removed by returning diphenylcarbonate that was volatilized therewith to the reactor. The reaction was performed for about 8 to 12 hours. Accordingly, bisphenol A-polycarbonate with a weight average molecular weight (Mw) of 5000 was synthesized depending on reaction time and vacuum degree.
Then, the bisphenol A-polycarbonate was used as an initiator to prepare a polylactic acid-polycarbonate copolymer, in which the polylactic acid had a weight average molecular weight (Mw) of 10,000, by ring-opening polymerization of a D,D-lactide monomer imported from Purac Co. as follows.
The ring-opening polymerization was performed at 190°C for 1 to 2 hours by adding 200g of D,D-lactide to a batch-type mixer purged with nitrogen, and then adding 100 to 200g of the low molecular weight polycarbonate as an initiator and 12mg of tin octylate as a catalyst. Then, the compatibilizer was vacuum-dried at 100°C to remove an unreacted monomer.
(b2) PC-PDLA-2: a polylactic acid-polycarbonate copolymer including polylactic acid with a weight average molecular weight (Mw) of 30,000 was prepared by using bisphenol-A polycarbonate with a weight average molecular weight (Mw) of 10,000 as an initiator to ring-opening polymerize the D-isomer polylactide. The compatibilizer was polymerized in the same method as the PC-PDLA-1, except with regard to its molecular weight.
(b3) PC-PDLA-3: a polylactic acid-polycarbonate copolymer including polylactic acid with a weight average molecular weight (Mw) of 60,000 was prepared by using bisphenol-A polycarbonate with a weight average molecular weight (Mw) of 15,000 as an initiator to ring-opening polymerize the D-isomer polylactide. The compatibilizer was polymerized in the same method as the PC-PDLA-1, except with regard to its molecular weight.
(C) Impact modifier METABLENE S-2001 of MRC (core-shell type MBS: methyl methacrylate-butyl acrylate and dimethyl siloxane copolymer) was used as an impact modifier.
(D) SAN-GMA compatibilizer
Styrene, acrylonitrile, and glycidyl methacrylate (GMA) in a weight ratio of 70.6:28.9:0.5 were prepared into a compound in a common method. The compound was prepared by grafting GMA into a styrene/acrylonitrile copolymer.
Example 1 50 wt% of a polylactic acid (PLA) resin and 50 wt% of a polycarbonate resin were mixed together. Then, 2 parts by weight of a PC-PDLA-1 compatibilizer was put into 100 parts by weight of the mixed resin, preparing an environmentally-friendly polylactic acid resin composition.
The polylactic acid resin composition was extruded in a temperature ranging of 200 to 230°C with a common screw extruder. The extruded product was shaped into pellets.
The pellets were dried at 80°C for 4 hours and then prepared as an ASTM dumbbell specimen by using an injection molding machine capable of injecting and molding 6 Oz and set at a cylinder temperature of 230°C, a molding temperature of 80°C, and a molding cycle of 60 seconds.
Example 2 A polylactic acid resin composition was prepared according to the same method as Example 1, except for using 5 parts by weight of the compatibilizer based on 100 parts by weight of a mixed resin.
Example 3 A polylactic acid resin composition was prepared according to the same method as Example 2, except for using PC-PDLA-2 instead of PC-PDLA-1 as a compatibilizer.
Example 4 A polylactic acid resin composition was prepared according to the same method as Example 2, except for using PC-PDLA-3 instead of PC-PDLA-1 as a compatibilizer.
Example 5 A polylactic acid resin composition was prepared according to the same method as Example 2, except for adding 5 parts by weight of an impact modifier.
Example 6 A polylactic acid resin composition was prepared according to the same method as Example 2, except for changing the ratio of polylactic acid resin and polycarbonate resin to 4:6.
Comparative Example 1 A polylactic acid resin composition was prepared according to the same method as Example 1, except for using no compatibilizer.
Comparative Example 2 A polylactic acid resin composition was prepared according to the same method as Example 1, except for using 5 parts by weight of an impact modifier but no compatibilizer.
Comparative Example 3 A polylactic acid resin composition was prepared according to the same method as Example 1, except for adding 2 parts by weight of a common compatibilizer.
Reference Example 1 A polylactic acid resin composition was prepared according to the same method as Example 1, except for increasing the amount of compatibilizer to 35 parts by weight.
The specimens according to Examples 1 to 6, Comparative Examples 1 and 2, and Reference Example 1 were evaluated regarding properties in the following method. The results are provided in the following Tables 1 and 2.
(1) Mechanical properties: measured based on ASTM D 638 and D 790.
(2) Thermal distortion temperature (HDT): measured based on ASTM D 648.
(3) Notched IZOD: measured based on ASTM D 256.
(4) Appearance: judged overall by observing the surface of a 2mm-thick pin-point specimen (50mm X 200mm) (o: excellent surface appearance without flow marks, Δ: generally good appearance except for bad appearance only at the gate, X: flow marks on overall surface of a specimen).
(5) Welding impact strength: impact strength specimen of mold gate 2 was measured based on ASTM D 256 without notch.
(Table 1)
Figure NL2002910AD00211
(Table 2)
Figure NL2002910AD00221
As shown in Tables 1 and 2, the specimens of Examples 1 to 2 had improved heat resistance, impact strength, and welding impact strength, and also excellent appearance. On the contrary, the specimen including no compatibilizer of Comparative Example 1 had sharply deteriorated impact strength, welding impact strength, and heat resistance, and also had a bad appearance.
In addition, comparing the specimens of Example 5 and Comparative Example 2, that including an impact modifier and a compatibilizer according to Example 5 had sharply-improved appearance, heat resistance, impact strength, welding impact strength, and the like.
As shown in Table 1, when a compatibilizer was increasingly included (comparing Example 1 with Example 2), the specimen had generally improved properties. The L-isomeric polylactic acid resin of a mixed resin and the polylactic acid segment of the D-isomer of a compatibilizer appear to act as a crystallizing agent, resultantly improving crystallinity.
Comparing the specimens of Examples 2, 3, and 4, the molecular weight of each segment in the compatibilizer was important. In other words, a copolymer of the D-isomeric polylactic acid resin with a weight average molecular weight ranging from 1000 to 200,000 and the polycarbonate with a weight average molecular weight ranging from 1000 to 100,000 effectively worked as a compatibilizer.
The specimen of Example 6 included more polycarbonate and more improved mechanical properties than that of Example 2, as shown in Table 1. The reason is that polycarbonate has better properties than polylactic acid.
Accordingly, the compatibilizer can work regardless of the composition ratio.
As shown in Table 2, the specimen including a conventional compatibilizer according to Comparative Example 3 had sharply deteriorated heat resistance and other mechanical strengths and had a particularly bad appearance compared with the specimen including the compatibilizer according to Example 1 of the present invention. In other words, it could not accomplish the stereo-complex of a compatibilizer and polylactic acid of a mixed resin and induce crystallinity, and thereby good properties and appearance, when it included a common compatibilizer.
Referring to Reference Example 1 of Table 2, when the specimen included a compatibilizer at a high amount, it did not have good mechanical strength, welding impact strength, or appearance. The reason is that, when the compatibilizer was included beyond an adherence improvement point among the media, the excessive amount may deteriorate properties due to low molecular weight and cause surface appearance problems with stains.
Referring to the results of Tables 1 and 2, the compatibilizer had high affinity between the L-isomeric polylactic acid of a mixed resin and the D-isomeric polylactic acid therein, and thereby had excellent compatibility therebetween, resultantly improving impact strength, heat resistance, appearance, and the like.
While this 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 appended claims

Claims (12)

1. Milieuvriendelijke samenstelling van polymelkzuurhars, omvattende: (A) een gemengde hars die (al) een polymelkzuur (PLA) hars en (a2) een polycarbonaathars omvat; en (B) een compatibiliseringsmiddel dat geschikt is om een stereocomplex te vormen met de polymelkzuur (PLA) hars.An environmentally friendly composition of polylactic acid resin, comprising: (A) a mixed resin comprising (a1) a polylactic acid (PLA) resin and (a2) a polycarbonate resin; and (B) a compatibilizing agent suitable for forming a stereo complex with the polylactic acid (PLA) resin. 2. Milieuvriendelijke polymelkzuurharssamenstelling volgens conclusie 1, waarbij het compatibiliseringsmiddel een copolymer is van een polymelkzuurhars die een optische isomeer is van de polymelkzuurhars (la) en polycarbonaat.An environmentally friendly polylactic acid resin composition according to claim 1, wherein the compatibilizing agent is a copolymer of a polylactic acid resin that is an optical isomer of the polylactic acid resin (1a) and polycarbonate. 3. Milieuvriendelijke polymelkzuurharssamenstelling volgens conclusie 1 of 2, met het kenmerk, dat de polymelkzuurhars (al) van de gemengde hars (A) een L-isomeer en het compatibiliteitsmiddel een copolymeer van een D-isomeer polymelkzuurhars en polycarbonaat is, of de polymelkzuurhars (al) van de gemengde hars (A) een D-isomeer en compatibiliteitsmiddel een copolymeer van een L-isomeer polymelkzuurhars en polycarbonaat is.An environmentally friendly polylactic acid resin composition according to claim 1 or 2, characterized in that the polylactic acid resin (a1) of the mixed resin (A) is an L-isomer and the compatibility agent is a copolymer of a D-isomeric polylactic acid resin and polycarbonate, or the polylactic acid resin ( a1) of the mixed resin (A) is a D isomer and compatibility agent is a copolymer of an L isomer polylactic acid resin and polycarbonate. 4. Milieuvriendelijke polymelkzuurharssamenstelling volgens één der voorgaande conclusies, waarbij de gemengde hars 25 tot 80 gew.% van de (al) polymelkzuurhars en 20 tot 75 gew.% van de (a2) polycarbonaathars omvat, en Het compatibiliteitsmiddel aanwezig is in een hoeveelheid van 0,01 tot 30 gewichtsdelen op basis van 100 gewichtsdelen van de gemengde hars.An environmentally friendly polylactic acid resin composition according to any one of the preceding claims, wherein the mixed resin comprises 25 to 80% by weight of the (a1) polylactic acid resin and 20 to 75% by weight of the (a2) polycarbonate resin, and The compatibility agent is present in an amount of 0.01 to 30 parts by weight based on 100 parts by weight of the mixed resin. 5. Milieuvriendelijke polymelkzuurharssamenstelling volgens één der voorgaande conclusies, waarbij de polymelkzuurhars (al) van de gemengde hars (A) een naar gewicht gemiddeld molecuulgewicht (Mw) van 90.000 tot 500.000 heeft en de polycarbonaathars een naar gewicht gemiddeld molecuulgewicht (Mw) van 10.000 tot 200.000 heeft.An environmentally friendly polylactic acid resin composition according to any one of the preceding claims, wherein the polylactic acid resin (a1) of the mixed resin (A) has a weight average molecular weight (Mw) of 90,000 to 500,000 and the polycarbonate resin a weight average molecular weight (Mw) of 10,000 to Has 200,000. 6. Milieuvriendelijke polymelkzuurharssamenstelling volgens conclusie 3, waarbij de D-isomeer polymelkzuurhars van het compatibiliteitsmiddel een naar gewicht gemiddeld molecuulgewicht (Mw) van 1000 tot 200.000 heeft en de polycarbonaathars van het compatibiliteitsmiddel een naar gewicht gemiddeld molecuulgewicht (Mw) van 1000 tot 100.000 heeft.The environmentally friendly polylactic acid resin composition according to claim 3, wherein the D-isomer polylactic acid resin of the compatibility agent has a weight average molecular weight (Mw) of 1000 to 200,000 and the polycarbonate resin of the compatibility agent has a weight average molecular weight (Mw) of 1000 to 100,000. 7. Milieuvriendelijke polymelkzuurharssamenstelling volgens één der voorgaande conclusies, waarbij de polycarbonaathars een lineaire polycarbonaathars, een vertakte polycarbonaathars, een polyesterse carbonaat-copolymeer of mengsels daarvan omvat.An environmentally friendly polylactic acid resin composition as claimed in any one of the preceding claims, wherein the polycarbonate resin comprises a linear polycarbonate resin, a branched polycarbonate resin, a polyester carbonate copolymer or mixtures thereof. 8. Milieuvriendelijke polymelkzuurharssamenstelling volgens één der voorgaande conclusies, met het kenmerk, dat de milieuvriendelijke polymelkzuurharssamenstelling verder een inslag-modificeringsmiddel omvat.An environmentally friendly polylactic acid resin composition according to any one of the preceding claims, characterized in that the environmentally friendly polylactic acid resin composition further comprises an impact modifier. 9. Milieuvriendelijke polymelkzuurharssamenstelling volgens conclusive 8, met het kenmerk, dat het inslag-modificeringsmiddel aanwezig is in een hoeveelheid van 0,01 tot 20 gewichtsdelen, gebaseerd op 100 gewichtsdelen van de gemengde hars.An environmentally friendly polylactic acid resin composition according to claim 8, characterized in that the impact modifier is present in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the mixed resin. 10. Milieuvriendelijke polymelkzuurharssamenstelling volgens conclusie 8 of 9, met het kenmerk, dat het inslag-modificeringsmiddel een copolymeer van het kern-schaaltype, een ketenvormig modificeringsmiddel of een combinatie daarvan is.An environmentally friendly polylactic acid resin composition according to claim 8 or 9, characterized in that the impact modifier is a core-shell type copolymer, a chain modifier or a combination thereof. 11. Milieuvriendelijke polymelkzuurharssamenstelling volgens één der voorgaande conclusies, met het kenmerk, dat de milieuvriendelijke polymelkzuurharssamenstelling verder een antioxidant, een weerbestendig middle, een loslaatmiddel, een kleurmiddel, een ultraviolet (UV) blokkeringsmiddel, een vulmiddel, een kernvormend middel, een plastificeringsmiddel, een hulpmiddel voor hechting, een hechtmiddel of mengsels daarvan, omvat.An environmentally friendly polylactic acid resin composition according to any one of the preceding claims, characterized in that the environmentally friendly polylactic acid resin composition further comprises an antioxidant, a weather-resistant agent, a release agent, a coloring agent, an ultraviolet (UV) blocking agent, a filler, a nucleating agent, a plasticizing agent, a adhesion promoter, an adhesive or mixtures thereof. 12. Gietproduct, vervaardigd onder gebruikmaking van de milieuvriendelijke polymelkzuurharssamenstelling volgens één der voorgaande conclusies.A cast product manufactured using the environmentally friendly polylactic acid resin composition according to any one of the preceding claims.
NL2002910A 2008-09-02 2009-05-20 Environmentally-friendly polylactic acid resin composition. NL2002910C2 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8367780B2 (en) 2008-12-11 2013-02-05 Cheil Industries Inc. Aliphatic polyester copolymer, method for preparing the same and polylactic acid resin composition using the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8367780B2 (en) 2008-12-11 2013-02-05 Cheil Industries Inc. Aliphatic polyester copolymer, method for preparing the same and polylactic acid resin composition using the same

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